CN101254674B - Hard laminated film - Google Patents

Abstract

A hard laminated film is provided, wherein a layer A and a layer B having specific compositions are deposited alternately so that the compositions of layer A and layer B are different. The thickness of layer A per layer is twice or more the thickness of layer B per layer, the thickness of layer B per layer is 0.5 nm or more, and the thickness of layer A per layer is 200 nm or less. Thereby, the invention provides a cutting tool used as the basis materials, such as the extra hard alloy, the ceramic metal or the high speed steel and the like, or the abrasion resistance capsule of the vehicle slide unit and the like.

Description

Hard laminated coating

This application is a divisional application of application number 200510005755.1, filing date: January 25, 2005, and title of the invention "hard laminated film, its manufacturing method and film forming device". the

technical field

The present invention relates to a hard laminated coating having excellent mechanical properties obtained by finely controlling the crystal particle diameter, a hard laminated coating having wear resistance formed on the surface of a cutting tool or a sliding part of an automobile, and a wear-resistant coating. Hard laminated coating with excellent damage or oxidation resistance. the

Furthermore, the present invention relates to a composite film-forming apparatus which has an arc evaporation source and a sputtering evaporation source and can form a hard laminated film having excellent characteristics. the

Background technique

In recent years, there has been increasing demand for improved wear resistance of cutting tools based on cemented carbide, cermets, high-speed tool steel, etc., or automotive sliding parts, and studies have been conducted on wear resistance for use on the surfaces of these parts Improvement of the coating. the

As the wear-resistant coating, conventionally, a hard coating such as TiAlN, which is a composite nitride film of TiN or TiCN, Ti and Al, is applied to the base material (on the member). the

To improve the wear resistance of these wear-resistant coatings, tests have been mainly conducted to improve the characteristics by adding a third element to refine the crystal particles of the coating. For example, in the case of a cutting tool, it has been reported that by adding Si or B to the TiAlN film, the oxidation resistance is improved, and at the same time, the method of achieving high hardness by miniaturization of the crystal grains (refer to U.S. Patent No. 5,580,653 , US Patent No. 5,318,840). In addition, a method of increasing hardness and improving wear resistance by adding B to CrN films used in sliding parts represented by automobile piston rings has also been proposed (see US Patent No. 6,232,003). the

In addition, for the purpose of improving the characteristics by adding elements to the conventional hard film, by using a device with an arc and sputtering evaporation source, an arc evaporation source is used to form a TiN film, and at the same time, Si is added to the target to form a TiSiN film. , Attempts to improve properties such as increasing hardness (refer to K.H.Kim et al.Surf.Coat.Technol, 298 (2002) 243-244, 247 pages). the

In the method of adding elements to such a wear-resistant coating to make the crystal particles of the coating finer, the degree of miniaturization of the crystal particles is determined by the addition amount of the element, and the particle size of the coating can be controlled only by changing the addition amount. diameter. Therefore, to fabricate coatings with different particle diameters, it is necessary to fabricate multiple targets with varying amounts of added elements. Therefore, it is extremely cumbersome to prepare a sample with a particle diameter that meets the purpose, that is, to produce a coating having properties that meet the purpose, and there are practical problems. the

In addition, as a hard coating for cutting tools with high hardness and excellent wear resistance, a hard coating whose crystal structure is mainly rock-salt structure type as a preferred form has also been proposed (refer to U.S. Patent No. 6,767,658, U.S. Patent No. Publication No. 2002-168552). These hard coatings are composed, for example, of (Tia, Alb, Vc)(C1-d Nd), however, 0.02≤a≤0.3, 0.5<b≤0.8, 0.05<c, 0.7≤b+c, a+b +c=1, 0.5≦d≦1 (a, b, and c respectively represent the atomic ratio of Ti, Al, and V, and d represents the atomic ratio of N) and the like. the

)，由于是高温高压相且是高硬度物质，因此维持岩盐结构的同时如果提高(TiAlV)(CN)中的Al的比率，则能够更加提高(TiAlV)(CN)膜的硬度。 In general, rock-salt structure-type hard coatings can be measured by X-ray diffraction using the θ·2θ method. For example, a hard coating such as (TiAlV)(CN) has a rock-salt structure-type crystal structure, and constitutes a rock-salt-type composite nitride in which Al and V are substituted on the Ti side of rock-salt-type TiN. In this case, rock-salt AlN (lattice constant

), since it is a high-temperature, high-pressure phase and a high-hardness substance, if the ratio of Al in (TiAlV)(CN) is increased while maintaining the rock-salt structure, the hardness of the (TiAlV)(CN) film can be further increased.

Regarding the film formation of the above-mentioned multilayer hard film, there is an apparatus and method for forming each hard film on a substrate by combining a plurality of arc evaporation sources, sputtering evaporation sources, or electron beam evaporation sources according to hard materials. . the

Among them, a device that combines a plurality of arc evaporation sources or sputtering evaporation sources to form each hard coating layer on the substrate separately or sequentially can perform film formation by utilizing the different characteristics of the arc evaporation sources or sputtering evaporation sources, In this respect, it can be said that it is a device with high film formation efficiency. the

For example, in comparing the characteristics of arc evaporation sources and sputtering evaporation sources, it was found that compared with sputtering evaporation, arc evaporation has a faster film formation rate, but it is difficult to adjust the film formation rate and it is difficult to accurately control the thickness of the film layer of the film. On the contrary, the sputtering evaporation source is slower than the arc evaporation source, but the adjustment of the film forming speed is easy, and since it works with a very small input power, it has the characteristics of being able to accurately control the thickness of the film layer. the

Therefore, if an arc evaporation source is used for a relatively thick film layer and a sputtering evaporation source is used for a relatively thin film layer, the thickness control of each film layer becomes easy, and the overall film formation rate can also be improved. the

As a film forming apparatus that combines such a plurality of arc evaporation sources or sputtering evaporation sources, there is known a film forming apparatus that arranges a plurality of arc evaporation sources and sputtering evaporation sources in the same film forming chamber. the

For example, it is proposed to operate the arc evaporation source or the arc evaporation source by alternating switching, stop the arc evaporation source after metal ion etching by the arc evaporation source, and use the sputtering evaporation source to form a hard Apparatus and method of coating (refer to US Pat. No. 5,234,561). the

In addition, a film forming apparatus having a magnetic field application mechanism in an arc evaporation source and a sputtering evaporation source has also been proposed (refer to European Patent Publication No. 0403552 and US Patent No. 6,232,003). In addition, FIG. 7 of US Pat. No. 6,232,003 describes, as a prior art, the influence of mutual interference of the magnetic fields of an arc evaporation source and a sputtering evaporation source that do not have a magnetic field application mechanism. the

In addition, it is known that a hard coating is formed by simultaneously operating an arc evaporation source and a sputtering evaporation source, or that the crystal particles of the coating are made finer by adding a third element to improve properties such as wear resistance. For example, by adding Si or B to a TiN film or a TiAlN film of a cutting tool, etc., oxidation resistance is improved, and at the same time, a method of achieving high hardness by miniaturization of crystal grains (refer to U.S. Patent No. 5,580,658, U.S. Patent No. Gazette No. 5,318,840, K.H.Kim et al. Surf. Coat. Technol, 298 (2002) 243-244, pp. 247). In addition, a method of increasing hardness and improving wear resistance by adding B to CrN films used in sliding parts represented by automobile piston rings has also been proposed (see US Patent No. 6,232,003). the

Even in a hard film whose crystal structure is mainly rock-salt structure type, when the crystal particle diameter (hereinafter also referred to as crystal particle size) of the rock-salt structure type hard film becomes coarse due to film-forming conditions, the use of There is also a limit to improving the wear resistance by increasing the hardness. the

In addition, in the above-mentioned conventional techniques, a specific element is uniformly added to the coating to form a single-layer coating having a single chemical composition. The film formed in this way improves the wear resistance by making the crystalline particles constituting the film finer, increasing the hardness, but there is still insufficient reduction in the friction coefficient of the film surface, and insufficient improvement in wear resistance and lubricity. As well as the increase in aggressiveness to target parts due to increased hardness, there is room for further improvement. the

In addition, hard coatings formed by these conventional methods or means cannot be said to have sufficient performance for cutting tools and sliding parts that are increasingly demanding, and further improvement in durability such as wear resistance is required. the

For example, in the method of making the crystal grains of the film finer by adding Si or B to the above-mentioned wear-resistant film, the degree of refinement of the crystal grains is determined by the amount of the element added, and only by changing the amount of addition can the The particle diameter of the film can be controlled. Therefore, to fabricate coatings with different particle diameters, it is necessary to fabricate multiple targets with varying amounts of added elements. Therefore, there is a problem of making a sample with a particle diameter that meets the purpose, that is, making a coating with a characteristic that meets the purpose, which is extremely cumbersome, and this brings practically difficult problems, and the wear resistance of the actually obtained hard coating There is also a limit to the improvement. the

In addition, as in the above-mentioned conventional device, when the arc evaporation source and the sputtering evaporation source are operated simultaneously in the same film forming chamber, even if the arc evaporation source or the sputtering evaporation source is operated by alternately switching, the hard film will Depending on the material or film-forming conditions, problems in film-forming, such as difficulty in forming a target dense hard film or a hard film with a target composition, and abnormal discharge during film-forming operations, inevitably arise. Therefore, in reality, there is a limit to improving the wear resistance by increasing the hardness of the obtained hard coating. the

For example, when forming a nitride hard film such as TiN, TiCN, or TiAlN, the film is formed in a protective atmosphere of a mixed gas of Ar and nitrogen in order to form the nitride. However, in the same film-forming chamber, electrons emitted from the arc evaporation source or the sputtering evaporation source are easily guided to the chamber side which is an anode like the substrate. As a result, the concentration of emitted electrons decreases, the collision with sputtering gas or reaction gas decreases, and efficient ionization of the gas becomes difficult. the

In addition, inert sputtering gases such as Ar (argon), Ne (neon), and Xe (xenon) are used as sputtering evaporation sources, and reactive gases (reactive gases) such as nitrogen, methane, and acetylene are used as arc evaporation sources. Therefore, when arc film formation and sputtering film formation are performed simultaneously in the same film formation chamber, especially in the case of film formation by increasing the partial pressure of reactive gas such as nitrogen in order to improve film performance, the The material used for the sputtering evaporation source, the sputtering target reacts with the above-mentioned reactive gas to produce an insulator (insulator) on the surface of the target, and due to this insulator, the possibility of abnormal discharge (arcing) in the sputtering evaporation source big. In addition, this problem also hinders efficient ionization of gas. the

When efficient ionization of gas is prevented in this way, ion irradiation to the substrate cannot be strengthened, densification of the hard coating layer cannot be achieved, and surface properties are also reduced due to roughening of the surface and the like. As a result, in the conventional film forming apparatus, especially when the arc evaporation source and the sputtering evaporation source are operated simultaneously in the same film forming chamber, the improvement in the characteristics or performance of the hard film such as high hardness There is a limit in terms of chemicalization. the

Contents of the invention

The present invention is proposed in view of such a fact, and its object is to provide a hard coating, wear resistance and other properties of the hard coating that are improved by making the particle size of the rock-salt structure type hard coating finer. Hard coatings with better abrasion resistance and lubricity than conventional hard coatings, and hard laminated coatings with excellent wear resistance and oxidation resistance. Another object is to provide a composite film-forming device and a sputtering evaporation source, which can obtain the required characteristics without any problem in the film formation under the condition that the arc evaporation source and the sputtering evaporation source are operated simultaneously in the same film-forming chamber. Hard coating. the

To achieve the above object, the structure of the hard laminate coating of the present invention, that is, the structure of the hard laminate coating commonly used in the following first to fourth inventions of the present invention is to alternately laminate layer A and layer A composed of a specific composition. B, the crystal structure of layer A is different from the crystal structure of layer B, the thickness of layer A of each layer is more than twice the thickness of layer B of each layer, the thickness of layer B of each layer is more than 0.5nm, each layer The thickness of layer A is below 200nm. the

The feature of the hard laminated film of the first invention of the present invention to achieve this purpose is: a fine crystalline hard film having alternately stacked hard film layers A having a cubic crystal rock-salt type structure, and hard film layers A having a cubic crystal rock-salt type structure. A coating structure formed of a hard coating layer B of a crystal structure other than the crystal structure. the

In the first invention, as described above, by combining hard coating layers with different crystal structures to form a laminated structure, it can be easily and arbitrarily finely controlled, and has a hard coating having a cubic crystal rock-salt crystal structure as the main phase. The crystal particle diameter of the film layer A. the

That is, in the case of alternately and sequentially forming (stacking) the hard coating layer A of the cubic rock salt crystal structure with the hard coating layer B not having the cubic rock salt crystal structure, the hard coating layer A part of B temporarily interrupts the crystal growth of the hard coating layer A below it. Then, when forming (stacking) the hard coating layer A, recrystallization growth of the hard coating layer A starts from the hard coating layer B above. Therefore, the crystal particle diameter of the hard coating layer A can be finely controlled. the

In addition, in the case where the hard coating layer B is not provided and only the hard coating layer A is laminated, or, even if the components are different, a hard coating having the same cubic crystal rock-salt crystal structure is laminated and formed. In the case of each layer of the layer A, the crystal growth of the hard coating layer A can be continued without interrupting the growth. As a result, coarse crystal particle diameters are easily formed. the

In the first invention, by making the crystal grains of the hard coating layer A finer in this way, it is possible to obtain excellent characteristics such as improvement in the hardness of the hard coating and wear resistance, which are not available in conventional hard coatings. . the

In the second aspect of the present invention, in the hard coating having the above-mentioned constitution, the compositions of the formation layer A and layer B respectively satisfy the following. the

Layer A: (Cr1-αXα)(BaCbN1-a-b-cOc)e

However, X is one or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, and Si, and 0≤α≤0.9, 0≤a≤0.15 , 0≤b≤0.3, 0≤c≤0.1, 0.2≤e≤1.1 (α represents the atomic ratio of X, and a, b, and c represent the atomic ratios of B, C, and O, respectively. The same applies below.). the

Layer B: B1-s-tCsNt

However, 0≤s≤0.25, (1-s-t)/t≤1.5 (s, t respectively represent the atomic ratio of C and N. The same below.) 

Or, Si1-x-yCxNy

However, 0≤x≤0.25, 0.5≤(1-x-y)/y≤1.4 (x, y respectively represent the atomic ratio of C and N. The same below.)

Or, C1-uNu

However, 0≤u≤0.6 (u represents the atomic ratio of N. The same applies below.). the

In the above-mentioned second invention, the α may be set to 0. the

In the above-mentioned second invention, the α may be set to 0.05 or more. the

In the above-mentioned second invention, the layer A has a cubic crystal rock-salt structure, and the diffraction lines from the (111) plane and (200) plane observed from the X-ray diffraction pattern measured by the θ-2θ method using CuKα rays At least one of the half-width values of can be 0.3° or more. the

According to the above-mentioned second invention, by alternately laminating the high-hardness layer A and the lubricating layer B on the surface of the substrate, the growth of crystal grains constituting the A layer is suppressed and made finer, thereby providing a A hard coating having better wear resistance and lubricity than conventional hard coatings and a method for producing the same.

The hard laminated film of the third invention of the present invention is characterized in that, in the hard laminated film of the above-mentioned constitution, layer A is represented by Formula 1: (Ti1-x-yAlxMy)(BaCbN1-a-b-cOc) [however, x, y, a, b, c represent the atomic ratio, 0.4≤x≤0.8, 0≤y≤0.6, 0≤a≤0.15, 0≤b≤0.3, 0≤c≤0.1, M is from 4A, 5A , 6A, and more than one metal element selected from Si], the layer B is composed of formula 2: B1-x-yCxNy [However, x, y represent the atomic ratio, 0≤x≤0.25, B/N ≤1.5],

Formula 3: Si1-x-yCxNy[However, x and y respectively represent the atomic ratio, 0≤x≤0.25, 0.5≤Si/N≤2.0],

Formula 4: C1-xNx [however, x represents the atomic ratio, 0≤x≤0.6],

Formula 5: Cu1-y(CxN1-x)y [however, x and y represent atomic ratios, respectively, and 0≤x≤0.1, 0≤y≤0.5] any composition selected. the

In the above-mentioned third invention, as shown in the above-mentioned characteristics, by combining layers A and B composed of a specific composition, a hard coating having a structure in which layers A and B are alternately stacked so that the compositions of these layers A and B are different from each other is formed. . the

In addition, among these laminated layers, the layer A is set to be composed of a specific composition of the (TiAlM)(BCNO) system, and the layer B is set to be composed of a (BCN) system, (SiCN) system, (CN) system, Cu (CN) Any selected specific composition constitutes in the system. the

Thus, for example, compared with a hard coating composed of a single composition such as layer A or a hard coating composed of a laminate of layers A, abrasion resistance or oxidation resistance can be greatly improved. the

The hard laminate coating according to the fourth aspect of the present invention is characterized in that, in the hard laminate coating having the above-mentioned constitution, layer A is composed of any one of the compositions in formula 1 or 2. the

The hard laminate coating according to the fourth aspect of the present invention is characterized in that, in the hard laminate coating having the above-mentioned constitution, layer A is composed of any one of the compositions in formula 1 or 2. the

Formula 1: (Ti1-x-yAlxMy)(BaCbN1-a-b-cOc) [However, x, y, a, b, c represent atomic ratios, 0.4≤x≤0.8, 0≤y≤0.6, 0≤a≤ 0.15, 0≤b≤0.3, 0≤c≤0.1, in addition, M is a metal element selected from one or more of 4A, 5A, 6A and Si],

Formula 2: (Cr1-αXα)(BaCbN1-a-b-cOc)e [However, α, a, b, c, e represent atomic ratios, 0≤α≤0.9, 0≤a≤0.15, 0≤b≤0.3 , 0≤c≤0.1, 0.2≤e≤1.1, in addition, X is an element selected from any one or more of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al and Si],

Layer B: Consists of the composition of the following formula 3. the

Formula 3: M1-dM1d(BaCbN1-a-b-cOc)

[However, M is a metal element selected from any one or more of W, Mo, V, and Nb,

M1 is a metal element selected from one or more of 4A, 5A, 6A, and Si in addition to W, Mo, V, and Nb, and a, b, c, and d represent atomic ratios, 0≤a≤0.15, 0≤ b≤0.3, 0≤c≤0.1, 0≤d≤0.3]. the

According to the above-mentioned fourth invention, for example, compared with a hard coating composed of a single composition such as layer A or a hard coating composed of a laminated layer of layer A, the wear resistance or oxidation resistance can be greatly improved. . the

In addition, the above-mentioned first to fourth preferred methods of forming the hard laminate coating of the present invention are characterized by using one or more arc evaporation sources and sputtering evaporation sources each equipped with a magnetic field application function. The method of forming the above-mentioned fine crystal film by a film-forming device, while evaporating the constituent components of the hard film layer A with an arc evaporation source, and evaporating the constituent components of the hard film layer B with a sputtering evaporation source, on the substrate The hard coating layers A and B are alternately laminated on top of each other. the

The composite film-forming device of the fifth invention of the present invention to achieve the above-mentioned object is characterized in that it is a film-forming system in which one or more arc evaporation sources and sputtering evaporation sources having the function of applying a magnetic field are respectively installed in the same film-forming chamber. The device has a mechanism for making the film-forming substrate move relatively sequentially between the arc evaporation source and the sputtering evaporation source, so as to connect the magnetic lines of force between the adjacent evaporation sources during film formation , constituting the magnetic field application mechanism. the

In addition, another feature of the composite film-forming device of the present invention to achieve this object is that it is a film-forming device in which one or more arc evaporation sources and sputtering evaporation sources with the function of applying a magnetic field are respectively installed in the same film-forming chamber. , having a mechanism for making the film-forming substrate move relatively sequentially between the arc evaporation source and the sputtering evaporation source, during film formation, introducing sputtering gas from the vicinity of the sputtering evaporation source, and simultaneously The reaction gas is introduced near the arc evaporation source. the

In addition, the sputtering evaporation source according to the sixth invention of the present invention to achieve the object is characterized in that it is a sputtering evaporation source used in the above-mentioned composite film forming apparatus, and an electric insulator material is used for parts other than the etching area. the

Similarly, the other feature of the sputtering evaporation source of the sixth invention is that it is a sputtering evaporation source used in the above-mentioned composite film-forming device, and the potential of the sputtering target is set at a portion other than the corrosion area. Shielding at floating or ground potential. the

In the composite film forming apparatus according to the fifth invention, as described above, the magnetic field applying means is configured so that the magnetic field lines between the adjacent evaporation sources are connected to each other during film forming. the

Therefore, the magnetic force lines in the same film-forming chamber are in a closed state (closed magnetic field structure). As will be described in detail later, the emitted electrons from the evaporation source are trapped in the closed magnetic field structure, and are not easily introduced into the same anode as the substrate. interior. As a result, even when arc evaporation and sputtering are performed simultaneously in the same film formation chamber, the concentration of emitted electrons is high, the collision with sputtering gas or reaction gas increases, and high-efficiency ionization of gas can be performed. change. the

In addition, in the composite film forming apparatus of the fifth invention described above, as described in the above other features, during film formation, the sputtering gas is introduced from the vicinity of the sputtering evaporation source, and the reaction gas is simultaneously introduced from the vicinity of the arc evaporation source. . Therefore, when arc evaporation and sputtering are performed simultaneously in the same film formation chamber, in addition, especially when the partial pressure of reactive gases such as nitrogen is increased in order to improve the film performance, and then the film is formed In this case, the reaction gas such as nitrogen is less likely to be mixed with the sputtering gas, so that it is possible to suppress the formation of an insulating film on the surface of the target by the ionized mixed gas and the occurrence of abnormal discharge. Therefore, high-efficiency ionization of gas can be performed. the

By carrying out the above-mentioned fifth invention and sixth invention individually or in combination, efficient ionization of gas can be promoted, ion irradiation to the substrate can be strengthened, and high characteristics such as high hardness can be realized by densification of the hard coating layer. . In addition, abnormal occurrences such as abnormal discharge during film formation can also be suppressed. the

In addition, as described in the above two features of the sputtering evaporation source of the sixth invention, by not applying a voltage to the non-etching area of the sputtering evaporation source, the particles sputtered from the etching area react with reactive gases such as nitrogen on the non-etching area. Reacts, combines, does not pile up. As a result, abnormal discharge caused by this can be prevented, and efficient ionization of gas can be performed. the

Description of drawings

Fig. 1 is a cross-sectional view schematically showing the laminated structure of the hard coating of the present invention. the

Fig. 2 is a cross-sectional view schematically showing a conventional hard coating. the

Fig. 3 is an explanatory view showing one embodiment of an apparatus for forming a hard coating of the present invention. the

Fig. 4 is an explanatory view showing another embodiment of the apparatus for forming a hard film of the present invention. the

Fig. 5 is an explanatory view showing another embodiment of the apparatus for forming a hard film of the present invention. the

Fig. 6 is an explanatory view showing another embodiment of the apparatus for forming a hard coating of the present invention. the

Fig. 7 is a view showing a microstructure of a cross-section in the thickness direction of the hard coating of the present invention, (a) is a schematic view, and (b) is a longitudinal sectional view. the

Fig. 8 is a front view showing another embodiment of the composite film forming apparatus of the present invention. the

Fig. 9 is a plan view showing still another embodiment of the composite film forming apparatus of the present invention. the

Fig. 10 is an explanatory diagram showing the relationship between the nitrogen partial pressure and the nitrogen content in the hard coating. the

11 is an explanatory diagram showing the relationship between the nitrogen partial pressure and the surface roughness Ra of the hard coating. the

FIG. 12 is an explanatory diagram showing the relationship between the nitrogen partial pressure and the Vickers hardness of the hard coating, respectively. the

Fig. 13 shows one form of the sputtering evaporation source of the present invention, Fig. 13(a) is a plan view of a sputtering target, and Fig. 13(b) is a front view of a sputtering evaporation source. the

Fig. 14 shows another embodiment of the sputtering evaporation source of the present invention, Fig. 14(a) is a plan view of a sputtering target, and Fig. 14(b) is a front view of a sputtering evaporation source. the

Fig. 15 shows one form of the sputtering evaporation source of the present invention, Fig. 15(a) is a plan view of a sputtering target, and Fig. 15(b) is a front view of a sputtering evaporation source. the

Detailed ways

First, an embodiment will be described below regarding the elements of the hard coating layer of the present invention. the

First, the method of controlling the particle size common to the above-mentioned first to third inventions will be described. the

(Control of crystal grain size of hard coating layer A)

The usual hard coating layer A such as TiN, CrN or TiAlN, which is formed by sputtering or ion plating and used for cutting tools or wear-resistant sliding parts, adopts the growth method of coating crystals as schematically shown in Figure 2, And after nuclei are produced from the substrate, columnar growth occurs, and the width of the columnar particles shows a tendency to expand along with the growth. the

On the other hand, for example, in the case of the above-mentioned first invention, as shown schematically in FIG. The plasma coating layers A are laminated alternately (film formation). In this case, the growth of each hard coating layer A is once interrupted by the insertion of each hard coating layer B, and each hard coating layer A repeats nucleation and growth from each hard coating layer B again. Therefore, as compared with FIG. 2 , the crystal grain sizes in both the film thickness direction and the direction parallel to the substrate surface (lateral direction) are made finer. In addition, in Fig. 1 and Fig. 2, the results obtained by TEM observation at 45,000 magnifications are shown in simplified diagrams for the cross-sections of hard coatings and laminated coatings. the

For example, if a TiAlN film is selected as the hard coating layer A and a TiAlN film is selected as the hard coating layer B, the thickness of layer A is set at about 50 nm, and the thickness of layer B is set at about 5 nm. As a result of cross-sectional TEM of the TiAlN/SiN laminated film at the time, as compared with the above-mentioned FIG. 2 , the growth of crystal grains in the film thickness direction was interrupted in each layer, and the crystal grains were miniaturized. Such miniaturization of the crystal grains enables the acquisition of excellent properties not found in conventional coatings, such as increased hardness of the coating. the

In the above-mentioned second invention, layer A is crystalline (Cr ₂ N type or CrN type), and layer B is amorphous. In this way, two layers with different crystal states are laminated alternately to form a film, and the crystal grains of layer A are inserted into layer B, so that the growth in the thickness direction of the film is interrupted on the way, and the crystal grain size equivalent to the thickness of layer A remains. As a result, the crystal grains are made finer and the hardness of the coating film is further improved than when no interruption of grain growth occurs in the above-mentioned conventional technique.

Next, elements of lamination of two types of hard coating layers common to the above-mentioned first to fourth inventions will be described. the

(thickness of hard lamination coating)

The necessity of the film thickness of the entire hard laminated film of the present invention varies depending on the application of cutting tools, sliding parts, and the like. When used for a cutting tool, the approximate standard is about 1 to 5 μm, and when used for a sliding member, the approximate standard is about 3 to 100 μm. Therefore, in order to achieve the thickness of these hard laminate coatings, after determining the thicknesses of layers A and B respectively according to the criteria described below, the film thickness can be controlled by changing the number of layers. the

(Relationship between film thickness of layer A and film thickness of layer B)

In the rigid laminate coating of the present invention, the thickness of the layer A of each layer is set to be twice or more than the thickness of the layer B of each layer. Layer A, which is the main phase of the hard laminated coating of the present invention, mainly defines the properties required for the hard laminated coating of the present invention, such as high hardness, wear resistance, and high oxidation resistance. When the thickness of layer A is less than twice the thickness of layer B, the properties of layer B dominate the properties of the hard laminated coating, failing to satisfy the required properties. Therefore, the thickness of layer A is set to be twice or more than the thickness of layer B. the

For example, in the case of the above-mentioned first invention, the hard coating layer A having a cubic rock-salt structure is basically a main phase having wear resistance, and has a hard coating having a crystal structure other than the cubic rock-salt structure. Layer B, although hard, is inferior to hard coating layer A in abrasion resistance. Therefore, in order to have excellent wear resistance as a hard coating, as a hard coating, it is necessary to secure a thickness at which the characteristics of the hard coating layer A having a cubic crystal rock salt structure can be dominant. the

(film thickness of layer A)

The thickness (film thickness) of the layer A of each layer is set at 200 nm or less, preferably 100 nm or less, more preferably 50 nm or less. When the thickness of layer A per layer is less than 200nm, etc., if it becomes thicker than the upper limit, there will be no composite effect as a laminated film, so instead of layer B, only the film-forming layer will be laminated There is no big difference in A. As a result, only the properties of layer A alone were found, and layer B could not assist the properties of layer A. the

For example, in the above-mentioned first invention, when the thickness of the layer A per layer exceeds 200 nm, the effect of crystal grain refinement is reduced, and the hard coating layer A is laminated without the hard coating layer B. As a result, before the formation of the hard coating layer B, the crystal growth of the hard coating layer A occurs, and a coarse crystal particle diameter is likely to be formed. Therefore, there is a possibility that the characteristics are equivalent to those of a conventional hard coating that grows crystals without interruption. the

In addition, it is preferable that the thickness of the layer A of each layer is 2 nm or more. If the thickness of layer A is less than 2 nm, even if the number of laminated layers of layer A is increased, the properties of layer A may not be guaranteed as a hard laminate coating. the

(film thickness of layer B)

The thickness of the layer B of each layer is set at 0.5 nm or more, preferably 1 nm or more. The thickness of layer B also varies with the thickness of layer A, but when it is less than 0.5 nm, etc., and the thickness is lower than the above-mentioned lower limit, there is no great difference from the case where only layer A is laminated without layer B. As a result, only the properties of layer A alone were found, and layer B could not assist the properties of layer A. the

For example, in the above-mentioned first invention, when the thickness of the hard coating layer B is less than 0.5 nm, the thickness of the layer B is too thin, and the effect of interrupting the grain growth of the layer B relative to the layer A may not exist. . Therefore, there is also a possibility that the crystal grains of the hard coating layer A cannot be refined. the

In addition, it is preferable that the upper limit of the thickness of the layer B per layer is set to 1/2 or less of the thickness of the layer A. When the thickness of layer B exceeds 1/2 of layer A, if the thickness of layer A is reduced, layer B will seriously affect the properties of the entire hard laminate coating, and it may be difficult to exert the properties of layer A. the

In addition, the thickness of the layer A and the layer B can be calculated|required from the average value of the value respectively measured from two visual fields of 500,000-1,500,000 magnifications by cross-sectional TEM observation. the

(Lamination method of hard coating layer A and hard coating layer B)

The composition of the layers of the hard laminate coating of the present invention is basically, if the compositions of layer A and layer B are set to be different from each other, it is preferably composed of layer A/layer B/layer A/layer B Alternate lamination of layers A and B (layer A/layer B) is regarded as a unit, and the lamination of this unit is repeated multiple times (multilayering). However, layer A/layer A/layer B/layer B or layer A/layer B/layer B/layer A, layer B/layer B/layer A/layer A, layer B/layer A/layer A/ Layer B and the like are used as one unit, and these units are respectively combined to alternately laminate. In addition, it is not necessarily necessary to set the layers A and B of these stacked layers to have the same composition. That is, within the scope of the present invention, depending on the purpose, the composition of laminated layers A or B may be different such as layer A1/layer B1/layer A2/layer B2. For example, in the above-mentioned first to third inventions, the third hard coating layer C has the same crystal structure as layer A (for example, a cubic crystal rock-salt structure), but it may also be composed of other components by selecting The hard coating layer (other substances) of the third hard coating layer C is sandwiched between them, for example, layer A/layer B/layer C or layer B/layer A/layer B/layer C, etc. as one units, stacked by combining these units individually. In addition, as for the number of laminations of these units, any number of laminations such as 20 to 1000 can be selected as long as it matches the thickness of the intended hard laminated film. the

Next, the compositions of the hard coating layers A and B of the first to fourth inventions described above will be described. the

[1st invention]

(Composition of Hard Coating Layer A)

The main phase of the hard coating of the present invention, that is, the composition of the hard coating layer A, needs to be selected to form a rock-salt crystal structure and have high hardness and wear resistance. In this regard, as a hard coating forming a rock-salt crystal structure, for example, TiN, CrN, or TiAlN, which is often used for cutting tools or wear-resistant sliding parts, can be used to contain any one of Ti, Cr, Al, and V. Any compound among nitrides, carbonitrides, and carbides of cubic crystal rock-salt structure. Besides these, compounds of elements selected from one or more of 4A, 5A, 6A, Al, and Si, and elements selected from one or more of B, C, and N can be used. These compounds all have a cubic crystal rock-salt structure as a crystal system, and are high in hardness and excellent in wear resistance. In addition, as long as the crystal structure of the hard laminate film A retains the rock-salt type structure, by adding a trace amount of oxygen to the layer A at a rate of 10% or less (atomic ratio, 0.1 or less), the hard laminate film layer can be A Forming an oxynitride or carbonitride layer of one or more elements selected from 4A, 5A, 6A, Al, and Si, or a layer containing these nitrogen oxides or carbonitrides, thereby, sometimes The characteristics can be improved, and these are also included in the scope of the present invention. the

The general formulas of these compounds that can be used for the hard coating layer A are Ti(C1-xNx), Cr(C1-xNx), V(C1-xNx) [but x is 0 to 1 The value of , the same below] and so on. In the binary system, TiAl(C1-xNx), TiSi(C1-xNx), TiCr(C1-xNx), TiV(C1-xNx), TiB(C1-xNx), CrAl(C1-xNx), CrSi (C1-xNx), CrV(C1-xNx), CrB(C1-xNx), VAl(C1-xNx), VSi(C1-xNx), VB(C1-xNx), etc. the

In the ternary system, use TiAlSi (C1-xNx), TiAlCr (C1-xNx), TiAlV (C1-xNx), TiAlB (C1-xNx), TiCrSi (C1-xNx), TiCrV (C1-xNx), TiCrB (C1-xNx), TiVSi(C1-xNx), TiVB(C1-xNx), CrAlSi(C1-xNx), CrAW(C1-xNx), CrAlB(C1-xNx), CrSiV(C1-xNx), CrSiB( C1-xNx), CrVB(C1-xNx), VAlSi(C1-xNx), VAlB(C1-xNx) and so on. the

In the quaternary system, use TiAlSiCr (C1-xNx), TiAlSiV (C1-xNx), TiAlSiB (C1-xNx), TiAlCrV (C1-xNx), TiAlCrB (C1-xNx), TiAlVB (C1-xNx), TiCrSiV (C1-xNx), TiCrSiB(C1-xNx), TiCrVB(C1-xNx), CrAlSiV(C1-xNx), CrAlSiB(C1-xNx), CrAlVB(C1-xNx), CrSiVB(C1-xNx), VAlSiB( C1-xNx) and so on. the

In addition, among these compounds, a compound containing any one of Ti, Cr, or Al has higher hardness. Examples of these compounds include compounds such as TiN, TiCN, TiAlN, CrN, TiCrAlN, and CrAlN. In particular, compounds containing Al have excellent oxidation resistance, and are preferably used for cutting tools that particularly require such oxidation resistance. In addition, compounds containing Cr (for example, CrN, TiCrN, CrCN) are suitable for applications to machine parts. the

)，由于是高温高压相，高硬度物质，因此维持岩盐结构，同时如果提高(TiAl)(CN)中的Al的比率，则能够更加提高(TiAl) (CN)膜的硬度。 In general, a rock-salt structure-type crystal structure hard coating can be measured and analyzed by X-ray diffraction using the θ·2θ method. The rock-salt structure-type hard film has high peak intensities in the (111) plane, (200) plane, and (220) plane of X-ray diffraction, respectively. For example, a hard coating such as (TiAl)(CN) has a rock-salt structure-type crystal structure, and constitutes a rock-salt-type composite nitride in which Al is substituted on the Ti side of rock-salt-type TiN. In this case, rock-salt AlN (lattice constant

), because it is a high-temperature, high-pressure phase, and a high-hardness substance, the rock-salt structure is maintained, and at the same time, if the ratio of Al in (TiAl)(CN) is increased, the hardness of the (TiAl)(CN) film can be further improved.

(Composition of Hard Coating Layer B)

Regarding the hard coating layer B, the hard coating layer B is preferably an element selected from (1) one or more of 4A, 5A, 6A, and Al, each of which does not have a crystal structure of a cubic crystal rock-salt structure. and compounds (hexagonal, etc.) of one or more elements selected from B, C, and N, or (2) elements selected from one or more of B, Si, Cu, Co, Ni, and C Selected from nitrides, carbonitrides, and carbides, or selected from (3) metal Cu, metal Co, and metal Ni, thereby forming. Among them, the above-mentioned group (2) is most preferable. the

Basically, as the hard coating layer B, if it has a crystal structure that does not have a rock-salt type cubic crystal structure, the above-mentioned crystal grain refinement effect can be exhibited. However, the hard coating of the present invention is preferably one of the above-mentioned groups having heat resistance and wear resistance in consideration of the conditions when cutting tools and the like are used at elevated temperatures and the required properties as sliding parts. Among them, in the above group (2), compounds containing B or Si, ie, BN, BCN, SiN, SiC, SiCN, B-C or Cu, CuN, CuCN, or metal Cu are more preferred. the

[Second invention]

The inventors of the present invention have found that by satisfying the above-mentioned lamination constituent elements, layer A having a chemical composition satisfying the following formula (1) and layer B having a chemical composition satisfying the following formula (2) are formed , a hard coating excellent in wear resistance and lubricity can be obtained, thereby completing the present invention. the

Layer A: Cr(BaCbN1-a-b-cOc)e

0≤a≤0.15, 0≤b≤0.3, 0≤c≤0.1, 0.2≤e≤1.1...(1)

Layer B: B1-s-tCsNt

0≤s≤0.25, (1-s-t)/t≤1.5...(2) 

The reason why the composition and thickness of layer A and layer B are defined in this way will be described in detail below. the

[Composition of layer A]

First, when layer A is used as a Cr (B, C, N, O) film, the ratios of B, C, N, and O shown in the above formula (1) are determined for the following reasons. That is, in order to maintain wear resistance in the coating, layer A is set to have a composition mainly composed of chromium nitride (CrN, Cr ₂ N) having high hardness. Then, by adding C, B, and O to chromium nitride, the hardness is further increased and the wear resistance is improved. However, due to the excessive addition of these elements, the hardness will decrease instead, so the upper limit of a (that is, B) is set At 0.15, it is preferably set at 0.1, the upper limit of b (i.e. C) is set at 0.3, preferably at 0.2, and the upper limit of c (i.e. O) is set at 0.1, preferably below 0.07.

In addition, the ratio e of the total of B, C, N, and O to Cr is preferably set in the range of 0.2 to 1.1, and this range corresponds to the case where the structure of the crystal constituting the layer A is a Cr ₂ N or CrN structure. scope. In addition, the crystal structure of layer A can be confirmed by cross-sectional TEM and electron beam diffraction as described later.

[Composition of layer B]

Next, in order to impart lubricity to the film, layer B is set to a BN compound that functions as a solid lubricant. Here, in order to form a BN compound, the ratio (1-s-t)/t of B to N needs to be set to 1.5 or less, preferably 1.2 or less. In addition, by adding C to the BN compound, lubricity can be imparted to the layer B and high hardness can be achieved, but excessive addition will conversely lower the hardness and lose lubricity, so the upper limit of s is set at 0.25. The ratio s/(1-s-t) of C to B is preferably at most 0.25, more preferably at most 0.1. the

[Modification of composition of layer A]

As described above, layer A is responsible for developing high hardness and wear resistance, and it is a layer that can further improve the properties by intercalating layer B to refine crystal grains. By substituting other elements, the hardness of the layer A can be further increased, and the wear resistance can be further improved. the

The above-mentioned other elements are one or two or more elements selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, and Si. Among these, Al, Si, W, and Ti are preferable as one element, and various combinations of Al and Si, Al and Ti, W and Si, and Ti and Si are preferable as two elements. the

If the ratio α of substitution with the above-mentioned other elements is too large, the effect of improving the hardness will be lost due to the excessive reduction of the original Cr ratio, so it is set at 0.9 or less. The lower limit of the substitution ratio α is not particularly limited, but it is preferably set at 0.05 or more in order to obtain a certain effect by substitution with the above-mentioned other elements. A more preferable range of the substitution ratio α varies depending on the type or combination of elements to be substituted, and is approximately 0.4 to 0.8 as a standard. the

In addition, in the case of combining the two elements of Ti and Al and substituting with Cr, the oxidation resistance of the film can be improved by increasing Al, so the ratio of Al is preferably larger than the ratio of Ti, but if the ratio of Al is too large, then Since the coating tends to be amorphous, the ratio of Al to the total amount of Cr, Ti, and Al is preferably set at 0.8 or less. the

In addition, when Si is contained in the substituting element, if the ratio of Si is too large, the layer A is likely to be amorphous, so the ratio of Si to the total amount of Cr and the substituting element is preferably set at Below 0.5. the

[Modification of composition of layer B]

As the layer B, a coating excellent in wear resistance can be obtained even if a SiCN-based or CN-based coating is used in addition to the BCN-based coating. the

When the SiCN-based coating is used for layer B, in general, the low friction coefficient of the BCN-based coating cannot be obtained, and the aggressiveness against the target material cannot be reduced. It is used for coatings such as cutting tools that do not need to consider the aggressiveness to the target material due to its excellent wear resistance. In addition, it becomes a film excellent in oxidation resistance. In addition, if carbon C is added too much, the hardness will decrease instead, so the upper limit of the addition ratio of C is set at 0.6. the

In addition, CN-based coatings are generally not used in high-temperature sliding environments due to their instability at high temperatures. can be used. The approximate standard of the addition ratio of N is 0.6 or less, preferably 0.4 or less. the

[Grain refinement degree of layer A]

As described above, layer A can form a hexagonal _Cr2N -type structure or a cubic rock-salt-type CrN-type structure depending on the ratio between Cr and the total amount of B, C, N, and O, but due to the CrN-type structure Since the wear resistance is excellent, a rock salt cubic crystal structure is set as a preferable aspect of the crystal structure of the layer A.

In addition, the gist of the present invention is that by laminating layer A and layer B at the film thicknesses and film thickness ratios described above, the growth of crystal grains in layer A is interrupted in layer B, resulting in miniaturization of crystal grains. the

Here, the degree of refinement of crystal grains can be represented by the half-amplitude (FWHM: Full Width Half Maximum ) as an index evaluation. Generally, the half-amplitude of the diffraction line has a certain relationship with the crystal grain size of the material to be measured, and the half-amplitude increases as the crystal grain size decreases. However, it is known that the half-amplitude of the diffraction line also changes due to other factors, such as the uneven stress generated on the film, so the relationship between the half-amplitude and the crystal grain size does not necessarily follow a linear ratio. the

Based on the above results, the present inventors studied the relationship between the half-amplitude of the above-mentioned diffraction lines and the hardness or wear resistance of the coating, and found that at least half-amplitudes of the diffraction lines from the (111) and (200) planes When one of them is 0.3° or more, the properties of the film can be further improved. More preferably, the lower limit of the half-amplitude is 0.4°. The upper limit of the above-mentioned half width is not particularly limited, but is substantially about 1°. the

In the present invention, the half-amplitude of the diffraction line is evaluated by X-ray diffraction by the θ-2θ method using CuKα rays (40 kV·40 mA). In addition, the conditions of other X-ray optical systems are set as follows: the divergence and scattering slit is 1°, the light receiving slit is 0.15mm, a graphite monochromator is used, and the light receiving slit before the counter is 0.8°, and the scanning Speed 2°/min (continuous scan), step amplitude 0.02°. the

[the third invention]

(Composition of layer A)

The composition of layer A, which is the main phase of the hard laminated coating of the present invention, needs to have high oxidation resistance especially for applications where sliding parts such as cutting tools reach high temperatures. In addition, layer A needs to have basic properties such as high hardness and abrasion resistance required for a hard coating. the

Therefore, the constituent composition as layer A is set to consist of:

Formula 1: (Ti1-x-yAlxMy)(BaCbN1-a-b-cOc) [However, x, y, a, b, c represent atomic ratios, 0.4≤x≤0.8, 0≤y≤0.6, 0≤a≤ 0.15, 0≤b≤0.3, 0≤c≤0.1, and M is a metal element selected from one or more of 4A, 5A, 6A, and Si]. the

Even in the composition represented by formula 1 of this layer A, it is more preferable to be composed of (Ti1-x-yAlxMy)(BaCbN1-a-b-cOc) [However, x, y, a, b, c represent atomic ratios respectively, and 0.5≤ x≦0.8, 0.05≦y≦0.6, 0≦a≦0.15, 0≦b≦0.3, 0≦c≦0.1, and M is a metal element selected from one or more of Cr, V, and Si]. the

In addition, in the above formula 1, the atomic ratio of (TiAlM) and (BCNO), in other words, the atomic ratio between the two parentheses of the metal element group and the non-metal element group, is usually 1:1, but not Must be limited to 1:1 only. In the actual film-forming Ti-based compounds exemplified below, the atomic ratio of (TiAlM) to (BCNO) is of course not limited to 1:1 due to differences in film-forming conditions, for example, 0.8 to 1.2:0.8 ~1.2 etc. swing range. Therefore, in the above-mentioned formula 1, the atomic ratio of (TiAlM) and (BCNO), the atomic ratio of the metal element group and the non-metal element group, of course, allows the swing width of the atomic ratio of the Ti-based compound actually formed into a film. the

(Ti system composition)

In the composition of the layer A, firstly, in order to have characteristics such as high hardness and high wear resistance as a hard coating, nitrides, carbonitrides, boronitrides, and carboronitrides containing Ti are most suitable, such as Components represented by Ti-based compounds such as TiAlN, TiAlCrN, TiAlVN, TiAlNbN, TiAlBN, and TiAlCrCN serve as the basis of the layer A portion of the present invention. the

(Al)

The hardness and oxidation resistance of layer A can be improved by containing Al which satisfies the above composition formula with respect to the Ti-based component. This effect is more remarkable when Al is contained in the range of 0.4 to 0.8 (the above range of 0.4≤x≤0.8), preferably 0.5 to 0.8 (the range of 0.5≤x≤0.8) in atomic ratio x. In addition, even if Al is contained, if the composition range is exceeded, the effect of improving hardness and oxidation resistance disappears or becomes small, and there is no meaning of including Al. the

(metal element M)

As in the composition formula above, in addition, when one or more metal elements selected from 4A, 5A, 6A, and Si represented by M are selectively contained, the hardness and oxidation resistance of layer A can be further improved. This effect is remarkable when the metal element is contained at an atomic ratio y of 0.6 or less (the above range of 0≤y≤0.6). The reason is that, when M is contained at an atomic ratio of more than 0.6, the total content of the basic Ti and Al is lower than 0.4 at an atomic ratio, and the hardness and oxidation resistance of the layer A are conversely lowered. the

In addition, as the metal element M that exerts the above-mentioned effects, it is preferable to use a combination of one or more selected from Cr, V, and Si, and the preferable content range for exerting the above-mentioned effects of these metal elements is 0.05 to 0.6 in terms of atomic ratio y. The range of 0.05 ≤ y ≤ 0.6, more preferably the range of 0.1 to 0.3 (the range of 0.1 ≤ y ≤ 0.3). the

(non-metallic elements)

Among the nonmetallic elements selected from B, C, and N in the composition formula of layer A above, nitrogen (N) is essential to form nitrides, carbonitrides, boronitrides, and carbonboronitrides. The content of this nitrogen is based on the content of B, C (the value of a or b in the above-mentioned composition formula) or the content of O (the value of c in the above-mentioned composition formula) that are selectively contained, as follows The composition formula of the above-mentioned layer A is defined as N1-a-b-c. the

Boron (B) is optionally contained in order to form boronitrides and carboronitrides. However, even if it is contained, if it is added excessively, soft borides will precipitate, and both the hardness and oxidation resistance of the layer A will be lowered. Therefore, in terms of the atomic ratio a, the upper limit is set to 0.15 (the above-mentioned 0≤a≤0.15), and preferably the upper limit is set to 0.1 or less (0≤a≤0.1). the

Carbon (C) is selectively contained in order to form carbides and carbonitrides. However, even if it is contained, if it is added excessively, the softening of the layer A will be caused, and the hardness and oxidation resistance of the layer A will be reduced. Therefore, in atomic ratio b, the upper limit is set to 0.3 (the above-mentioned 0≤a≤0.3), and preferably the upper limit is set to 0.2 or less (0≤b≤0.2). the

In addition, oxygen (O) may be included in a small amount to increase the hardness of layer A, but if it is contained in an atomic ratio c of more than 0.1, the proportion of oxides in the film will increase and the toughness of the film will be impaired. Therefore, the upper limit is set to 0.1 or less (0≤c≤0.1). the

(Composition of layer B)

Layer B generally has the role of imparting properties that layer A does not have or improving the properties of layer A. Therefore, in the present invention, when laminating alternately with the layer A, in addition to the characteristics and purposes of each composition, each compound represented by the four composition formulas of the following formulas 1 to 4 is selected. the

Formula 2: B1-x-yCxNy[However, x and y respectively represent the atomic ratio, 0≤x≤0.25, B/N≤1.5],

Formula 3: Si1-x-yCxNy[However, x and y respectively represent the atomic ratio, 0≤x≤0.25, 0.5≤Si/N≤2.0],

Formula 4: C1-xNx [however, x represents the atomic ratio, 0≤x≤0.6],

Formula 5: Cu1-y(CxN1-x)y [However, x and y respectively represent atomic ratios, 0≤x≤0.1, 0≤y≤0.5]. the

Each compound represented by the above four formulas has a crystal structure different from that of the above-mentioned layer A compound, and by laminating these compounds on the layer A, there is an effect of breaking the grain growth of the layer A, and the crystal grain size can be improved. Miniaturization. As a result, the hardness of the hard laminate coating can be significantly improved. the

In each compound represented by the above-mentioned 4 formulas, the nitride or carbonitride-based compound of B in Formula 2 and the carbon or carbonitride-based compound of Formula 4, when both are stacked with layer A, can Provides lubricity not present in layer A. Among them, the B-series compound of Formula 2 is stable at high temperature and has excellent lubricity at room temperature to high temperature. In addition, the C-based compound of Formula 4 is superior to the B-based compound of Formula 2 in terms of lubricating properties at low temperatures. The above-mentioned formulas (composition ranges) of the B-based compound of Formula 2 and the C-based compound of Formula 4 are all composition ranges necessary to ensure lubricity. the

In the above-mentioned formula 2 of the B-based compound, in order to ensure the lubricity, the atomic ratio x of the amount of C is 0.25 or less (above 0≤x≤0.25), preferably 0.2 or less. In addition, in the case of a B-rich compound in which B/N in Formula 2 exceeds 1.5, it does not have lubricity. Therefore, the upper limit of B/N, that is, the ratio of B and N is 1.5 or less (the above-mentioned B/N≦1.5), more preferably 1.2 or less (the above-mentioned B/N≦1.2). In addition, in Formula 2, since the atomic ratio y of the amount of nitrogen is determined by the ratio of B and N described above in combination with the amount of C, the range cannot be determined by y alone. That is, if the amount of C is determined, since the respective amounts of B and N are determined from B/N including y, it is not necessary to determine the range with y alone as long as the range of B/N is determined. the

The Si nitride or carbonitride-based compound, that is, the Si-based compound of Formula 3, when combined with layer A, has the effect of further improving oxidation resistance. In Formula 3, when the amount of C (atomic ratio x) is large, the hardness of the film tends to decrease, so the upper limit of the atomic ratio x of C is set to 0.25 or less (the above 0≤x≤0.25), More preferably, it is set at 0.2 or less (0≤x≤0.2). In addition, the reason for specifying Si/N, that is, the ratio of Si and N, is because if the range of the specified Si/N ratio (the above-mentioned 0.5≤Si/N≤2.0), more preferably 0.5≤Si/N≤1.4, the hardness Remarkably, the hardness characteristics of the entire laminated film deteriorate. In addition, in Formula 3, the atomic ratio y of the amount of nitrogen is determined by the above-mentioned ratio of Si and N in combination with the amount of C, so the range cannot be determined by y alone. That is, if the amount of C is determined, since the respective amounts of Si and N are determined from B/N including y, it is not necessary to determine the range with y alone as long as the range of Si/N is determined. the

In Formula 4 of carbon or carbon nitride-based compounds, when the atomic ratio x of the amount of C exceeds 0.6 and is excessively contained, the lubricity is deteriorated. Therefore, the upper limit of the atomic ratio x of the amount of C is set to 0.6 or less (the above-mentioned 0≤x≤0.6). the

The compound of Formula 5, which is a Cu nitride or carbonitride-based compound, can increase the hardness by combining with layer A within a predetermined composition range. When the upper limit of the atomic ratio x of the amount of C exceeds 0.1, or the atomic ratio y of the above-mentioned (CxN1-x)y exceeds 0.5, etc., if the composition range is exceeded, even if combined with layer A, there is no effect of increasing hardness. Therefore, as described above, x and y are respectively set to 0≤x≤0.1 and 0≤y≤0.5. the

[4th invention]

(Composition of layer A)

The composition of layer A, which is the main phase of the hard laminated film of the fourth invention, needs to have high oxidation resistance especially for applications where sliding parts such as cutting tools reach high temperatures. In addition, layer A needs to have basic properties such as high hardness and wear resistance required for hard coatings. Therefore, the composition of the layer A is selected from Ti-based or Cr-based compounds with a specific composition. the

(Ti compound)

However, the Ti-based layer A is set to be composed of the composition of the following formula 1. the

Formula 1: (Ti1-x-yAlxMy)(BaCbN1-a-b-cOc) [However, x, y, a, b, c represent atomic ratios, 0.4≤x≤0.8, 0≤y≤0.6, 0≤a≤ 0.15, 0≤b≤0.3, 0≤c≤0.1, in addition, M is a metal element selected from at least one of 4A, 5A, 6A, and Si]

In addition, in the above formula 1, the atomic ratio of (TiAlM) and (BCNO), in other words, the atomic ratio between the two parentheses of the metal element group and the non-metal element group, is usually 1:1, but not Must be limited to 1:1 only. In the actual film-forming Ti-based compounds exemplified below, the atomic ratio of (TiAlM) to (BCNO) is of course not limited to 1:1, depending on the film-forming conditions, for example, 0.8-1.2:0.8- 1.2 and so on swing range. Therefore, in the above-mentioned formula 1, the atomic ratio of (TiAlM) and (BCNO), the atomic ratio of the metal element group and the non-metal element group, of course, allows the fluctuation range of the atomic ratio of these Ti-based compounds actually formed into a film. the

In the composition of this layer A, firstly, in order to have characteristics such as high hardness and high wear resistance as a hard coating, it is most suitable to contain nitrides, carbonitrides, boronitrides, and carboronitrides based on Ti, That is, the components that serve as the basis of the layer A portion of the present invention are typified by Ti-based compounds such as TiAlN, TiAlCrN, TiAlVN, TiAlNbN, TiAlBN, and TiAlCrCN. the

(Al)

The hardness and oxidation resistance of the layer A are improved by containing Al having the above-mentioned compositional formula with respect to the Ti-based component. This effect is remarkable when Al is contained in the range of 0.4 to 0.8 (the above-mentioned range of 0.4≤x≤0.8), preferably in the range of 0.5 to 0.8 (the range of 0.5≤x≤0.8) in atomic ratio x. In addition, even if Al is contained, if the composition range is exceeded, the effect of improving hardness and oxidation resistance disappears or becomes small, and there is no meaning of including Al. the

(metal element M)

As in the composition formula above, in addition, when one or more metal elements selected from 4A, 5A, 6A, and Si represented by M are selectively contained, the hardness and oxidation resistance of layer A can be further improved. This effect is remarkable when the metal element M is contained at an atomic ratio y of 0.6 or less (the above range of 0≤y≤0.6). The reason is that, when M is contained in an atomic ratio of more than 0.6, the total content of the basic Ti and Al is lower than 0.4 in an atomic ratio, and the hardness and oxidation resistance of the layer A are conversely reduced. the

In addition, as the metal element M that exerts the above-mentioned effects, it is preferable to be a combination of one or more selected from Cr, V, and Si, and the preferable content range for exerting the effects is the range of 0.06 to 0.6 in atomic ratio, more preferably 0.1 ~0.3 range. the

(non-metallic elements)

Among the nonmetallic elements selected from B, C, and N in the composition formula of layer A above, nitrogen (N) is essential to form nitrides, carbonitrides, boronitrides, and carbonboronitrides. The content of this nitrogen is determined by the content of B and C (the value of a or b in the above-mentioned compositional formula) or the content of O (the value of c in the above-mentioned compositional formula) that are selectively contained, such as the above-mentioned layer A. The composition formula of the composition is stipulated as N1-a-b-c. the

Boron (B) is optionally contained in order to form boronitrides and carboronitrides. However, even if it is contained, if it is added excessively, soft borides are precipitated, and the hardness and oxidation resistance of the layer A are lowered. Therefore, the upper limit of the atomic ratio a is set to 0.15 (the above-mentioned 0≤a≤0.15), and preferably the upper limit is set to 0.1 or less (0≤a≤0.1). the

Carbon (C) is selectively contained in order to form carbides and carbonitrides. However, even if it is contained, if it is added excessively, the softening of the layer A will be caused, and the hardness and oxidation resistance of the layer A will be reduced. Therefore, in atomic ratio b, the upper limit is set to 0.3 (the above-mentioned 0≤a≤0.3), and preferably the upper limit is set to 0.2 or less (0≤b≤0.2). the

In addition, oxygen (O) may be included in a small amount to increase the hardness of layer A, but if it is contained in an atomic ratio c exceeding 0.1, the proportion of oxides in the coating will increase, impairing the toughness of the coating. . Therefore, the upper limit is set to 0.1 or less (0≤c≤0.1). the

(Cr compound)

In addition, the Cr-based layer A is set to be composed of the composition of the following formula 2. the

Formula 2: (Cr1-αXα)(BaCbN1-a-b-cOc)e [However, α, a, b, c, e represent atomic ratios, 0≤α≤0.9, 0≤a≤0.15, 0≤b≤0.3 , 0≤c≤0.1, 0.2≤e≤1.1, in addition, X is a metal element selected from any one or more of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al and Si]

In the Cr-based component composition of this layer A, in order to have characteristics such as high hardness and high wear resistance as a hard coating, it is most suitable to use Cr nitrides, carbonitrides, boronitrides, and carbonboronitrides. Cr-based compounds such as CrN, Cr ₂ N, CrSiN, CrAlN, CrBN, and CrSiBN are typified, and these are used as the basic component of the layer A part of the present invention.

When the amount of Cr is small, the hardness of the Cr-based component composition is lower than that of the Ti-based component composition. However, when used for sliding parts, it is more suitable for sliding parts because of its relatively low aggressiveness to materials compared with the composition of Ti-based components. In addition, even when the amount of Cr is small, high hardness can be obtained by adding elements, and it is also very suitable for cutting tools. the

(add element X)

The additive element X for increasing the hardness is a specific metal element selected from any one or more of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al, and Si. When these metal elements X are contained in an atomic ratio α of 0.9 or less (the above range of 0≦α≦0.9), the effect can be exhibited particularly. The reason is that when the metal element X is contained at an atomic ratio of more than 0.9, the basic Cr content is lower than 0.1 at an atomic ratio, and the hardness and oxidation resistance of the layer A are conversely reduced. the

Especially when used for sliding parts, if the amount of Cr is small, the aggressiveness with the target material increases, so it is necessary to secure a certain amount of Cr. For this reason, when used in sliding parts, the above-mentioned atomic ratio α is preferably set to 0.5 or less, more preferably 0.3 or less, so as to ensure the amount of Cr. In addition, in the case of use in a cutting tool, it is conversely preferable to set the above-mentioned atomic ratio α at 0.5 or more, more preferably at 0.7 or more, in order to increase the hardness. the

(non-metallic elements)

The predetermined values and meanings of the non-metallic elements selected from B, C, and N in the compositional formula of layer A are the same as those of the above-mentioned Ti-based compound. However, the atomic ratio e of (BaCbN1-a-b-cOc)e in the above formula 3 is set in the range of 0.2 to 1.1 (the above-mentioned 0.2≤e≤1.1). If e is less than 0.2, the non-metallic elements selected from B, C, and N will be insufficient, and the hardness and oxidation resistance of layer A will decrease. In addition, even if e exceeds 1.1, if the metal elements such as Cr and X are insufficient, the hardness and oxidation resistance of the layer A will conversely decrease. the

(Composition of layer B)

Layer B generally has the role of imparting properties such as high-temperature lubricity that layer A does not have or improving properties such as oxidation resistance of layer A. Such characteristics can be exhibited when the layer B has a composition of the following formula 3. the

Formula 3: M(BaCbN1-a-b-cOc) [However, M is a metal element selected from any one or more of W, Mo, V, and Nb, a, b, and c represent atomic ratios, 0≤a≤0.15 , 0≤b≤0.3, 0≤c≤0.1]. the

In addition, in the above formula 3, the atomic ratio of M and (BCNO), in other words, the atomic ratio of the metal element M and the non-metal element group, is usually 1:1, but it is not necessarily limited to 1:1 , which is the same as the case of Equation 1 above. Therefore, the atomic ratio of the metal element M and the non-metal element group is allowed to fluctuate in the range of 0.8-1.2:0.8-1.2 and the like. the

The compound represented by the composition formula of the above formula 3 has a different crystal structure from the Ti-based or Cr-based compound of the specific composition of the above-mentioned layer A. Therefore, the hardness of the hard laminate coating can be significantly increased, thereby improving the properties of the layer A. the

That is, the compound of layer A generally has a cubic crystal rock-salt crystal structure, although it is related to the content of elements, it also has a lattice constant in the range of 0.41 to 0.43 nm. In contrast, the compound containing W, Mo, V, and Nb represented by the composition formula of Formula 3 above has a relatively large lattice constant of 0.44 nm or more. Therefore, when these compounds are used as layer B to be laminated (film-formed) with the above-mentioned compound of layer A, a large strain is introduced into the interface between layer A and layer B. As a result, when the coating is used, even when deformation is applied from the outside of the coating and cracks in the coating extend up and down the coating (thickness direction), there is a high probability that the cracks in the coating will be prevented by the portion due to the strain at the interface. For this reason, it is presumed that the hardness and durability of the layer A can be improved as described above. the

Among the compounds represented by the composition formula of Formula 3 above, when a compound containing W, Mo, and Nb is laminated on the layer A, the oxidation resistance of the layer A can be improved. For compounds containing W, Mo, and Nb, the oxidation initiation temperature of the monomer is as low as 600 to 700°C. However, in the case of laminating with layer A having a thickness twice or more that of layer B, in an oxide film in which T contained in layer A is formed of i, Al, Cr, etc., the above-mentioned W, Mo, Nb The element diffuses to densify the above-mentioned oxide film, and as a result, the oxidation resistance of the layer A is improved. the

Among the compounds represented by the composition formula of Formula 3 above, the compound containing V cannot improve the oxidation resistance of the layer A, but can improve the lubricity of the layer A at high temperature. V forms soft oxides (V ₂ O _{5 ,} etc.) at high temperatures, and this oxide can improve the lubricity of layer A at high temperatures.

In the composition formula of Formula 3 above, when two or more of W, Mo, V, and Nb are contained, the necessary composition ratio may be appropriately selected in order to exert the above-mentioned effects. the

The predetermined values and meanings of the non-metallic elements of (BaCbN1-a-b-cOc) in the composition formula of Formula 3 above are the same as in the case of layer A described above. Nitrogen (N) is necessary for the formation of nitrides, carbonitrides, boronitrides, carboronitrides. The content of this nitrogen, by other selectively contained B, C content (the value of a or b in the above-mentioned composition formula) or O content (the value of c in the above-mentioned composition formula), has the above-mentioned layer The compositional formula of B is thus specified as N1-a-b-c. the

Boron is selectively contained to form boronitrides and carboronitrides. However, even if it is contained, if it is added excessively, soft borides will be precipitated, and the hardness and oxidation resistance of layer B and even layer A will be lowered. Therefore, the upper limit of the atomic ratio a is set to 0.15 (the above-mentioned 0≤a≤0.15), and preferably the upper limit is set to 0.1 or less (0≤a≤0.1). the

Carbon (C) is selectively contained to form carbides and carbonitrides. However, even if it is contained, if it is added excessively, layer B and layer A will be softened, and the hardness and oxidation resistance of the coating will be lowered. Therefore, in atomic ratio b, the upper limit is set to 0.3 (the above-mentioned 0≤a≤0.3), and preferably the upper limit is set to 0.2 or less (0≤b≤0.2). the

In addition, oxygen (O) may be included in a small amount to increase the hardness of layer B and layer A, but if it is contained in an atomic ratio c of more than 0.1, the proportion of oxides in the coating will increase, detrimental film toughness. Therefore, the upper limit is set to 0.1 or less (0≤c≤0.1). the

(Replacing the metal element M of layer B with other metal elements M1)

In the composition formula 3 of the above-mentioned layer B, in addition to the above-mentioned W, Mo, V, and Nb, it is also possible to replace the metal with a metal element M1 selected from one or more of 4A, 5A, 6A, and Si other than these. Element M. This has the meaning of allowing the inclusion of the metal element M1 within the range that does not inhibit the effect of the metal element M, and has the property that the layer B can be given the selected metal element M1 by including the metal element M1 and combining with the metal element M. Or it means improving the performance of layer B (and further layer A or coating). the

For example, by substituting any of Ti, Al, Si, and Cr as the metal element M1 for W, Mo, and V as the metal element M, the film hardness can be increased. the

The ratio of the amounts when these elements are substituted is such that the atomic ratio b is set within the range of 0.3 or less (the above-mentioned 0≤b≤0.3) in M1-bM1b. When the atomic ratio b exceeds 0.3 to replace the metal element M1, the effect of improving the hardness or durability of the layer A by the metal element M, that is, W, Mo, V, and Nb, and the effect of W, Mo, and Nb on the other hand are hindered. The above-mentioned effect of improving oxidation resistance or the effect of improving the above-mentioned high-temperature lubricity of Nb. the

Hereinafter, embodiments of the composite film-forming apparatus of the fifth invention suitable for producing the hard laminate coatings of the first to fourth inventions will be described in detail with reference to the drawings. Fig. 5 is a plan view showing one embodiment of the device of the present invention for film formation. In addition, FIG. 6 is a plan view showing a coating device of a comparative example. Fig. 8 is a front view showing another embodiment of the composite film forming apparatus of the present invention. Fig. 9 is a plan view showing still another embodiment of the composite film forming apparatus of the present invention. the

In the film forming apparatus shown in FIG. 5 and FIG. 6 , the substrate 1 is arranged on a plurality of (in FIG. 5 , four symmetrical) rotating disks 9 in common in the film forming chamber 8 , and around them, In the circumferential (circumferential) form, the sputtering evaporation sources 2, 3 and the arc evaporation sources 5, 6 are arranged so as to face each other. In addition, sputtering evaporation sources and arc evaporation sources are alternately arranged adjacent to each other. the

Then, each substrate 1 is rotated by the rotation of the rotary disk 9 , and the substrate 1 alternately passes in front of the arc evaporation sources 5 , 6 and the sputter evaporation sources 2 , 3 . In this case, the arc evaporation sources 5, 6 and the sputtering evaporation sources 2, 3 may be rotated around the substrate 1 without rotating either the rotary disk 9 or the substrate 1. A mechanism for sequentially moving the substrate on which the film is formed relative to each other between the arc evaporation source and the sputtering evaporation source may be used. the

In addition, as another form, in the film forming chamber 8, the sputtering evaporation sources 2, 3 and the arc evaporation sources 5, 6 may not be arranged in a circumferential shape, but may be arranged alternately in series in a linear form, so that the film-forming substrate The arc evaporation source and the sputtering evaporation source are relatively moved sequentially. the

In addition, when arc evaporation sources 5 and 6 are used to form a hard coating such as TiAlN, nitrogen, methane, acetylene and other reactive gases are introduced into the film forming chamber 8, and the pressure of the reactive gas containing several Pa In the protective atmosphere of the area, the TiAl target material is used for film formation. the

In addition, when using the sputtering evaporation sources 2 and 3 to form a hard film such as TiAlN in the same way, it is the same as forming a film by arc in terms of using a TiAl target. However, inert gases such as Ar, Ne, and Xe used as sputtering gases are mixed with reactive gases such as nitrogen, and the total pressure of the protective atmosphere is about several tenths of Pa, which is lower than arc film formation. the

In addition, each substrate 1 is rotated by the rotation of the rotary disk 9, and then the substrate 1 is alternately passed in front of the arc evaporation sources 5, 6 and the sputtering evaporation sources 2, 3, so that each sputtering film formation or each Arc film formation, and the same or different hard materials can be used here, and hard coatings of the same or different composition or thickness can be sequentially formed on the substrate 1 in multiple layers. the

(Magnetic field external mechanism)

Here, the film forming apparatuses shown in FIG. 5 and FIG. 6 are used in common with the above-mentioned arc evaporation sources 5, 6 and sputtering evaporation sources 2, 3, and utilize magnetic field application mechanisms such as permanent magnets provided by these evaporation sources respectively. 4 generation and control of the magnetic field 10 . the

However, in the case of using this magnetic field 10, in the film forming apparatus of the present invention shown in FIG. between. That is, the above-mentioned magnetic field applying mechanism 4 is configured so that the lines of magnetic force (magnetic field 10 ) between the adjacent evaporation sources are connected to each other during film formation. the

Therefore, the magnetic field 10 (magnetic force lines) in the same film forming chamber 8 is in a closed state (closed magnetic field structure), so that the electrons emitted from the above-mentioned evaporation sources are trapped in the closed magnetic field structure, and are not easily guided to the substrate 1. Inside the chamber 8 which also becomes the anode. As a result, the concentration of emitted electrons is high, and collisions with the sputtering gas or reaction gas increase, enabling efficient ionization of the gas. the

Thus, even in the case of simultaneously performing arc film formation and sputtering film formation in the same film formation chamber, the film formation device of the present invention in FIG. 1 can also improve the directivity of ions from two adjacent evaporation sources, By increasing the ion irradiation to the substrate 1, a film with better characteristics can be formed. the

Corresponding to this, in the comparative example film forming apparatus of FIG. 6 , the magnetic fields 10 of two adjacent evaporation sources are not connected to each other, for example, the magnetic fields 10 of the arc evaporation source 5 and the sputtering evaporation sources 2 and 3 are independently formed. . the

Therefore, the magnetic field 10 (magnetic force lines) in the same film forming chamber 8 is in a closed state (closed magnetic field structure), and the electrons emitted from the above-mentioned evaporation sources are easily guided quickly (easy) along the directions of the respective magnetic field 10 (magnetic force lines). into the film-forming chamber 8. As a result, even when arc film formation and sputter film formation are performed simultaneously in the same film formation chamber, the concentration of emitted electrons is low, and collisions with sputtering gas or reaction gas are reduced, resulting in a decrease in gas ionization efficiency. the

Therefore, in the case of the film-forming apparatus of the comparative example in FIG. 6 , the directivity of ions from the two evaporation sources is slow, the amount of ion irradiation to the substrate is reduced, and the possibility of hindering film properties and film-forming efficiency increases. the

(Basis for increasing ion irradiation effect)

The ion current flowing in the substrate 1 was measured using the film forming apparatus shown in FIGS. 5 and 6 . In the film-forming apparatus of the present invention shown in FIG. 5 , an ion current of about 14 mA/cm ² flowing in the substrate 1 was obtained, and the ion current flowing in the substrate 1 increased significantly. On the other hand, in the film-forming apparatus of the comparative example in FIG. 6 , the ion current flowing in the substrate 1 was only about half of that, about 7 mA/cm ² , and the ion current flowing in the substrate 1 did not increase. This result also shows that, in the film forming apparatus of the present invention, by increasing the ion irradiation to the substrate, a film with more excellent characteristics can be formed.

(Other Embodiments of Film Formation Device)

Next, another embodiment of the film forming apparatus of the present invention will be described using FIG. 8 . In the film forming apparatus shown in FIG. 8 , sputtering evaporation sources 2 and 3 and arc evaporation sources 5 and 6 are not circumferentially arranged in film forming chamber 8 as in FIG. 5 , but are alternately arranged in series. The arrangement of each evaporation source is not necessarily linear, but may also be curved, and the arrangement number of each evaporation source can also be freely selected. the

In the case of the film-forming device of the present invention shown in FIG. 8 , the substrate 1, the object to be processed, or the arc evaporation sources 5, 6 and the sputtering evaporation sources 2, 3 can be relatively moved through an appropriate mechanism, and then the substrate 1 alternately passes in front of the arc evaporation sources 5,6 and the sputter evaporation sources 2,3. In addition, in the protective atmosphere containing reaction gas in the film forming chamber 8, the components of the hard coating layer are evaporated using the arc evaporation sources 5 and 6, and the components of the hard coating layer are evaporated using the sputtering evaporation sources 2 and 3. 1. Hard coating layers and hard coating layers are laminated alternately and sequentially on the substrate 1 to form a target hard coating. the

In addition, even in the film forming apparatus of the present invention shown in FIG. 8 , the magnetic fields 10 of two adjacent evaporation sources, for example, the magnetic fields 10 of the arc evaporation source 5 and the sputtering evaporation sources 2 and 3 are also connected. That is, during film formation, the magnetic field applying means is configured so that the lines of magnetic force between adjacent evaporation sources are connected to each other. Therefore, the magnetic field 10 in the same film forming chamber 8 is in a closed state (closed magnetic field structure), and the electrons emitted from the above-mentioned evaporation source are trapped in the closed magnetic field structure, and are not easily guided to the same anode as the substrate 1. Inside the membrane chamber 8. As a result, similar to the film-forming apparatus of the present invention in FIG. 5 , the concentration of emitted electrons is high, and collisions with sputtering gas or reaction gas increase, enabling efficient ionization of gas. the

(nitrogen partial pressure)

In the film-forming apparatus of the present invention such as FIGS. At the same time, it is preferable to set the partial pressure of nitrogen mixed at 0.5 Pa or more. the

As described above, the shielding gas conditions and pressure conditions are largely different between arc film formation and sputtering film formation. Therefore, in K.H.Kim et al.Surf.Coat.Technol mentioned above, for example, when the arc evaporation source and the sputtering evaporation source are operated simultaneously to form a film, Ar and nitrogen, etc., which will become the sputtering gas, react The gas ratio is set to 3:1, the total pressure is set at about 0.08Pa and the partial pressure of nitrogen is set at about 0.02Pa, so that Ti is evaporated with an arc evaporation source and Si is evaporated with a sputtering evaporation source. Film TiSiN and other hard coatings. the

However, when the film is formed under such conditions, since the partial pressure of nitrogen mixed is too low, nitrogen added to the hard coating is insufficient, and macroscopic particles in the hard coating also increase. Therefore, it is difficult to form a dense film. the

In this regard, in order to sufficiently add nitrogen to the hard coating, suppress the generation of macroscopic particles in the hard coating, and form a dense coating with excellent surface shape, as described above, it is preferable to mix nitrogen in the sputtering gas. The partial pressure is set at 0.5 Pa or more. the

The influence of the nitrogen partial pressure was studied in the case of forming a TiAlCrN hard film by simultaneously operating the arc evaporation source and the sputtering evaporation source using the film forming apparatus shown in FIG. 3 above. While using an arc evaporation source to evaporate TiAl alloy (Ti50:Al50), while using a sputtering evaporation source to evaporate Cr, in this way, the ratio (nitrogen partial pressure) of Ar that becomes the sputtering gas and nitrogen that becomes the reaction gas is formed through various changes. . In addition, for each example, the nitrogen content (atomic %) in the hard coating, the surface roughness Ra and the Vickers hardness (Hv) of the hard coating were measured. the

10 to 12 show the results of sorting the above items in relation to the nitrogen partial pressure. Figure 10 shows the relationship between the nitrogen partial pressure and the nitrogen content in the hard coating, Figure 11 shows the relationship between the nitrogen partial pressure and the surface roughness Ra of the hard coating, and Figure 12 shows the relationship between the nitrogen partial pressure and the Vickers hardness of the hard coating relation. the

It can be seen from FIG. 10 that the nitrogen partial pressure is bounded by 0.5 Pa, and the nitrogen content in the hard coating has a clear difference. That is, in the region where the nitrogen partial pressure is lower than 0.5 Pa, the nitrogen content in the hard coating decreases substantially monotonously compared with the region where the nitrogen partial pressure is 0.5 Pa or higher. On the other hand, in the region where the partial pressure of nitrogen is 0.5 Pa or more, the nitrogen content in the hard coating is stable and kept at a high level of about 50 atomic %. the

In addition, it can be seen from FIG. 11 that the surface roughness Ra in the hard coating has a clear difference when the nitrogen partial pressure is set at 0.5 Pa. That is, in the region where the nitrogen partial pressure is lower than 0.5 Pa, the surface roughness Ra in the hard coating sharply increases to about 0.38 μm. On the other hand, in the region where the nitrogen partial pressure is 0.5 Pa or higher, the surface roughness Ra in the hard coating is substantially stable and kept at a low level of 0.1 μm or less. the

In addition, it can be seen from FIG. 12 that the Vickers hardness in the hard coating has a clear difference when the nitrogen partial pressure is set at 0.5 Pa. That is, in the region where the nitrogen partial pressure is lower than 0.5 Pa, the Vickers hardness in the hard coating is significantly reduced to a level of 1100 Hv. In the region where the nitrogen partial pressure is above 0.5Pa, the Vickers hardness in the hard coating is stable, maintaining a high level of about 2500Hv. the

The above results show that in order to sufficiently add nitrogen to the hard coating so that the coating can suppress the occurrence of macroscopic particles in the hard coating and make the film dense and have a good surface shape, the nitrogen content mixed in the sputtering gas needs to be adjusted. The pressure is set above 0.5Pa. In addition, the above-mentioned results and tendencies are also applicable to other hard coatings such as TiN, TiCN, or TiAlN other than TiAlCrN studied. the

(Abnormal discharge problem caused by insulator)

However, in the film formation in which the nitrogen partial pressure is set to be 0.5 Pa or more, when arc film formation and sputtering film formation are simultaneously performed in the same film formation chamber, the material used for the sputtering evaporation source may cause other questions. That is, the sputtering target reacts with the reactive gas to form an insulator (insulator) on the surface of the target, and there is a possibility that abnormal discharge (arcing) may occur in the sputtering evaporation source due to the insulator. For example, when Si is used as a target and sputtered in nitrogen, Si reacts with nitrogen to easily form a SiN insulator on the surface of the target, so this problem of abnormal discharge is particularly likely to occur. the

In addition, no matter in the case where such an insulator is not produced, or in the case where the sputtering target reacts with the reactive gas to generate a compound on the surface of the target, the presence of the compound layer on the surface reduces the evaporation of the sputtering evaporation source. rate possibility. In addition, these problems also become the main factors hindering the efficient ionization of gas. the

In the past, to deal with such problems, the partial pressure of reactive gases such as nitrogen was kept at a low pressure relative to the inert sputtering gas, and the reaction between the above-mentioned reactive gases such as nitrogen and the sputtering target was suppressed, so that the sputtering target was preferentially used. Sputtering target work with sputtering gas. the

In the above-mentioned K.H.Kim et al.Surf.Coat.Technol etc., in the case of forming a hard film such as TiSiN by making the arc evaporation source and the sputtering evaporation source work simultaneously, as mentioned above, the reduction relative to the sputtering This is also the reason for the partial pressure of reactive gases such as Ar and nitrogen in the emissive gas. the

However, as described above, when film formation is performed using the film formation apparatus shown in FIG. 5 or FIG. 6 , the composition and pressure range of the protective atmosphere are largely different between arc film formation and sputtering film formation. Therefore, when forming a film by simultaneously operating an arc evaporation source and a sputtering evaporation source that require a relatively high pressure, it is also necessary to increase the reaction of nitrogen or the like to the sputtering gas in view of the above-mentioned film characteristics. The partial pressure of the gas, which increases the likelihood of the above-mentioned problems occurring. the

(Introduction method of shielding gas)

The above-mentioned problems can be overcome by introducing sputtering gas into the film-forming chamber from the vicinity of the sputtering evaporation source and introducing reaction gas into the film-forming chamber from the vicinity of the arc evaporation source during film formation. Figure 9 shows this approach. The basic structure of the film-forming device of the present invention shown in FIG. 9 is the same as that of the above-mentioned FIG. 5, but it is characterized in that, in film-forming, the sputtering gas is introduced from the vicinity of the above-mentioned sputtering evaporation source, and the reaction gas is introduced from the vicinity of the above-mentioned arc evaporation source. . the

More specifically, the film forming apparatus of FIG. 9 introduces sputtering gas from the vicinity of the above-mentioned sputtering evaporation sources 3 and 4 through the conduit 12 and the branch pipes 12a and 12a during film formation. In addition, the reactive gas is introduced from the vicinity of the arc evaporation sources 5 and 6 through the conduit 11 and the branch pipes 11a and 11a. the

As a result, in the vicinity of the sputtering evaporation sources 3 and 4, the partial pressure of the reactive gas such as nitrogen relative to the inert sputtering gas is maintained at a low pressure state, and the reaction between the reactive gas such as nitrogen and the sputtering target is suppressed, making it The target can be sputtered preferentially using sputtering gas. the

In this regard, from the viewpoint of improving the above-mentioned film performance, the ratio (nitrogen partial pressure) of nitrogen used as the reaction gas to the sputtering gas in the total protective atmosphere in the film formation chamber can be increased. In addition, in the vicinity of the arc evaporation sources 5 and 6, the pressure of the reactive gas can also be increased according to the arc film forming conditions. the

When these shielding gases are introduced in combination with the above-mentioned magnetic field application mechanisms such as Fig. 5 and Fig. 9, or independently, it is not easy to mix reactive gases such as nitrogen in the inert sputtering gas, and the ionized mixed gas suppresses the sputtering on the target. The problem of abnormal discharge due to the formation of an insulating film on the surface of the material. Therefore, high-efficiency ionization of gas can be performed. the

(abnormal discharge formed by magnetic field)

In addition, the abnormal discharge on the sputtering target does not occur when the above-mentioned reactive gas such as nitrogen forms an insulator on the surface of the target, but may occur due to other reasons. the

This can also be said to be a unique problem when sputtering is controlled using the magnetic field of the above-mentioned magnetic field applying mechanism 4 or the like. This problem will be described with reference to Fig. 13(a) and (b). Fig. 14 (a), (b) shows the detailed structure of sputtering evaporation source 2,3, and Fig. 13 (a) is only the top view of target material 20 in sputtering evaporation source 2,3, and Fig. 13 (b) is the sputtering evaporation source 2,3. The front view of the evaporation sources 2 and 3. In Fig. 13(b), 4 is the magnetic field application mechanism, 13 is the shielding of the target 20, 15 is the gland ground wire of the shielding 13, 14 is the backing plate of the target 20, 16 is the sputtering power supply, and 17 is the carrier. Set the fixture for the target 20. the

As shown in Figure 13(b), the magnetron sputtering evaporation sources 2, 3 using a magnetic field form a horizontal magnetic field 10 on the surface of the target 20, as mentioned above, intentionally trap electrons, increase the electron density, and promote Ionization of the sputtering gas, thereby increasing sputtering efficiency. the

In this case, on the surface of the target material 20 shown in FIG. 13( a ), corroded regions 21 and non-corroded regions 22 are necessarily produced. The hatched part is the corrosion area 21, where more ions of the sputtering gas are generated, and the electron density is high, and sputtering is preferentially performed. On the other hand, in the non-corroded region 22 at the center part of the target 20 and the peripheral part of the corroded region 21, sputtering hardly occurs. As a result, the particles sputtered from the corroded region 21 react and combine with reactive gases such as nitrogen to easily deposit on the non-corroded region 22 . Therefore, this deposit becomes an insulator (insulating film) on the surface of the target, and abnormal discharge may occur. the

(sputtering evaporation source)

To solve this problem, it is preferable not to apply a voltage to the non-etching region 22 of the sputtering evaporation source during film formation. the

As a solution to this problem, an electrically insulating material may be used for the portion of the sputtering evaporation source that is a non-etching area other than the above-mentioned etching area 21 . Fig. 14(a), (b) shows an example of this method, and the basic configuration of the device is the same as Fig. 13(a), (b). In FIGS. 14( a ) and ( b ), an insulator 23 is formed using an electrically insulating material on the center portion of the target 20 and the non-etched region 23 at the periphery of the corroded region 21 . As such a material, heat-resistant BN (boron nitride), aluminum oxide, or the like that can withstand heat generated by a sputtering evaporation source is preferably used. the

FIG. 15 shows an example of a method of providing a shield at a floating potential or a ground potential with respect to the potential of the sputtering target in a portion other than the corroded region as another means of not applying a voltage to the non-corroded region. the

The basic configuration of the device in Fig. 15(a), (b) is also the same as that in Fig. 13(a), (b) above. In FIGS. 15( a ) and ( b ), on the non-etching region 25 at the center of the target 20 , a shield serving as a floating potential is provided. In addition, a shield serving as the ground potential (connected to the gland ground 15 ) is provided on the non-corroded area 24 in the peripheral portion of the corroded area 21 . the

In the modes of FIGS. 9 and 10 of the above-mentioned configuration in which no voltage is applied to the non-corrosion region 22, the particles sputtered from the corrosion region 21 will not react and combine with reactive gases such as nitrogen on the non-corrosion region 23 to form deposits. . Therefore, it is possible to prevent the occurrence of the above-mentioned abnormal discharge problem. the

Next, the methods of forming the hard laminate coatings according to the first to fourth inventions will be described. the

First, problems and solutions in common formation methods in the first to fourth inventions will be described. the

As a method of forming the hard laminate coatings of the first to fourth inventions, for example, as shown in FIG. and B's method. In this case, for example, on the substrate 1, the hard coating layer A component is vapor-deposited as the evaporated product 2a from the sputtering evaporation source 2, and the hard coating layer A component is evaporated as the evaporated product 3b from the sputtering evaporation source 3. Coating layer B component. the

In addition, as shown in FIG. 4 , there is a method of forming respective hard coating layers A and B on the substrate 1 using a plurality of electron beam evaporation sources 5 and 6 . In this case, for example, on the substrate 1, as the evaporated product 5a from the electron beam evaporation source 5 using the electron beam 7, the hard coating layer A component is vapor-deposited as the evaporation product from the electron beam evaporation source 5 using the electron beam 7. Evaporation product 6b of 6, hard film layer B component is vapor-deposited. the

However, in the present invention, as shown in the above-mentioned FIG. 5, the following method is most preferable, that is, the components of the hard coating layer A are evaporated using an arc evaporation source, and the components of the hard coating layer B are evaporated using a sputtering evaporation source. The film of the present invention is formed in a protective atmosphere containing a reactive gas. In this way, by arranging the arc evaporation source and the sputtering evaporation source in combination, the substrate is moved sequentially and even passes in front of these arc evaporation sources and the sputtering evaporation source, and the hard coating layer A is stacked on the substrate alternately and sequentially using the arc evaporation source. and the composition of the hard coating layer B are laminated using a sputtering evaporation source to form a coating. This forming method has the following advantages as the coating film forming method shown in FIGS. 3 and 4 described above. the

In particular, arc evaporation has a faster film formation rate than sputtering evaporation. Therefore, by forming a film of the components of the hard coating layer A using an arc evaporation source, it is possible to form a layer A having a thickness five times or more that of the layer B at high speed. In addition, compared with the arc evaporation source, the sputtering evaporation source is easy to adjust the film formation speed and operates with a very small input power (for example, 0.1kW), so it has the characteristics of being able to accurately control the thickness of the coating layer of thin films such as layer B. . the

In addition, by combining the characteristics of these arc evaporation and sputter evaporation, after setting the ratio of the thickness of layer A and layer B within a preferable range according to the ratio of input power of the arc evaporation source and the sputter evaporation source, by The repetition period of layer A+layer B can be arbitrarily determined by changing the number of revolutions of the substrate (rotational speed, moving speed). In addition, the thickness of the layer A (that is, the crystal particle diameter in the first to third inventions) can be set arbitrarily. the

Embodiments will be described below regarding the method of forming the hard laminate coating (film formation method) of the first invention. the

Taking the case where layer A is made of TiN and layer B is made of SiN as an example, the reason why the apparatus of FIG. 5 is preferably used will be described. In the case of the combination of the sputtering evaporation sources 2 and 3 shown in FIG. 3 above, as a method, when TiN and SiN are used as targets, Ti and Si can be considered as targets, and the sputtering gas Ar A method of alternately performing sputtering in a protective atmosphere of a mixed gas of nitrogen and reactive gas. The thickness of each layer A and layer B can be determined by controlling the working time of each sputtering evaporation source or using the shutter located in front to control the film forming time. However, in the sputtering method, since the film formation rate is slow, it takes time to form layer A whose film thickness is required to be about 5 times that of layer B, and it cannot be said to be efficient. the

In addition, in the case of using the electron beam evaporation shown in FIG. 4 above, Ti and Si are dissolved in the electron beam evaporation sources 5 and 6, respectively, to form the respective layers A and B. In the electron beam method, since the evaporation rate changes depending on the remaining amount of evaporation material in the electron beam evaporation sources 5, 6 (crucible), it is difficult to control the film thickness of each layer. the

In addition, in the protective atmosphere containing reactive gas in the film forming chamber 8, the components of the hard coating layer A are evaporated by the arc evaporation sources 5 and 6, and the components of the hard coating layer B are evaporated by the sputtering evaporation sources 2 and 3. components, and alternately and sequentially stacked on the substrate 1 to form the hard coating of the present invention. the

If layer A is set as TiN and layer B is set as SiN as an example, in the present invention, arc evaporation sources 5 and 6 are used to evaporate the component Ti of layer A, and sputtering evaporation sources 2 and 3 are used to evaporate layer Ti. The composition of B is Si. In addition, film formation is carried out in the sputtering gas Ar+reactive gas nitrogen. As described above, by rotating the substrate 1, the substrate alternately passes in front of the arc evaporation source and the sputtering evaporation source, and TiN and TiN are alternately and sequentially stacked on the substrate 1. SiN can easily form the hard coating of the laminated structure of TiN+SiN of the present invention. the

Next, an embodiment of the method for forming the hard laminate coating (film formation method) according to the second invention will be described below. the

The formation method of the hard lamination coating film of the recommended second invention is to adopt a film-forming device (refer to FIG. Film forming device".), in the mixed gas of Ar, Ne, Xe and other sputtering gases and nitrogen, methane, acetylene, oxygen and other reactive gases, by rotating the substrate, while alternately evaporating layer A with an arc evaporation source A method of alternately evaporating the constituent components of the layer B using a sputtering evaporation source, reacting to form a film, and laminating layers A and B alternately. The reason for changing the method of evaporation source between layer A and layer B in this way is as follows. the

In addition, as layer B, when forming a layer composed of (B, N), (Si, C, N) or (C, N), it is necessary to use B, BN, B ₄ C, Si, C targets, etc. Film formation, but because B and BN are insulating substances, they do not cause discharge in the arc evaporation source, so they cannot form a film. In addition, although B ₄ C, Si, and C are conductive substances, they are difficult to use due to unstable discharge. Arc evaporation source for film formation.

On the one hand, in the case where the sputtering evaporation source is used for both the film formation of layer A and layer B, the sputtering evaporation source is different from the arc evaporation source and also works with low input power, but the film forming speed is faster than the arc evaporation source. In addition to being slow, the hardness of the film formed is also worse than that of the arc evaporation source. the

Therefore, in the present embodiment, in the formation of layer A, an arc evaporation source is used, and as a target material, Cr or CrX is used (however, X is formed from Ti, Zr, Hf, V, Nb, Ta, Mo, One or more elements selected from the group consisting of W, Al and Si), in the formation of layer B, a sputtering evaporation source is used, and B, BN, B ₄ C, Si or C targets are used, Then, in a mixed gas of a sputtering gas and a reactive gas, the layers A and B are alternately stacked while rotating the substrate to form a film.

In addition, in the case of using B and BN targets, since they do not have conductivity, RF sputtering is used as the sputtering evaporation source, but in the case of using B ₄ C, Si, and C targets, since they have conductivity Therefore, as a sputtering evaporation source, both DC and RF methods can be used.

In addition, when layer A is formed, not only metal Cr or CrX (however, X is one or two selected from the group consisting of Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al and Si) The above elements), and using a target added with any one or more elements of B, C, O, N, can also form Cr (B, C, O, N) or (Cr, X) (B, C , O, N). the

The partial pressure of the reactive gas in the mixed gas composed of the sputtering gas and the reactive gas during film formation is preferably 0.6 Pa or higher, more preferably 1 Pa or higher. The total pressure of the mixed gas is not particularly limited, but the basic standard is set at 1 Pa or more in consideration of injecting the sputtering gas in an amount approximately equal to that of the reaction gas. However, since both sputtering evaporation sources and arc evaporation sources are prone to abnormal discharge under high pressure, the basic standard is set below 5Pa. the

Next, an embodiment of the method for forming the hard laminate coating (film formation method) according to the third invention will be described. the

In the third invention, also as shown in the above-mentioned FIG. 5, a film forming apparatus having one or more arc evaporation sources and sputtering evaporation sources respectively in the same vacuum container is adopted, and in a film forming protective atmosphere containing a reaction gas, by Make the arc evaporation source and the sputtering evaporation source work at the same time, use the arc evaporation source to evaporate the composition of layer A, and use the sputtering evaporation source to evaporate the composition of layer B, and at the same time, relative to the above-mentioned evaporation sources, move the substrate relatively, and alternately stack on the substrate Layer A and Layer B. And this method is the most preferred method. the

One of the reasons is that the above-mentioned sputtering method has a slow film formation rate. In addition, as in the above formulas 2 to 5, the layer B is mainly composed of B, Si, C, and Cu. Therefore, a target mainly composed of these elements (for example, pure Si, B ₄ C, C) has a problem that the discharge electrode is unstable during arc discharge. In addition, there are also problems such as cracking of these targets due to thermal load during arc discharge. In addition, the Cu target tends to emit a large number of molten droplets (macroscopic particles) during evaporation by an arc evaporation source. Therefore, from the viewpoint of the properties of these layer B targets, it is preferable to form the layer B using a sputtering evaporation source.

If layer A is set as TiAlN and layer B is set as BCN as an example, in the present invention, the components Ti and Al of layer A are evaporated with arc evaporation sources 5 and 6, and the components of layer A are evaporated with sputter evaporation sources 2 and 3 Components B, C of layer B are evaporated. In addition, film formation was performed in sputtering gas Ar+reactive gas nitrogen. Moreover, as mentioned above, by rotating the substrate 1, the substrate alternately passes through the front of the arc evaporation source and the sputtering evaporation source, and TiAlN and BCN are laminated alternately and sequentially on the substrate, so that the hard layer structure of the present invention can be easily formed. film. the

In the film-forming method of the third invention described above, when the above-mentioned arc evaporation source and the sputtering evaporation source are operated simultaneously to form a hard film containing nitrogen, the above-mentioned film-forming protective atmosphere is set to nitrogen, methane, A mixed gas of a reactive gas (reactive gas) such as acetylene and an inert gas for sputtering such as Ar (argon), Ne (neon), or Xe (xenon). the

In addition, it is preferable to set the partial pressure of the reactive gas to be mixed at 0.5 Pa or more. When the film is formed under a low pressure condition where the partial pressure of the mixed reactive gas is less than 0.5 Pa, the addition of nitrogen and the like to the hard coating is insufficient, and macroscopic particles in the hard coating also increase. Therefore, it is difficult to form a dense film. the

In this regard, in order to fully add nitrogen to the hard coating, suppress macroscopic particles in the hard coating, and form a dense coating with excellent surface properties, as described above, it is preferable to mix the reactive gas in the sputtering gas. The pressure is set above 0.5Pa. the

Next, an embodiment will be described below regarding the method for forming the hard laminate coating (film formation method) according to the fourth invention. the

In the fourth invention, also as shown in the above-mentioned FIG. 5, a film-forming device having one or more arc evaporation sources and sputtering evaporation sources each in the same vacuum vessel is adopted, and in a film-forming protective atmosphere containing a reactive gas, the Make the arc evaporation source and the sputtering evaporation source work at the same time, use the arc evaporation source to evaporate the composition of layer A, and use the sputtering evaporation source to evaporate the composition of layer B, and at the same time, relative to the above-mentioned evaporation sources, move the substrate relatively, and alternately stack on the substrate The method of layer A and layer B is the most preferred method. the

One of the reasons is that the above-mentioned sputtering method has a slow film formation rate. In the case of only using the above-mentioned multiple sputtering evaporation sources to stack layer A and layer B respectively on the substrate, the thickness of each layer A and layer B can be controlled by controlling the working time of the respective sputtering evaporation sources or using The shutter located on the front controls the film formation time to determine. However, in the sputtering method, since the film formation rate is slow, it takes time to form the layer A whose film thickness is required to be about twice that of the layer B, and it is not efficient. the

In addition, as shown in the composition of the above formula 3, layer B contains W, Mo, V, and Nb, and the target material mainly composed of these elements has a high melting point. During arc discharge, the discharge may be unstable due to an increase in voltage. . From this point of view, it is also preferable to form the layer B with a sputtering evaporation source, and it is preferable to form the layer B with an arc evaporation source. the

If layer A is set as TiAlN and layer B is set as WN as an example, in the present invention, the components Ti and Al of layer A are evaporated with arc evaporation sources 5 and 6, and the components of layer A are evaporated with sputtering evaporation sources 2 and 3 Composition W of layer B is evaporated. In addition, film formation was performed in sputtering gas Ar+reactive gas nitrogen. As described above, by rotating the substrate 1, the substrate alternately passes in front of the arc evaporation source and the sputtering evaporation source, and TiAlN and WN are alternately and sequentially laminated on the substrate 1, thereby easily forming the hard film of the laminated structure of the present invention. the

(reaction gas partial pressure)

In the film-forming method of the fourth invention described above, when the above-mentioned arc evaporation source and the sputtering evaporation source are operated simultaneously to form a hard coating film containing nitrogen, the above-mentioned film-forming protective atmosphere is set to nitrogen, methane, A mixed gas of a reactive gas (reactive gas) such as acetylene and an inert gas for sputtering such as Ar (argon), Ne (neon), or Xe (xenon). the

In addition, it is preferable to set the partial pressure of the reactive gas to be mixed at 0.5 Pa or more. When the film is formed under a low pressure condition where the partial pressure of the mixed reactive gas is less than 0.5 Pa, the addition of nitrogen and the like to the hard coating is insufficient, and macroscopic particles in the hard coating also increase. Therefore, it is difficult to form a dense film. the

In this regard, in order to sufficiently add nitrogen to the hard coating, suppress macroscopic particles in the hard coating, and form a dense coating with excellent surface properties, as described above, it is preferable to mix the components of the reactive gas mixed in the sputtering gas. The pressure is set above 0.5Pa. the

Hereinafter, the present invention will be described in more detail by enumerating the examples, but the present invention is not limited by the following examples at all, within the scope of meeting the purposes described before and after, it can certainly be implemented by adding appropriate changes, and this also All are included in the technical scope of the present invention. First, an embodiment of the first invention will be described. the

[Example 1-1]

The influence of the crystal structure of layer B is investigated below. That is, it was confirmed that when a material having a cubic crystal rock-salt structure is selected as the layer A, and a material having the same cubic rock-salt structure or a material having a different crystal structure is selected as the layer B, the crystal grains The presence or absence of the miniaturization effect. the

Specifically, the film having the laminated structure shown in Table 1 was formed using the sputtering film forming apparatus having the two sputtering evaporation sources 2 and 3 shown in FIG. 3 above. A cemented carbide (surface mirror-polished) for hardness measurement was used as the substrate 1 . After loading the substrate into the apparatus shown in FIG. 3, the temperature of the substrate is heated to a range of 400 to 500° C., while the vacuum is evacuated to below 3×10 ⁻³ Pa, and purification is carried out by using Ar ions (pressure 0.6 Pa, After the substrate voltage was 500V and the processing time was 5 minutes), film formation was sequentially performed.

In this film formation, in an Ar protective atmosphere when forming a metal film, in a protective atmosphere of a mixed gas of Ar and nitrogen (mixing ratio 65:35) when forming a nitride, in an Ar and nitrogen protective atmosphere when forming a carbonitride Film formation was performed in a protective atmosphere of a mixed gas of nitrogen and methane (mixing ratio 65:30:5) while keeping the total pressure constant at 0.6 Pa. the

The thickness of layer A and layer B is adjusted according to the time of operating each sputtering evaporation source 2, 3, but the thickness of layer A is fixed at 50nm, and the thickness of layer B is fixed at 10nm, and a total of 50 layers of layer A and layer The repetition of B (lamination unit) forms a film with a thickness of about 3000 nm. The test material after film formation was observed by TEM at 45,000 magnification along the cross-section of the film to confirm the presence or absence of the miniaturization effect of the crystal grains found in the above-mentioned FIG. 1 . In addition, when there is such an effect, it is evaluated as ◯, and when there is no effect, it is evaluated as ×. Table 1 shows the results. the

As shown in Table 1, in the case of comparative examples Nos. 1 to 4, as the layer A, a material having a cubic crystal rock salt structure was selected as the layer A, but as the layer B, the crystal structure was also selected to be a cubic crystal rock salt structure. s material. Therefore, it was confirmed that the crystal grains continued to grow without breaking up the crystal grain growth between the layer A and the layer B, and it was confirmed that there was no crystal grain miniaturization effect. the

Correspondingly, in the case of the inventive examples of Nos. 5 to 13, as the layer B, when a material having a crystal structure different from that of the layer A is selected, as found in the above-mentioned FIG. Growth continues between layers B, and as a result, crystal grains of layer A are miniaturized to the thickness range of layer A (50 nm). In addition, the AlN used in the layer B of Comparative Example 4 is a material with a stable hexagonal B4 structure. However, in the case of laminating with the material of the layer A of the rock-salt structure as in this example, in the formed film , the AlN layer has a rock-salt structure, and the effect of layer A's grain refinement was not found. the

From the above results, it has been confirmed that when forming a hard film with a laminated structure composed of layer A having a cubic rock-salt structure, as layer B, unless a crystal structure different from layer A having a cubic rock-salt structure is selected, material, there is no grain miniaturization effect. the

[Example 1-2]

Based on the results of this Example 1-1, the crystal structure of layer B was investigated in more detail. That is, it was confirmed that a hard coating material having a rock-salt cubic crystal structure such as TiAlN, CrN, and TiN was selected as the layer A, and a material having a crystal structure other than the rock-salt cubic crystal structure such as Cu, Co, SiN, and BN was selected as the layer B, or In the case of materials having a rock-salt cubic crystal structure such as CrN, MoN, WN, TaN, and AlN, or in the case where layer B is not provided, whether there is an effect of refining crystal grains and the strength of the film. the

Specifically, the sputtering film-forming device having the two sputtering evaporation sources 2 and 3 shown in FIG. 3 and the composite film-forming device of arc and sputtering shown in FIG. layered film. As the substrate, the same cemented carbide (mirror-polished) for hardness measurement as in Example 1-1 was used. After loading the substrate into the above-mentioned two devices, while heating the substrate temperature to the range of 400-500°C, the vacuum is evacuated to below 3× ^10-3 Pa, and purification is carried out by using Ar ions (pressure 0.6Pa, substrate voltage 500V, treatment time 5 minutes), each film was formed.

In the case of the sputtering film forming apparatus shown in FIG. 3 , in the film forming, in the protective atmosphere of a mixed gas of Ar and nitrogen (mixing ratio 65:35) when forming the nitride, when forming the carbonitride In the protective atmosphere of a mixed gas of Ar, nitrogen and methane (mixing ratio 65:30:5), the total pressure was set at 0.6 Pa, and the film was formed, and the layer A was adjusted with the time when the respective evaporation sources were operated. and the thickness of layer B. the

In the case of the composite film-forming apparatus shown in FIG. 5, when forming a nitride during film formation, in a protective atmosphere of a mixed gas of Ar and nitrogen (mixing ratio 50:50), when forming a carbonitride Film formation was carried out under the condition of a total pressure of 2.66 Pa in a protective atmosphere of a mixed gas of Ar, nitrogen and methane (mixing ratio 50:45:5). The thicknesses of layer A and layer B are determined according to the power ratio input to each evaporation source, and the ratio of the thickness of layer A+layer B is determined by the rotation period of the substrate. The film thickness was approximately fixed at 3 μm. In addition, layer A is formed using an arc evaporation source, and layer B is formed using a sputter evaporation source. the

The hardness evaluation of the mechanical properties of the formed film was measured with a micro Vickers hardness meter (load: 25 gf). In addition, the crystal structure of layer A and layer B was analyzed by TEM observation at 45,000 times the cross-section of the film, and the thickness and grain size of layer A and layer B were determined from the cross-sectional TEM photographs, and evaluated in the same manner as in Example 1-1. Presence or absence of crystal grain refinement effect of layer A. Table 2 shows these evaluation results. the

It can be seen from Table 2 that, as Invention Examples 20, 21, 24-27, and 29, only hard film materials with rock salt cubic crystal structures such as TiAlN, CrN, and TiN are selected as layer A, and layers with Cu, Co, Co, etc. are selected as layer B. In the case of materials with a crystal structure other than the rock salt cubic crystal structure such as SiN and BN, the effect of refining the crystal grains and the accompanying significant increase in the hardness of the coating were found. the

On the other hand, as in Comparative Examples 14 to 19, when layer B was not provided, and in Comparative Examples 22, 23, and 28, when a material having a rock-salt cubic crystal structure was selected as layer B, there was no effect of refining crystal grains, and the film The hardness is also relatively low. the

[Example 1-3]

Next, the effect of the thickness of the layer B made of a material having a crystal structure other than the rock-salt cubic crystal structure on the effect of refining the crystal grains of the layer A was examined. the

As a film forming apparatus, a test material was prepared under the same conditions using the same sputtering apparatus and composite film forming apparatus as in Example 1-2 above. As the layer A, (Ti0.5A10.5)N, CrN, and TiN, which are materials having a rock-salt cubic crystal structure and having high hardness, are selected, and as the layer B, SiN, BN, and Cu are selected. For the formation of layers such as SiN, BN, and Cu, Si, B ₄ C, and Cu targets are used, respectively.

In addition, by fixing the thickness of layer A at 30nm and changing the thickness of layer B in the range of 0.2 to 100nm, the effect of the thickness of layer B on the miniaturization effect of crystal grains was studied. About the test material after film formation, similarly to Example 1-2, the presence or absence of crystal grain refinement was confirmed by hardness measurement and cross-sectional TEM, Table 3 shows the result. the

Conditions other than the thickness of layer B in Table 3 were the same. In the comparison within each group of numbers 30 to 36, 37 to 43, and 44 to 50, no matter in each group, when the thickness of layer B is less than 0.2 nm of 0.5 nm, that is, numbers 30, 37, and 44 In the case of the examples, the crystal grains were not made finer. Therefore, the thickness of the layer B preferably has a thickness of about 0.5 nm or more not less than the minimum of 0.2 nm. the

In addition, in Table 3, in the case where the thickness of layer B exceeds 1/2 of the thickness of layer A relative to layer A, which is relatively large, that is, the serial number is 35, 36 or 42, 43 or 49, 50 In contrast, the properties of the layer B become the dominant properties of the overall properties of the film to be formed. As a result, compared with the examples in which the thickness of the layer B is relatively small relative to the layer A in each group, that is, compared with 31 to 34 or 38 to 41 or 45 to 48, it can be seen that no significant hardness increasing effect was found. Therefore, it is preferable that the thickness of layer B is 1/2 or less of the thickness of layer A. the

[Example 1-4]

Next, the effect of the thickness of the layer A on the grain refinement or hardness of the hard coating was examined. the

As a film-forming device, the composite film-forming device of FIG. 5 used in Example 1-2 was used, and (Ti0.5Al0.5)N was formed as layer A under the same conditions as in Example 1-2, and (Ti0.5Al0.5)N was formed as layer A B forms SiN. In this way, a test material in which the thickness of the layer B was fixed at 2 nm and the thickness of the layer A was varied within the range of 1 to 300 nm was produced. For the test material, similarly to Example 1-2, the refinement of crystal grains was confirmed by hardness measurement and cross-sectional TEM. Table 4 shows the results. the

As can be seen from Table 4, in the case of No. 51 in which the thickness of layer A is reduced to 1 nm with respect to the thickness of layer B of 2 nm, the characteristics of layer B become the dominant characteristics as a whole of the film, and despite the finer crystal grains , but compared with other serial numbers 52-55 and other examples, the hardness decreases instead. In addition, in the case of the No. 53 example in which the thickness of the layer A exceeds 200 nm, since there is no crystal grain refinement effect, the size of the crystal grains is close to that of the conventional product, so the hardness is almost the same as that of the conventional product. Therefore, the thickness of the layer A is preferably set within a range of 2 to 200 nm. the

[Example 1-5]

Next, according to the kind of material selected as the layer B, according to the oxidation initiation temperature of the hard coating, the effect of improving the oxidation resistance was studied. the

As a film-forming device, the composite film-forming device of FIG. 5 that was also used in the above-mentioned Examples 1-2 was used, and (Ti0.5Al0.5)N was formed as layer A, and (Ti0.5Al0.5)N was formed as layer B on a platinum foil (0.1 mm thick). SiN, BN, MoN and Ti are formed. The film thicknesses of layer A and layer B were fixed at 30 and 2 nm, and a total of about 90 layers were laminated in units of layer A+layer B to form a film. the

The oxidation resistance of the formed film was measured up to a temperature range of 1000° C. to investigate the oxidation resistance. In the investigation of oxidation resistance, using a thermal balance, in dry air, it was heated to 1000°C at a rate of temperature increase of 4°C/min, and the oxidation start temperature was determined from the weight increased by oxidation. Table 5 shows the evaluation results thereof. the

It can be seen from Table 5 that in the case of Invention Examples 58 and 59 in which SiN and BN were selected as the layer B, the oxidation started compared to Comparative Example 57 which was equivalent to the conventional material without layer B or Comparative Example 60 which had a rock-salt crystal structure. With a temperature of 850°C, the oxidation onset temperature increased to 900°C in these cases. Therefore, in the film structure of the present invention, when SiN and BN are selected as the layer B, SiN and BN not only increase the hardness but also improve the oxidation resistance. In addition, Invention Example 61 in which Ti is selected as the layer B has the crystal grain refinement effect of the layer A, but the oxidation initiation temperature is relatively low. the

[Example 1-6]

Next, as a difference in film formation conditions, the effects of connecting the magnetic force lines of the arc evaporation source and the sputtering evaporation source and not connecting the magnetic force lines of each evaporation source on the formation of the film were investigated. Regarding the film formation, in the same manner as in the above example, a total of about 90 layers were stacked in units of layer A + layer B, wherein, as layer A, (Ti0.5Al0.5)N was formed with 30 nm, and as layer B Form 3nm SiN, BN. the

In this film formation, the composite film formation apparatus shown in FIG. 5 was used, but for comparison, the mutual arrangement of the magnetic force lines connecting the arc evaporation source and the sputtering evaporation source in FIG. 5 and the respective evaporation sources not connected in FIG. The mutual arrangement of the magnetic field lines and the respective film formation were used to compare and study its characteristics. Table 6 shows the evaluation results thereof. In addition, the film formation conditions of the apparatus of FIG. 5 and FIG. 6 were set to be the same as the film formation conditions of the apparatus of FIG. 5 in Example 1-2. the

As can be seen from Table 6, the serial numbers 62 and 64 when connecting the magnetic lines of force (of Figure 5) are compared with the serial numbers 63 and 65 when not connecting the magnetic lines of force (of Figure 5) (between 62 and 63, 64 and 65), with regard to oxidation resistance, the characteristics are roughly the same, but the hardness is higher. These results show that, as shown in FIG. 5 , the film formed by connecting the lines of magnetic force can form a film with higher hardness by increasing the ion density. the

Table 1

Table 2

table 3

Table 4

table 5

Table 6

Next, an embodiment of the second invention will be described. the

[Example 2-1]

Adopt the sputtering film-forming device that has 2 sputtering evaporation sources shown in Figure 3 or have the composite film-forming device of 2 sputtering evaporation sources shown in Figure 5 and arc evaporation source respectively, form the Laminate structure coating. the

As the substrate, a cemented carbide (mirror-polished) for hardness measurement was used. In the case of using either a sputtering film-forming device or a composite film-forming device, the substrate is placed in the device, and the temperature of the substrate is kept in the range of 400 to 500°C while evacuating. After reaching a vacuum state of 3×10 ^-3 Pa or less and performing purge with Ar ions (pressure 0.6 Pa, substrate voltage 500 V, treatment time 5 minutes), film formation was performed.

In the case of using a sputtering film forming device, when forming a metal film during film formation, in a pure Ar protective atmosphere, in a mixed gas of Ar and nitrogen (volume mixing ratio 65:35) protective atmosphere when forming a nitride In the process of forming carbonitrides, film formation was carried out in a protective atmosphere of a mixed gas of Ar, nitrogen and methane (volume mixing ratio 65:30:5), and under the condition that the total pressure was set to 0.6Pa, and The thicknesses of layer A and layer B were adjusted by changing the operating time of each evaporation source. Metal Cr and B were used as the target. the

In the case of using a composite film-forming device, in the protective atmosphere of a mixed gas of Ar and nitrogen (volume mixing ratio 50:50), in the case of carbonitrides in a mixed gas of Ar, nitrogen and methane (volume mixing ratio 50) : 45: 5), and the film is formed under the condition that the total pressure is 2.66Pa, and the thickness ratio of layer A and layer B is adjusted according to the power ratio input into each evaporation source, while the thickness of layer A and layer B is It is adjusted by the rotation speed of the substrate. the

The total thickness of the film to be formed was approximately constant at 3 μm. In addition, layer A was formed using an arc evaporation source, and layer B was formed using a sputtering evaporation source. As the target material, metal Cr was used as the arc evaporation source, and conductive B ₄ C was used as the sputtering evaporation source.

First, a sputtering film-forming device and a composite film-forming device are used respectively, layer A is set to be composed of CrN, layer B is set to be composed of B0.45C0.1N0.45, and the thickness of layer A is fixed at 30nm, so that The thickness of the layer B was varied in a range of 0.2 nm to 50 nm, and film formation was performed (test numbers 2 to 7, 9 to 14). In addition, for comparison, as a conventional method, film formation of only layer A was also performed (test numbers 1 and 8). the

In addition, using only the composite film-forming apparatus, the layer A was changed according to the composition of Cr ₂ N, and the film was formed under the same conditions as above (Test Nos. 15 to 21).

Cross-sectional TEM observation was carried out on the test material after film formation, and as a result, the effect of miniaturization of crystal grains seen in FIG. 7 was confirmed. The crystal grain size was evaluated as x when it was equivalent to the conventional coating that did not form a laminated structure, and was evaluated as ○ when it was smaller than the conventional coating. the

In addition, the thicknesses of the respective layers A and B after film formation were measured at a magnification of 500,000 to 1,500,000 times and observed in 2 fields of view. the

The proportions of metal elements and elements such as N, C, and O in each film were calculated by Auger electron spectroscopy, while sputtering with Ar ions from the surface, and obtained from the obtained composition profile in the depth direction. the

In addition, the hardness of the obtained film was measured with a micro Vickers hardness meter (load 25 gf [≒0.245 N], holding time 15 seconds). the

In addition, the wear resistance of the coating and the aggressiveness to the target material were evaluated using a ball veneer type reciprocating sliding type wear friction tester. As the target material (ball), a bearing steel (SUJ2, HRC60) with a diameter of 9.53mm was used, and a sliding test was carried out in a dry environment at a sliding speed of 0.1m/s, a load of 2N, and a sliding distance of 250m, and the coefficient of friction during sliding was measured. , the respective friction speeds of the ball and the coating, and evaluated the properties of the coating. the

In addition, X-ray diffraction measurement of θ·2θ using Cukα rays was carried out, and the half amplitude values of the (111) and (200) planes were measured. the

Table 7 shows the results of the above tests. In addition, the number of laminations shown in Table 7 is a number calculated by taking the state in which layer A and layer B are laminated one by one as one lamination (the same applies to Tables 8 to 10). the

The following conclusions are clarified from the above test results. That is, when the thickness of the layer B is less than 0.5 nm, the effect of crystal grain refinement cannot be obtained, and the degree of increase in the hardness of the film is small (see test numbers 1, 2, 8, 9, 15, and 16). On the one hand, when the thickness of the layer B is too thick, although the crystal grains are refined, since the ratio of the thickness of the layer B with a low hardness to the thickness of the layer A with a high hardness is too large, the overall thickness of the coating appears. The hardness tends to decrease instead (refer to Test Nos. 7, 14, and 21). Therefore, the film thickness of layer B is preferably 0.5 times or less the film thickness of layer A (see test numbers 3 to 6, 10 to 13, and 17 to 20). the

The wear resistance coefficient of the film also tends to be roughly the same as the hardness, but the wear rate of the film hardly changes when the thickness of layer B is lower than that of layer A (refer to test numbers 1-6, 8-13, 15-20 ), and if it is greater than the thickness of layer A, it tends to rise sharply, which instigates a decrease in wear resistance (refer to test numbers 7, 14, and 21). the

In addition, in addition to satisfying the formulas (1) to (3), in the layer A formed of CrN having a rock-salt cubic crystal structure, at least one of the half-amplitude values of the diffraction lines from the above-mentioned (111) and (200) planes In the case of 0.3° or more, a film having high hardness and excellent abrasion resistance can be obtained (see test numbers 3 to 6, and 10 to 13). the

[Example 2-2]

In this embodiment, the same composite film-forming device used in the above-mentioned embodiment 2-1 is used, and the same as the above-mentioned embodiment 2-1, the layer A is set as CrN, and the layer B is set as B0.45C0. 1N0.45 composition, but the thickness of layer B was fixed at 2nm, and the thickness of layer A was varied in the range of 1 to 300nm to form a film. In addition, other test conditions are the same as in Example 2-1. the

Table 8 shows the results of the above tests. The following conclusions are clarified from the above test results. the

When the thickness of layer A is smaller than that of layer B, since the characteristics of layer B with relatively low hardness become the dominant characteristics, the degree of increase in film hardness is small (see test No. 31). On the other hand, when the film thickness of layer A exceeds 300 nm, the effect of fragmentation and miniaturization of crystal grains of layer B is reduced, and the hardness of the film tends to decrease on the contrary (see Test No. 36). Therefore, the thickness of layer A is preferably 200 nm or less, and the film thickness of layer B is preferably 0.5 times or less than the film thickness of layer A. the

[Example 2-3]

In this embodiment, the same sputtering film-forming device or composite film-forming device used in the above-mentioned embodiment 2-1 is used to fix the thickness of layer A at 30 nm and the thickness of layer B at 2 nm respectively, and pass The composition of layer A and layer B was changed variously to form a film. When layer A contains C or O, methane or oxygen is added to the reaction gas, and when layer B is contained, a Cr—B alloy target containing B is used as a target material. In addition, other test conditions are the same as in Example 2-1. the

Tables 9 and 10 show the results of the above tests. The above test results show that by setting layer A and layer B to have compositions satisfying the above formula (1) or (2), respectively, a coating having high hardness and excellent abrasion resistance can be obtained. the

In addition, when layer B is made of SiCN-based composition, compared with the case of BCN-based composition, the coefficient of friction of the coating is relatively slightly increased, and the wear rate of the ball is also slightly increased, but the coating can be obtained. A value equal to or slightly higher in hardness forms a coating suitable for cutting tools, etc., where aggressiveness with the target material is not considered. the

This shows that if the layer B is set to a composition other than the SiCN-based composition among the compositions specified in the present invention, the effect of reducing the aggressiveness to the target material can be obtained compared with the conventional coating. the

Next, an embodiment of the third invention will be described. the

[Example 3-1]

Formed a hard laminated film and a single-layer hard film under various conditions, studied the hardness of the film, and evaluated the effect of alternately laminating layers A and B of the present invention, as well as the respective thicknesses of layers A and B Effect. the

At this time, in the case of using the arc film forming method, film formation was performed using only the arc evaporation source in the film forming apparatus having the arc evaporation source and the sputtering evaporation source shown in FIG. 5 above. In the case of employing the sputtering film-forming method, film-forming is performed using a film-forming apparatus having only the two sputtering evaporation sources shown in FIG. 3 above. In addition, in the case of using the arc+sputtering film forming method, as shown in FIG. 5 above, each film having the composition shown in Table 11 was formed using a film forming apparatus having an arc evaporation source and a sputtering evaporation source. the

After loading the substrate in common with these film forming apparatuses, the substrate temperature is heated to a range of 400 to 500°C, while the vacuum is evacuated to 3×10 ^-3 Pa or less, and purification is performed with Ar ions ( After a pressure of 0.6 Pa, a substrate voltage of 500 V, and a treatment time of 5 minutes), film formation was performed.

In addition, together with these film forming apparatuses, the temperature at the time of film forming is set between 400° C. and 500° C. in common. The substrate is made of mirror-polished superhard alloy. When forming the film of layer A, targets containing metal components in the composition of layer A in Table 11 were used, and when forming layer B, various targets such as B ₄ C, C, Si, and Cu were used.

At this time, in each example, the film thickness (film thickness) of the laminated film was approximately constant at 3 μm (3000 nm). In addition, the thickness of the layer A is varied in a range of 2 to 250 nm, and the thickness of the layer B is varied in a range of 0.2 to 30 nm. the

In the case of using the above-mentioned sputtering film-forming device in Fig. 3, when forming a film, in a pure Ar protective atmosphere when forming a metal film, when forming a nitride, use a mixed gas of Ar and nitrogen (mixing ratio 65:35 ), and a mixed gas of Ar, nitrogen and methane (mixing ratio 65:30:5) and a total pressure of 0.6 Pa were used for film formation when carbonitrides were formed. At this time, the thicknesses of layer A and layer B are adjusted by the time of operating the respective evaporation sources. the

In the case of using the above-mentioned composite film-forming device of FIG. ), and maintain the condition of the total pressure of 2.66Pa to form a film. In addition, layer A was formed using an arc evaporation source, and layer B was formed using a sputtering evaporation source. In addition, the thickness ratio of layer A and layer B is determined according to the power ratio input to each evaporation source, and the thickness of layer A+layer B is determined by the rotation cycle of the substrate. the

For each of these formed coatings, the Vickers hardness of the coating was evaluated with a micro Vickers hardness meter (measurement load: 25 gf: Hv0.25). the

In addition, the lamination cycle and the thicknesses of layer A and layer B were confirmed by cross-sectional TEM photographs. In addition, the depth direction of each film was analyzed by Auger electron spectroscopy. Table 11 shows the results thereof. the

As shown in Table 11, comparative examples No. 1 to No. 5 have a single-layer structure with no layer B and only layer A. Corresponding to this, in Comparative Example 1 and Inventive Examples 7-8, Comparative Example 3 and Inventive Examples 12-14, Comparative Example 4 and Inventive Examples 17-19, Comparative Example 5 and Inventive Examples 22-24, etc., layer A has the same In the mutual comparison of the compositions, these invention examples ensured high hardness compared with the comparative examples. Therefore, first of all, the effect of alternately stacking the layers A and B of the present invention is ensured. the

Then, the Nos. 6 to 15 examples showed the effect of the film thickness of the layer B. In the comparison within each group of Nos. 6 to 10 and 11 to 15 in which Layer A and Layer B of the same composition within the scope of the present invention were respectively provided, in Comparative Examples 6 and 11, the thickness of Layer B was less than the lower limit of 0.5 nm . In addition, in Comparative Examples 10 and 15, the thickness of the layer A was less than twice the thickness of the layer B. As a result, compared with Invention Examples 7 to 9 or Invention Examples 12 to 14 of the same group in which the thickness of layer A and layer B or the relationship between the thicknesses of layer A and layer B satisfies the provisions of the present invention, the hardness of these comparative examples was compared. Low. the

Examples of Nos. 16 to 25 show the effect of the film thickness of the layer A. In the comparison within each group of Nos. 16 to 20 and 21 to 25 in which Layer A and Layer B of the same composition within the scope of the present invention were respectively provided, the thickness of Layer A in Comparative Examples 16 and 21 was lower than that of Layer B. 2 times the thickness. In addition, in Comparative Examples 20 and 25, the thickness of layer A exceeded the upper limit of 200 nm. As a result, compared with Inventive Examples 17 to 19 or Inventive Examples 22 to 24 of the same group in which the thickness of layer A or the relationship between the thicknesses of layer A and layer B satisfies the provisions of the present invention, the hardness in these comparative examples is relatively low. . the

Therefore, it can be proved that the regulation of the thickness of layer A or the relationship between the thicknesses of layer A and layer B in the present invention is more preferable. the

[Example 3-2]

Then, layers A with various compositions were formed, and the film hardness was examined to evaluate the influence (effect) of the composition of the layer A of the present invention on the film hardness. the

Films with various compositions shown in Table 12 were formed under the same film-forming conditions as in Example 3-1 above. With respect to the formed film, the Vickers hardness of the film was evaluated with a micro Vickers hardness meter (measurement load: 25 gf). The lamination cycle and the thicknesses of layer A and layer B were confirmed by cross-sectional TEM photographs. In addition, the depth direction of each film was analyzed by Auger electron spectroscopy. Table 12 shows the results thereof. the

As shown in Table 12, comparative examples numbered 1 to 6 have a single-layer structure with no layer B and only layer A. Correspondingly, in Comparative Example 1 and Inventive Example 12, Comparative Example 2 and Inventive Example 17, Comparative Example 3 and Inventive Example 13, Comparative Example 4 and Inventive Example 29, etc., in the comparison between layers A having the same composition, These respective inventive examples secured higher hardness than the respective comparative examples. In addition, although it is a comparison between the same comparative examples, in the comparison between the comparative examples 6 and 7 in which the layer A is TiN, the hardness Lower than Comparative Example 7 in which layers A and B are alternately laminated. Therefore, from the results in Table 12, the effect of alternately laminating the layers A and B of the present invention was also confirmed. the

In the present invention, as described above, layer A is represented by Formula 1: (Ti1-x-yAlxMy)(BaCbN1-a-b-cOc) [However, 0.4≤x≤0.8, 0≤y≤0.6, 0≤a≤0.15, 0≦b≦0.3, 0≦c≦0.1, and M is a metal element selected from one or more of 4A, 5A, 6A, and Si]. the

Here, the example of the same component in Table 12 was compared. First, in the (TiAl)N system, Comparative Examples 8 and 11 in which the Al content exceeds the specified range of 0.4≤x≤0.8, the content is too low or too high, and Inventive Examples 9 and 10 in which the Al content is within the range , 12 compared to lower hardness. the

In the (TiAlCr)N system, the Al content exceeds the specified range of 0.4≤x≤0.8 and the content is too low in Comparative Example 16, and the Cr content exceeds the above specified range of 0≤y≤0.6 and is too high, but the Al content x The hardness was lower than that of Invention Examples 13 to 15, which were within the above-mentioned predetermined range of 0.4 to 0.8, that is, 0.45 to 0.65, and more preferably within the predetermined range of 0.55 to 0.75. the

These results therefore also demonstrate the significance of the specification or more preferred specification of the Al content x of layer A according to the invention. the

In the (TiAl)(BN) system, Comparative Example 25 in which the B content exceeds the above-mentioned prescribed range of 0 ≤ a ≤ 0.15 and the content is excessively high is the same as that in which the B content a is within the aforementioned prescribed range of 0.15 or less and more preferably 0.1 or less. Compared with Invention Examples 23 to 24 within the predetermined range, the hardness was lower. the

Therefore, these results demonstrate the significance of the regulation or more preferable regulation regarding the B content a of the layer A of the present invention. the

In the (TiAlCr)(CN) system, the C content in Comparative Example 28 that exceeds the above-mentioned specified range of 0 ≤ b ≤ 0.3 and the content is too high is the same as that in which the C content is within the above-mentioned specified range of 0.3 or less and more preferably 0.1 or less. Compared with Invention Examples 26 and 27 in the range, the hardness was lower. the

Therefore, these results prove the significance of the regulation or more preferable regulation of the C content b of the layer A of the present invention. the

In the (TiAlV)(ON) system, Comparative Example 30 in which the O content was too high outside the prescribed range of 0≤c≤0.1 had a lower hardness than Inventive Example 29 in which the O content was in the prescribed range of 0.1 or less. the

Therefore, these results can prove the meaning of regulation or more preferable regulation of the O content of layer A of this invention. the

In addition, Invention Examples 13 to 15 and 17 to 22 in Table 12 contain Cr, Si, Zr, Nb, Ta, and V as the additive element M. Among these elements M, especially those containing Cr, Si, V, etc. have higher hardness. Thus, the hardness-improving effect of these elements M was demonstrated. the

[Example 3-3]

Next, layers B of various compositions were formed to examine the hardness of the coating, and the influence (effect) of the composition of the layer A of the present invention on the hardness of the coating was evaluated. the

Films with various compositions shown in Table 13 were formed under the same film-forming conditions as in Example 3-1 above. Regarding the formed coating, the Vickers hardness of the coating was evaluated in the same manner as in Examples 3-1 and 3-2. In addition, the lamination cycle and the thicknesses of layer A and layer B were confirmed by cross-sectional TEM photographs. In addition, the depth direction of each film was analyzed by Auger electron spectroscopy. Tables 13 and 14 (continued from Table 13) show the results. the

In addition, in this example, the sliding properties of each coating were evaluated using a ball veneer type reciprocating sliding wear friction tester. The evaluation conditions were as follows: bearing steel (SUJ2, HRC60) with a diameter of 9.53 mm as the target material (ball), room temperature, sliding speed 0.1 m/s, load 2 N, sliding distance 250 m, and conducted a sliding test in a dry environment to evaluate the test The coefficient of friction (μ) in . the

In addition, in this example, the oxidation resistance of each film was evaluated based on the oxidation initiation temperature. That is, a film sample of about 3 μm formed on a platinum foil was heated at a rate of 4 °C/min from room temperature to 1100 °C in dry air using a thermal balance, and the oxidation initiation temperature was determined from the oxidation weight increase curve. Tables 13 and 14 also show the results. the

As shown in Tables 13 and 14, the comparative examples numbered 1 to 6 have a single-layer structure with no layer B and only layer A. Correspondingly, in the comparison between Comparative Example 1 and Invention Examples 7-10 or Comparative Example 11, the comparison between Comparative Example 3 and Invention Examples 12, 13, 16-19, the comparison between Comparative Example 4 and Invention Examples 25-28, etc., Each of these inventive examples secured high hardness compared with each comparative example. Therefore, from the results of these Tables 3 and 4, the effect of alternately laminating the layers A and B of the present invention was also demonstrated. the

Layer B in the present invention is selected from the compounds represented by the following four composition formulas as described above. the

Formula 2: B1-x-yCxNy[However, x and y respectively represent the atomic ratio, 0≤x≤0.25, B/N≤1.5],

Formula 3: Si1-x-yCxNy[However, x and y respectively represent the atomic ratio, 0≤x≤0.25, 0.5≤Si/N≤2.0],

Formula 4: C1-xNx [however, x represents the atomic ratio, 0≤x≤0.6],

Formula 5: Cu1-y(CxN1-x)y [However, x and y respectively represent atomic ratios, 0≤x≤0.1, 0≤y≤0.5], constituted by a composition selected from any one of the above compositions. the

Here, in Tables 13 and 14, examples of the same component system of the layer B were compared. First, in the above-mentioned B1-x-yCxNy system, Comparative Example 11 in which the C content x was too high outside the prescribed range of 0≤x≤0.25 had a lower hardness than Inventive Examples 7 to 10 in which the C content was within the prescribed range. Low. In addition, Comparative Examples 14 and 15, in which B/N was too high beyond the specified range of 1.5 or less, had lower hardness and higher coefficient of friction than Inventive Examples 12 and 13, which were within the specified range. From this, it can be seen that when B/N is 1.5 or less, the hardness of the film and the coefficient of friction can both be improved. the

In the above-mentioned Si1-x-yCxNy system, the C content x exceeds the above-mentioned specified range of 0 ≤ x ≤ 0.25 and the comparative example 20 is too high. and low oxidation resistance. From this, it can be seen that when the C content x is 0.25 or less, both the hardness and the oxidation resistance of the film become good. In addition, Comparative Example 24, which exceeded the Si/N limit of 0.5 to 2.0 and was too low, had lower hardness than Inventive Examples 21 to 23, which were within the specified range. the

In the above-mentioned Cu1-y(CxN1-x)y system, the coefficient y of the ratio of CN to Cu exceeds the above-mentioned predetermined range of 0≤y≤0.5 and is too high in Comparative Example 29, and the N content x is within the predetermined range Compared with Invention Examples 25 to 28, the hardness was lower. This result shows that the hardness increases when the coefficient y of the ratio of CN to Cu is in the range of 0 to 0.5, and that the hardness increases when the C content x is in the range of 0≤x≤0.1. the

In the above-mentioned C1-xNx system, Comparative Example 34, in which the N content x was too high outside the specified range of 0≤x≤0.6, had lower hardness and friction The coefficient increases. From this, it can be seen that when the N content x is within the specified range, the hardness increases and the friction coefficient decreases. the

In addition, in all the examples in Table 3 and Table 4, the coefficient of friction was lowered by laminating BCN-based and C-based layers as the layer B, and the oxidation resistance was slightly increased in the BCN-based layer. The friction coefficient of the SiCN system hardly changed, but the oxidation resistance increased significantly. The CuCN system increases the hardness and slightly increases the oxidation resistance. the

Therefore, from the above-mentioned results, the significance of each composition definition of the layer B of this invention can be demonstrated. the

Table 7

Table 8

Table 9

Table 10

Table 11

Table 12

Table 14

Next, an embodiment of the fourth invention will be described. the

[Example 4-1]

Formed a hard laminated film and a single-layer hard film under various conditions, studied the hardness of the film, and evaluated the effect of alternately laminating layers A and B of the present invention, as well as the respective thicknesses of layers A and B Effect. the

At this time, in the case of using the arc film forming method, only the arc evaporation source in the film forming apparatus having the arc evaporation source and the sputtering evaporation source shown in FIG. 5 above is used for film formation. In the case of employing the sputtering film-forming method, a film is formed using a film-forming apparatus having only the two sputtering evaporation sources shown in FIG. 4 above. In addition, in the case of using the arc+sputtering film forming method, as shown in FIG. 5 above, each film having the composition shown in Table 15 was formed using a film forming apparatus having an arc evaporation source and a sputtering evaporation source. the

After loading the substrate in common with these film forming apparatuses, the substrate temperature is heated to a range of 400 to 500°C, while the vacuum is evacuated to 3×10 ^-3 Pa or less, and purification is performed with Ar ions ( After a pressure of 0.6 Pa, a substrate voltage of 500 V, and a treatment time of 5 minutes), film formation was performed.

In addition, together with these film forming apparatuses, the temperature at the time of film forming is set between 400° C. and 500° C. in common. The substrate is made of mirror-polished superhard alloy. When forming the film of layer A, targets containing metal components in the composition of layer A in Table 15 were used, and when forming layer B, various targets such as B ₄ C, C, Si, and Cu were used.

At this time, in each example, the film thickness (film thickness) of the laminated film was approximately constant at 3 μm (3000 nm). In addition, the thickness of the layer A is varied in a range of 2 to 250 nm, and the thickness of the layer B is varied in a range of 0.2 to 30 nm. the

In the case of using the above-mentioned sputtering film-forming device of FIG. 4, when forming a film, in a pure Ar protective atmosphere when forming a metal film, when forming a nitride, use a mixed gas of Ar and nitrogen (mixing ratio 65:35 ), and when forming carbonitrides, a mixed gas of Ar, nitrogen and methane (mixing ratio 65:30:5) is used to form a film at a total pressure of 0.6Pa. At this time, by adjusting the working time of each evaporation source Instead, the thickness of layer A and layer B is controlled. the

Under the situation of adopting the composite film-forming device of above-mentioned Fig. 5, with the mixed gas of Ar and nitrogen (mixing ratio 50: 50), carbonitride is formed with the mixed gas of Ar, nitrogen and methane (mixing ratio 50: 45: 5), and form a film with a total pressure of 2.66Pa. In addition, layer A was formed using an arc evaporation source, and layer B was formed using a sputtering evaporation source. In addition, the thickness ratio of layer A and layer B is adjusted according to the power ratio input to each evaporation source, and the thickness of layer A+layer B is determined by the rotation cycle of the substrate. the

For each of these formed coatings, the Vickers hardness of the coating was evaluated with a micro Vickers hardness meter (measurement load: 25 gf: Hv0.25). the

In addition, the lamination cycle and the thicknesses of layer A and layer B were confirmed by cross-sectional TEM photographs. In addition, the depth direction of each film was analyzed by Auger electron spectroscopy. Table 15 shows the results thereof. the

As shown in Table 15, comparative examples numbered 1 to 6 have a single-layer structure with no layer B and only layer A. Correspondingly, in the comparison between Comparative Example 1 and Inventive Examples 8-10, Comparative Example 3 and Inventive Examples 13-15, Comparative Example 4 and Inventive Examples 18-20, etc., in which the layer A has the same composition, these Each inventive example secured high hardness compared with the comparative example. Therefore, the effect of alternately stacking the layers A and B of the present invention was demonstrated first. the

Then, the Nos. 7 to 16 examples showed the effect of the film thickness of the layer B. In the comparison within each group of Nos. 7 to 11 and 12 to 16 in which Layer A and Layer B of the same composition were respectively provided, in Comparative Examples 7 and 12, the thickness of Layer B was less than the lower limit of 0.5 nm. In addition, in Comparative Examples 11 and 16, the thickness of the layer A was less than twice the thickness of the layer B. As a result, these comparative examples, compared with Invention Examples 8 to 10 or Invention Examples 13 to 15 of the same group in which the thickness of layer A and layer B or the relationship between the thicknesses of layer A and layer B satisfies the provisions of the present invention, the hardness is relatively high. Low. the

Then, the Nos. 7 to 16 examples show the effect of the film thickness of the layer B. In comparison within each group of Nos. 7 to 11 and 12 to 16 in which layers A and B of the same composition were provided, the thickness of layer B in Comparative Examples 7 and 12 was less than the lower limit of 0.5 nm. In addition, in Comparative Examples 11 and 16, the thickness of the layer A was less than twice the thickness of the layer B. As a result, these comparative examples, compared with Invention Examples 8 to 10 or Invention Examples 13 to 15 of the same group in which the thickness of layer A and layer B or the relationship between the thicknesses of layer A and layer B satisfies the provisions of the present invention, the hardness is relatively high. Low. the

In the following, examples Nos. 17 to 26 show the effect of the film thickness of the layer A. In the comparison within each group of Nos. 17 to 21 and 22 to 26 in which layers A and B of the same composition were respectively provided, the thickness of layer A in Comparative Examples 17 and 22 was less than twice the thickness of layer B. In addition, in Comparative Examples 21 and 26, the thickness of the layer A exceeded the upper limit of 200 nm. As a result, these comparative examples had relatively lower hardness than Inventive Examples 18 to 20 or Inventive Examples 23 to 25 of the same group in which the thickness of layer A or the relationship between the thicknesses of layer A and layer B satisfies the provisions of the present invention. the

In addition, Invention Examples 23 to 25 of the Cr-based component composition of the layer A have lower hardness than Inventive Examples 8-10, 13-15, 18-20, etc. of the Ti-based component composition. However, as described above, when used for sliding parts, it has a characteristic of being less aggressive to the target material than the Ti-based component composition. the

Therefore, from the above results, the definition of the composition or thickness of layer A, layer B, and the relationship between the thicknesses of layer A and layer B in the present invention, and more preferably the meaning of the definition can be proved. the

[Example 4-2]

Then, layers A with various compositions were formed, and the film hardness was examined to evaluate the influence (effect) of the composition of the layer A of the present invention on the film hardness. the

Films with various compositions shown in Table 16 were formed under the same film-forming conditions as in Example 4-1 above. With respect to the formed film, the Vickers hardness of the same film as in Example 4-1 was evaluated with a micro Vickers hardness meter (measurement load: 25 gf). The lamination cycle and the thicknesses of layer A and layer B were confirmed by cross-sectional TEM photographs. In addition, the depth direction of each film was analyzed by Auger electron spectroscopy. Table 16 and Table 17 (continued from Table 16) show the results. the

As shown in Tables 16 and 17, the comparative examples No. 1 to No. 7 have a single-layer structure with no layer B and only layer A. Correspondingly, in Comparative Example 1 and Inventive Example 11, Comparative Example 2 and Inventive Example 18, Comparative Example 3 and Inventive Example 14, Comparative Example 4 and Inventive Example 23, etc., the layer A has the same or substantially similar composition. In the comparison of each of these invention examples, compared with each comparative example, high hardness was ensured. In addition, although both are comparisons between comparative examples, in the comparison between comparative examples 6 and 7 in which layer A is TiN, comparative example 7, which does not provide layer B and only has a single layer of layer A , the hardness is lower than that of Comparative Example 8 in which layers A and B are alternately laminated. Therefore, from the results in Table 16, the effect of alternately stacking the layers A and B of the present invention was also demonstrated. the

In the present invention, as described above, layer A is represented by Formula 1: (Ti1-x-yAlxMy)(BaCbN1-a-b-cOc) [However, 0.4≤x≤0.8, 0≤y≤0.6, 0≤a≤0.15, 0≦b≦0.3, 0≦c≦0.1, and M is a metal element selected from one or more of 4A, 5A, 6A, and Si]. the

Here, the example of the same component in Table 16 was compared. First, in the (TiAl)N system, Comparative Examples 9 and 13 in which the Al content exceeds the specified range of 0.4≤x≤0.8, or is too low or too high, are compared with Inventive Examples 10 to 12 in which the Al content is within the specified range. , low hardness. the

In the (TiAlCr)N system, Comparative Example 17 in which the Al content exceeds the specified range of 0.4 ≤ x ≤ 0.8 is too low, and the Cr content exceeds the above specified range of 0 ≤ y ≤ 0.6 and is too high, and the Al content x is 0.45 The hardness is lower than that of Invention Examples 14 to 16, which is within the above-mentioned predetermined range of 0.4 to 0.8, that is, 0.65, and more preferably within the predetermined range of 0.55 to 0.75. the

These results therefore also demonstrate the significance of the specification or more preferably specification of the Al content x of layer A according to the invention. the

In the (TiAl)(BN) system, the B content exceeds the above-mentioned specified range of 0≤a≤0.15, and the content of Comparative Example 26 is too high, and the B content a is within the above-mentioned specified range of 0.15 or less, and more preferably 0.1 The hardness was lower than Invention Examples 24 and 25 in the following predetermined range. the

Therefore, from these results, the definition or more preferable regulation of the B content a of the layer A of the present invention also proves. the

In the (TiAlCr)(CN) system, the C content exceeds the specified range of 0≤b≤0.3, and the content of Comparative Example 29 is too high, and the C content is within the specified range of 0.3 or less, and more preferably 0.1 or less. The hardness was lower than that of Invention Examples 27 and 28, which were within the specified range. the

Therefore, from these results, the significance of the regulation or more preferable regulation of the C content b of the layer A of the present invention can be demonstrated. the

In the (TiAlV)(ON) system, Comparative Example 31, in which the O content was too high outside the above-mentioned specified range of 0≤c≤0.1, had a lower hardness than Inventive Example 30, in which the O content was within the above-mentioned specified range of 0.1 or less. . the

Therefore, from these results, the significance of regulation or more preferable regulation of the O content of layer A of this invention can be demonstrated. the

In addition, Invention Examples 14 to 16 and 18 to 23 in Table 16 contain Cr, Si, Zr, Nb, Ta, and V as the additive element M. Among these elements M, those containing Cr, Si, V, and the like in particular have improved hardness. Thus, the hardness-improving effect of these elements M was demonstrated. In addition, Invention Examples 32 to 37 of the Cr-based component composition of the layer A have lower hardness than the above-mentioned Inventive Examples of the Ti-based component composition. However, as described above, when used for sliding parts, it has a characteristic of being less aggressive to the target material than the Ti-based component composition. the

[Example 4-3]

Then, layer B with various compositions was formed, the film hardness was examined, and the influence (effect) of the composition of layer B of the present invention on the film hardness was evaluated. the

Films with various compositions shown in Table 17 were formed under the same film-forming conditions as in Example 4-1 above. Regarding the formed coating, the Vickers hardness of the coating was evaluated in the same manner as in Examples 4-1 and 4-2. In addition, the lamination cycle and the thicknesses of layer A and layer B were confirmed by cross-sectional TEM photographs. In addition, the depth direction of each film was analyzed by Auger electron spectroscopy. Table 18 shows the results thereof. the

In addition, in this example, the sliding properties of each film were evaluated using a ball veneer type reciprocating sliding type wear friction tester. The evaluation conditions were as follows: bearing steel (SUJ2, HRC60) with a diameter of 9.53 mm as the target material (ball), room temperature, sliding speed 0.1 m/s, load 2 N, sliding distance 250 m, and conducted a sliding test in a dry environment to evaluate the test The coefficient of friction (μ) in . the

In addition, in this example, the oxidation resistance of each film was evaluated from the oxidation start temperature. That is, a sample with a film of about 3 μm formed on a platinum foil was heated in dry air from room temperature to 1100°C at a rate of 4°C/min using a thermal balance, and the oxidation initiation temperature was determined from the oxidation weight increase curve. Table 18 also shows the results. the

As shown in Table 18, comparative examples No. 1 to No. 7 have a single-layer structure with no layer B and only layer A. Corresponding to this, in the comparison of Comparative Example 1 and Invention Examples 8-10 or Comparative Example 11, in the comparison of Comparative Example 3 and Invention Examples 12, 13, 15-17, 19-21, these each Invention Examples, and each Comparative Example Compared to ensure high hardness. Therefore, from the results in Table 18, the effect of alternately stacking the layers A and B of the present invention was also confirmed. the

In the present invention, layer B is composed of the composition represented by the following 3, as described above. the

Formula 3: M(BaCbN1-a-b-cOc) [However, M is a metal element selected from any one or more of W, Mo, V, and Nb, a, b, c, and e represent atomic ratios, 0≤a ≤0.15, 0≤b≤0.3, 0≤c≤0.1]

Here, in Table 18, the examples of the same component system of the layer B are compared. First, in the above-mentioned W(CN) system, Comparative Example 11, in which the C content b was too high outside the prescribed range of 0≤b≤0.3, had lower hardness and Poor oxidation resistance. the

In the V(NO) system, Comparative Example 14, in which the O content c was too high outside the specified range of 0 ≤ c ≤ 0.1, had lower hardness and oxygen resistance than Inventive Examples 12 and 13 in which the O content c was within the specified range. Poor chemical properties. the

In the Nb(BN) system, Comparative Example 18 in which the B content was too high outside the prescribed range of 0≦a≦0.15 had lower hardness than Inventive Examples 15 to 17 in which the O content c was in the prescribed range. the

Invention Examples 16 and 17 (including Comparative Example 18) of the Nb(BN) system containing Nb as the composition of the layer B, Invention Example 20 of the (MoNb)(CN) system containing Mo, (MoNb)(CN) system Invention Example 22 of Invention Example 22 of W-containing (WAl)N-based Invention Example 21, although the hardness of the film is also high, the oxidation resistance is particularly improved. In addition, the hardness of the film in (WV)N-based Invention Example 19 was high. the

Invention Examples 12, 13, and 26 (including Comparative Example 14) in which V was contained as the composition of layer B had a particularly low coefficient of friction. the

In addition, in Invention Examples 21, 22, 23, and 25, in the composition formula 3 of the above-mentioned layer B, the metal element M is selected from 4A, 5A, and 6A other than the above-mentioned W, Mo, V, and Nb. 1. Si is substituted by one or more selected metal elements M1 while satisfying the substitution within the range of atomic ratio of 0.3 or less. Inventive Example 21 replaced W with Al. Invention Example 22 replaced Mo with Si. Inventive Example 23 replaces V with Ti. This result shows that the hardness of the film is improved. the

In addition, Inventive Examples 24 to 28, in which Layer A has a Cr-based component composition, have lower hardness than the aforementioned Inventive Examples with a Ti-based component composition. However, as described above, when used for sliding parts, it has a characteristic of being less aggressive to the target material than the Ti-based component composition. the

Therefore, from the above results, the significance of defining each composition of the layer B of the present invention can be demonstrated. the

As described above, the hard coating and the method for controlling the crystal particle diameter of the hard coating according to the present invention can improve the wear resistance of the hard coating by making the crystal particle diameter of the rock-salt structure type hard coating finer. Therefore, it can be used for wear-resistant coatings of cutting tools, automotive sliding parts, and the like based on cemented carbide, cermets, high-speed tool steel, and the like. the

Furthermore, according to the present invention, it is possible to provide a hard laminated coating excellent in wear resistance or oxidation resistance and a method for forming a hard laminated coating. Therefore, it can be used for wear-resistant coatings of cutting tools, automotive sliding parts, and the like based on cemented carbide, cermets, high-speed tool steel, and the like. the

In addition, according to the present invention, it is possible to provide a composite film-forming device and a sputtering evaporation source, and to obtain a hard coating with required characteristics without any problem in film-forming. the

Table 15

Table 16

Table 17

Table 18

Claims (4)

1. hard laminated film is characterized in that:

Layer A and layer B that alternative stacked is made of specific composition, the crystal structure of the crystal structure of layer A and layer B is inequality, and the thickness of every layer layer A is more than 2 times of thickness of every layer layer B, and the thickness of every layer layer B is more than 0.5nm, the thickness of every layer layer A is below 200nm

Wherein, by specific composition constitute the layer A and the layer B, with layer A and the layer B the mutual different modes alternative stacked of composition;

Layer A is by constituting any one composition the in following formula 1 or 2;

Formula 1:(Ti _1-x-yAl _xM _y) (B _aC _bN _1-a-b-cO _c),

But x, y, a, b, c represent atomic ratio respectively, 0.4≤x≤0.8,0≤y≤0.6,0≤a≤0.15,0≤b≤0.3,0≤c≤0.1,

In addition, M for the metallic element in 4A family from the periodic table of elements, 5A family, the 6A family, and Si in the element selected;

Formula 2:(Cr _1-αX _α) (B _aC _bN _1-a-b-cO _c) _e,

But α, a, b, c, e represent atomic ratio respectively, 0≤α≤0.9,0≤a≤0.15,0≤b≤0.3,0≤c≤0.1,0.2≤e≤1.1,

In addition, X be the element selected more than a kind of any from Ti, Zr, Hf, V, Nb, Ta, Mo, W, Al and Si,

Layer B: by constituting forming of following formula 3;

Formula 3:M _1-dM1 _d(B _aC _bN _1-a-b-cO _c),

But, M be the metallic element selected more than a kind of any from W, Mo, V, Nb,

M1 is except that W, Mo, V, Nb, the metallic element in the 4A family from the periodic table of elements, 5A family, the 6A family, and Si in select element,

A, b, c, d represent atomic ratio respectively, 0≤a≤0.15,0≤b≤0.3,0≤c≤0.1,0≤d≤0.3

2. hard laminated film as claimed in claim 1 is characterized in that:

Described layer A is with (Ti _1-x-yAl _xM _y) (B _aC _bN _1-a-b-cO _c) expression,

But x, y, a, b, c represent atomic ratio respectively, 0.5≤x≤0.8,0.05≤y≤0.6,0≤a≤0.15,0≤b≤0.3,0≤c≤0.1, in addition, a kind or more the element of M for from Cr, V, Si, selecting.

3. hard laminated film as claimed in claim 1 is characterized in that:

In described layer B, d=0.

4. hard laminated film as claimed in claim 1 is characterized in that:

In described layer B, M is V.

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