JP7035726B2 - Ceramic laminate - Google Patents

Description

The present invention relates to a ceramic laminate in which a ceramic film is formed on a base material and has an excellent bonding force between the ceramic film and the base material.

Ceramic laminates made by forming ceramics with excellent mechanical properties, reactivity resistance, heat resistance, insulation, heat dissipation, etc. on a base material such as metal, ceramics, and resin are wear-resistant members and corrosion-resistant members. , Widely used for insulating heat dissipation members. The usage environment of the ceramic laminate in these applications is harsh, and the ceramic film and the base material are firmly bonded to the ceramic laminate under stress of various types and sizes during use without peeling. That is, high bonding force (bonding strength) is required.

As a method for producing a ceramic laminate having a relatively high bonding force, an aerosol deposition method, which is one of the ceramic film forming methods, can be mentioned. The aerosol deposition method is a technology that forms a dense ceramic film on a substrate at room temperature by mixing ceramic fine particles with gas to make it into an aerosol and injecting it onto the substrate at high speed in a depressurized film formation chamber. be. When the jetted ceramic fine particles collide with the base material, they are deformed while being crushed, thereby realizing the formation of chemical bonds between the fine particles / base material or between the fine particles / fine particles and the densification of the film. Further, particularly between the fine particles / the base material, the fine particles scrape the surface of the base material and dig into it to form an uneven anchor bond. In the film formation by the aerosol deposition method, a dense film can be formed and a high bonding force can be exhibited by going through the above processes.

Various methods for manufacturing ceramic laminates to which such an aerosol deposition method is applied have been developed (see Patent Documents 1 to 3).

Patent Document 1 discloses that by increasing the hardness of the base material, the ceramic fine particles are easily broken and the film forming efficiency is improved.

According to Patent Document 2, by setting the surface roughness of the surface of the substrate within a specific range, the ceramic fine particles receive stress at the minute protrusions on the surface of the substrate, and the shear stress due to shrinkage is relaxed, so that the film formation efficiency is reduced. Is disclosed to increase.

According to Patent Document 3, by setting the ratio of the hardness of the fine particles to the hardness of the surface of the substrate within a specific range, the fine particles can be crushed into the substrate in a crushed state, and the bonding force and the film forming efficiency can be obtained. It is disclosed that will increase.

Japanese Unexamined Patent Publication No. 2007-284949 Japanese Unexamined Patent Publication No. 2008-11154 Japanese Patent No. 4769979

However, in the ceramic laminates produced by the methods of Patent Documents 1 to 3, since the film forming efficiency in the manufacturing process is emphasized, the interface shape and the bonding force between the ceramic film and the base material of the ceramic laminate are considered. Was not properly controlled and the bonding force was inadequate.

The present invention has been made in view of the above problems, and an object of the present invention is to provide a ceramic laminate having an excellent bonding force between a ceramic film of a ceramic laminate and a base material.

The ceramics laminate of the present invention is a ceramics laminate in which a ceramics film is laminated on a substrate, and the interface between the ceramics film and the substrate that appears in the cross section of the ceramics laminate has a high wavenumber component and a low wavenumber component. The wavelength range λ _short of the high wavenumber component is 0.1 μm or more, the maximum value D _max or less of the crystal grain size of the ceramic film, and the wavelength range λ _long of the low wavenumber component is the above. It is larger than the maximum value D _max and is 10 μm or less, and the average power spectral density P _high of the high wavenumber component calculated from the curve is 2 × ^10-5 μm ³ or more, and the low wavenumber calculated from the curve. The average power spectral density P _low of the components is 0.5 × 10 ^-3 μm ³ or more.

In the present invention, the average power spectral density Power of the _high wavenumber component is 2 × 10 ^-5 μm ³ or more, and the average power spectral density Power of the _low wavenumber component is 0.5 × 10 ^-3 μm ³ or more. A ceramic laminate having an excellent bonding force can be realized because the region of the film / base material interface where the unevenness exhibiting the anchor effect is present is large and there are many irregularities exhibiting the anchor effect.

FIG. 1A is a schematic view showing a cross section of the ceramic laminate of the embodiment of the present invention in the film thickness direction, and FIG. 1B is a schematic view showing a wave with a high wave number and a wave with a low wave number. FIG. 2A is a schematic diagram showing an example of a wavelength range of a wave having a high wave number of a curve formed by a film / substrate interface, and FIG. 2B is a schematic diagram showing an example of a wavelength range of a wave having a low wave number. It is the schematic which provides the explanation of the measuring method of the maximum value of the crystal grain size of a ceramic film. It is a schematic diagram which shows an example of the graph of the relationship between a wave number and a power spectral density. It is a schematic diagram which shows an example of the aerosol deposition apparatus which manufactures the ceramics laminate of this invention.

(1) Overall Configuration of Ceramic Laminates of the Embodiment of the Present Invention FIG. 1A is a schematic view showing a cross section of the ceramic laminate 1 of the embodiment of the present invention in the film thickness direction. The ceramic laminate 1 is composed of a base material 2 and a ceramic film 3 laminated on the base material 2. In practice, the base material 2 is made of, for example, a plate-shaped, columnar, or cylindrical member, and the ceramic film 3 is formed on the entire outer peripheral surface of the base material 2 or a part thereof. The film / substrate interface 4 of the base material 2 and the ceramic film 3 appears in the cross section of the ceramic laminate 1 in the film thickness direction, and as shown in FIG. 1A, the film / substrate interface 4 is gentle. It is a curve in which small irregularities are formed on the irregularities.

The small irregularities at the film / substrate interface 4 are formed when the ceramics are formed into a film in the manufacturing process, serve as an anchor for fixing the ceramic film 3 to the substrate 2, and exhibit an anchor effect. Further, the gentle unevenness at the film / base material interface 4 increases the total distance (that is, the total surface area) of the region where the unevenness that exerts the anchoring effect exists, although the unevenness itself does not exert the anchor effect, and the film / It increases the number of irregularities that exert an anchoring effect on the substrate interface 4, and exerts the effect of strengthening the bonding force between the substrate 2 and the ceramic film 3. As described above, since the ceramic laminate 1 has gentle irregularities on the film / substrate interface 4, the number of small irregularities exhibiting the anchor effect is large, and the ceramic laminate 1 is excellently bonded between the substrate 2 and the ceramic film 3. Have power.

The base material 2 is, for example, copper (Cu), aluminum (Al), iron (Fe), stainless steel, nickel (Ni), titanium (Ti), molybdenum (Mo), zirconium (Zr), tungsten (W), silver. It is preferably formed of (Ag) and a metal material such as an alloy mainly composed of these. In general, the hardness of a metal material is lower than that of ceramics. Therefore, by using the base material 2 as a metal material, the crystal grains of the ceramics are easily sunk into the metal material in the manufacturing process described later, and the film / base material interface 4 is anchored. It becomes easy to form unevenness that exerts an effect.

Further, the surface texture of the metal material is easier to adjust by methods such as polishing, etching, blasting, and heat treatment than the ceramic material and the resin material. Therefore, by forming the base material 2 with a metal material, it becomes easy to form unevenness that increases the region where the unevenness exhibiting the anchor effect exists, and it becomes easy to produce the form of the ceramic laminate 1 of the present embodiment.

The ceramic film 3 includes aluminum oxide (Al ₂ O ₃ ), aluminum nitride (Al N), silicon nitride (Si ₃ N ₄ ), zirconium oxide (ZrO ₂ ), silicon carbide (SiC), and yttrium oxide (Y ₂ O ₃ ). , Silicon oxide (SiO ₂ ) and other ceramic materials.

As described above, in the ceramic laminate 1, the film / base material interface 4 appearing in the cross section in the film thickness direction exhibits the anchor effect on the gentle unevenness that increases the region where the unevenness exhibiting the anchor effect exists. It is a form in which small irregularities are formed, that is, a curved form in which gentle irregularities and small irregularities are superposed. Therefore, when the small unevenness is made to correspond to the wave 4a having a high wave number (short wavelength) shown in FIG. 1B and the gentle unevenness is made to correspond to the wave 4b having a low wave number (long wavelength) shown in FIG. 1B, a curved film is formed. / Curve z (x) (x is the position in the in-plane direction, z is the position (height) in the film thickness direction) in which the wave 4a having a high wave number and the wave 4b having a low wave number are superimposed on the substrate interface 4. ) Can be regarded. Therefore, in the present embodiment, the film / substrate interface 4 is defined as the curve z (x), the curve z (x) is acquired from the image obtained by capturing the film / substrate interface 4, and the high wave number is obtained from the curve z (x). The morphology of the film / substrate interface 4 is evaluated by separating the component of the wave 4a (also referred to as a high wavenumber component) and the component of the wave 4b having a low wavenumber (also referred to as a low wavenumber component). The high wavenumber wave 4a and the low wavenumber wave 4b each contain a plurality of wavenumber components, but FIG. 1B shows a wave with one representative wavenumber component.

Here, as shown in FIG. 2A, the wave 4a having a high wave number is a wave having a wavelength λ equal to or less than the maximum value D _max of the crystal grain size of the crystal grain 5 of the ceramic film 3. At this time, the lower limit of the wavelength λ of the high wave number wave 4a is set to 0.1 μm, and even if the curve z (x) includes a wave having a wavelength shorter than 0.1 μm, the wave is the high wave number wave 4a. It will not be regarded as. Therefore, the wavelength range λ _short of the wave 4a having a high wave number is 0.1 μm ≤ λ _short ≤ D _max . For example, if the maximum value of the crystal grain size of the ceramic film 3 is D _max = 0.4 μm, the wavelength range λ _short of the wave 4a having a high wave number is 0.1 μm ≤ λ _short ≤ 0.4 μm.

On the other hand, the low wavenumber wave 4b is a wave having a wavelength λ larger than the upper limit of the wavelength range λ _short of the high wavenumber wave 4a, and the wavelength range λ _long is D _max <λ _long ≦. It is set to 10 μm. For example, if the wavelength range λ _short of the high wave number wave 4a is 0.1 μm ≤ λ _short ≤ 0.4 μm, the wavelength range λ _long of the low wave number wave 4b is 0.4 μm <λ _long ≤ 10 μm. .. In the case of a wave having a wavelength exceeding 10 μm, the corresponding unevenness becomes almost a straight line in a minute region, so that the effect of increasing the total distance (total surface area) of the region where the unevenness exhibiting the anchor effect as described above exists is effective. I don't have it. Therefore, the upper limit of the wavelength range λ _long is set to 10 μm.

That is, if the curve z (x) formed by the film / substrate interface 4 of the ceramic film 3 and the substrate 2 includes the high wavenumber component of the wavelength range λ _short and the low wavenumber component of the wavelength range λ _long . The high wave number wave 4a and the low wave number wave 4b are superimposed, and the unevenness corresponding to the low wave number wave 4b increases the total distance of the region where the unevenness corresponding to the high wave number wave 4a exerting the anchor effect exists. Therefore, the ceramic laminate 1 having a high bonding force can be obtained.

Specifically, in the ceramics laminate 1, the average power spectral density P _high of the high wavenumber component calculated from the curve z (x) by the method described later is 2 × 10 ^-5 μm ³ or more, and the low wavenumber component. It is desirable that the average power spectral density of P _low is 0.5 × 10 ^-3 μm ³ or more. In such a ceramic laminate 1, the curve z (x) is a superposition of a wave 4a having a high wave number and a wave 4b having a low wave number, and the unevenness corresponding to the wave 4b having a low wave number has an unevenness that exerts an anchor effect. It has excellent bonding strength because it increases the total distance of the existing area.

Here, the average power spectral density _High means that if this value is equal to or higher than a predetermined value, unevenness that exerts an anchor effect is formed on the film / substrate interface 4. The average power spectral density P _low means that the unevenness that increases the total distance of the region where the unevenness exhibiting the anchor effect exists in the film / base material interface 4 is formed. The average power spectral densities _High and _Plow are calculated by the methods described in "(3) Acquisition method of curve z (x)" and "(4) Calculation method of average power spectral density" described later.

The average power spectral density _Power is preferably 1 × 10 ^-3 μm ³ or more, and more preferably the average power spectral density _Power is 3 × 10 ^-3 μm ³ or more. By setting the average power spectral density Power to 1 × 10 ^-3 μm ³ or more and the average power spectral density _Power to 3 × 10 ^-3 μm ³ or more, the unevenness corresponding to the _low wavenumber wave 4b can be obtained. Since the total distance (total surface area) of the region where the unevenness exhibiting the anchor effect exists is further increased, the ceramic laminate 1 having a higher bonding force can be obtained.

On the other hand, when the average power spectral density P _high is smaller than 2 × 10 ^-5 μm ³ , even if the unevenness corresponding to the wave 4b having a low wave number exists, the unevenness itself that exerts the anchor effect is reduced. The bonding force is greatly reduced. Further, when the average power spectral density P _low is smaller than 0.5 × 10 ^-3 μm ³ , the total distance of the region where the unevenness exhibiting the anchor effect exists is reduced, so that the bonding force is reduced. It ends up.

Further, the ceramic laminate 1 is formed by an aerosol deposition method capable of forming a dense ceramic film 3 on the base material 2 by injecting the ceramic fine particles mixed with gas into an aerosol at high speed onto the base material 2. It is preferable that 3 is formed. By forming the ceramic film 3 by the aerosol deposition method, the ceramic fine particles collide with the base material 2 to cause a film forming phenomenon, and at the same time, the ceramic fine particles are formed by being embedded, which is the same as the crystal grain size of the ceramic film 3. It becomes easy to form unevenness (unevenness corresponding to a wave 4a having a high wave number) having a wavelength in the range and exhibiting an anchor effect on the film / base material interface 4.

(2) Method for measuring the maximum value D _max of the crystal grain size In the SEM image obtained by capturing the cross section of the ceramic laminate 1 in the film thickness direction, 100 or more crystal grains 5 of the ceramic film 3 are randomly selected and shown in FIG. As described above, the maximum length of each crystal grain 5 in the in-plane direction is measured. The maximum value in the maximum length of the measured crystal grains 5 is defined as the maximum value D _max of the crystal grain size.

(3) Acquisition method of curve z (x) In the SEM image of the cross section in the film thickness direction in which the film / substrate interface 4 of the ceramic laminate 1 is clearly photographed, the film / substrate interface 4 is used by image analysis software or the like. The curve z (x) is obtained by acquiring N = 1024 pieces of the coordinate data (x, z) of No. 1 in the in-plane direction (horizontal direction) at intervals of Δx = 0.0212 μm. The data interval X is X = Δx × N = 21.7088 μm. In order to obtain the curve z (x) as described above, the SEM image to be used needs to have a length of 0.0212 μm or less per pixel and a number of pixels in the in-plane direction (horizontal direction) of 1024 pixels or more. be. When a plurality of z are obtained for a specific x when acquiring the coordinate data, the coordinate with the maximum z is adopted, and the other coordinates are removed.

(4) Method for calculating average power spectral density First, the curve z (x) is discretely Fourier transformed by the following equations (1), (2) and (3), and the Fourier transform Z (k) of the curve z (x) is obtained. obtain. Specifically, the equation (2), the equation (3), and the curve z (x) are substituted into the equation (1), the equation (1) is calculated for each wave number k, and Z (k) is calculated.

Next, using Z (k), the power spectral density P (k) (μm ³ ) is obtained by the following equation (4). The power spectral density P (k) represents the power of a wave having a wave number k. FIG. 4 shows a schematic diagram of the relationship between the wave number k and the power spectral density P (k). In FIG. 4, the horizontal axis is the wave number k, and the vertical axis is the power spectral density P (k).

Finally, the wavenumber range k _high (k _high = 1 / λ _short ) corresponding to the wavelength range λ _short of the high wave number component described above, and the wave number range k _low (k _low ) corresponding to the wavelength range λ _long of the low wave number component described above. = 1 / λ _long ), the pre-average of the high wavenumber component by adding the P (k) contained in each range and dividing the summing result by the number of P (k) contained in each range. The power spectral density P _{high (p)} and the pre-average power spectral density P _{low (p)} of the low wavenumber component are calculated. This calculation is performed three times for one ceramic laminate 1 by changing the imaging location of the SEM image, and three sets of pre-average power spectral densities P _{high (p)} and _{Low (p)} are calculated. The calculated average values of the three sets of pre-average power spectral densities P _{high (p) and} P _{low (p)} were calculated, and the calculated average values were used as the average power spectral densities P _high (μm ³ ) of the ceramic laminate 1 and. The average power spectral density is P _low (μm ³ ).

(5) Method for manufacturing ceramic laminate 1 according to the embodiment of the present invention The method for manufacturing the ceramic laminate 1 of the present invention will be described. The method for producing the ceramic laminate is not particularly limited, such as PVD method, CVD method, thermal spraying method, cold spray method, solgel method, etc. The aerosol deposition method of spraying to form the ceramic film 3 on the base material 2 is desirable in that a dense ceramic film can be formed at room temperature. Further, in the aerosol deposition method, the ceramic fine particles collide with the base material 2 to cause a film forming phenomenon, and at the same time, the ceramic fine particles dig into the base material 2 and have a high wave having a wavelength in the same range as the crystal grain size of the ceramic film 3. It is desirable that the number of waves 4a, that is, the size of the same as the crystal grain size, facilitates the formation of irregularities exhibiting an anchor effect on the film / substrate interface 4. Hereinafter, a method for manufacturing the ceramic laminate 1 will be described by taking the aerosol deposition method as an example.

First, a general method for manufacturing a ceramic laminate will be described. The ceramic laminate is manufactured, for example, by using the aerosol deposition device 11 illustrated in FIG. The aerosol deposition device 11 of FIG. 5 includes an aerosolizing container 12, a film forming chamber 13, an aerosol transport pipe 14, a vacuum pump 15, and a gas supply system 16. The aerosolization container 12 and the film forming chamber 13 are connected by an aerosol transfer pipe 14. The vacuum pump 15 is connected to the film forming chamber 13 and can reduce the pressure in the film forming chamber 13. The gas supply system 16 and the aerosolization container 12 are connected by a transport gas pipe 18 and a hoisting gas pipe 19.

The aerosolized container 12 contains a ceramic powder (powder of fine particles of ceramics) 17 inside the container, and _N2 gas or He gas is supplied as a hoisting gas into the ceramic powder 17 from the hoisting gas pipe 19. _N2 gas or He gas can also be supplied as the transport gas from the transport gas pipe 18 to the internal space of the aerosolization container 12. The aerosolizing container 12 is provided with a vibration mechanism (not shown) for stirring the ceramic powder 17 and a heating mechanism (not shown) for drying the ceramic powder 17.

Inside the film forming chamber 13, a stage 20 is provided so that the substrate fixing surface faces the nozzle port of the aerosol transfer tube 14. The base material 2 can be fixed to the base material fixing surface of the stage 20. The stage 20 is provided with a horizontal drive mechanism 21 for repeatedly spraying the aerosol onto the surface of the base material 2 by changing the position where the aerosol hits the base material 2 by moving the stage 20.

In the aerosol deposition device 11 having the above configuration, _N2 gas or He gas is supplied from the gas supply system 16 into the aerosolizing container 12 through the hoisting gas pipe 19, and the aerosol containing the ceramic fine particles is made into an aerosol. Generated in the container 12. At this time, the aerosol deposition device 11 supplies N _{2 gas or He gas into the aerosolization container 12 through the transport gas pipe 18, and the supplied N 2 gas} or He gas is used to dissipate the aerosol in the aerosolization container 12. , Is supplied to the film forming chamber 13 through the aerosol transfer tube 14.

In the film forming chamber 13, aerosol can be injected from the nozzle port of the aerosol transport pipe 14 toward the base material 2 fixed to the stage 20 in the film forming chamber 13 decompressed by the vacuum pump 15. At this time, the aerosol deposition device 11 reciprocates the stage 20 in the horizontal direction (direction of the arrow in FIG. 5) by the horizontal drive mechanism 21, and the aerosol ejected from the nozzle port of the aerosol transfer pipe 14 is used as a base material. Repeatedly spray on the surface of 2.

The aerosol deposition device 11 injects aerosol onto the surface of the base material 2 and causes the ceramic fine particles to collide with the base material 2, thereby crushing and deforming the ceramic fine particles by kinetic energy. Then, chemical bonds are formed between the particles / base material or between the new surfaces between the particles / particles, and the film is densified. In addition, between the particles / base material, the ceramic fine particles scrape the surface of the base material, and the ceramic fine particles are formed. Is sunk into the base material 2 to produce a ceramic laminate having irregularities that exert an anchoring effect.

In the film formation of the ceramic film 3 by the aerosol deposition method using the aerosol deposition device 11, there are optimum film forming conditions for each of the ceramic materials to be formed. Among them, the effect of the particle size of the ceramic powder 17 which is the raw material powder is particularly large, and the film forming phenomenon cannot occur unless the film is formed using the raw material powder containing the ceramic fine particles having the optimum particle size. For example, if the particle size is too large, the ceramic fine particles are not crushed or deformed, and the base material 2 is scraped off like a blast, so that a film is not formed. If the particle size is too small, the ceramic fine particles follow the gas, so that the ceramic fine particles do not collide with the base material 2 and the film is not formed.

Generally, the particle size of the ceramic fine particles that can be formed by the aerosol deposition method is several hundred nm to several μm. However, this differs depending on the type of ceramic material, and in the above particle size range, there may be cases where a large particle size is better and conversely a small particle size is better. Therefore, naturally, the crystal grain size of the ceramic film 3 after film formation (= particle size of the ceramic fine particles contributing to film formation) also differs depending on the type of ceramic material. Further, from the above, it is generally considered desirable to use the raw material powder containing the ceramic fine particles having the optimum particle size in as much as possible from the viewpoint of the yield of the raw material powder and the film forming speed. ing.

However, even if a powder made of ceramic fine particles having an optimum particle size that contributes to film formation is simply used as it is to form a film by using the aerosol deposition method as described above, the film / substrate interface 4 is formed. Since the unevenness corresponding to the wave 4a having a high wave number is only formed and the unevenness corresponding to the wave 4b having a high wave number is not formed, the ceramic laminate 1 of the present embodiment cannot be obtained. The curve z (x) formed by the film / substrate interface 4 is a superposition of the high wavenumber wave 4a and the low wavenumber wave 4b, that is, the average power spectral density P of the high wavenumber component of the curve z (x). The _high is 2 × 10 ^-5 μm ³ or more, and the average power spectral density P _low of the low wavenumber component is 0.5 × 10 ^-3 μm ³ or more, preferably 1 × 10 ^-3 μm ³ or more, more preferably. In order to manufacture the ceramics laminate 1 having a size of 3 × 10 ^-3 μm ³ or more, for example, the following method needs to be used.

When manufacturing by the aerosol deposition method alone, when forming the ceramic film by the aerosol deposition method, not only the powder containing the ceramic fine particles of the particle size that contributes to the film formation is used, but the wave 4b (low wave number) of the low wave number is used. It is necessary to perform film formation using a raw material powder mixed with a powder containing ceramic fine particles having a particle size in the same range as the wavelength range λ _long of the wave number component). As a result, at the same time as the film formation, both the unevenness corresponding to the high wave number wave 4a and the unevenness corresponding to the low wave number wave 4b can be formed. A powder containing ceramic fine particles having a particle size in the same range as λ _long tends to form irregularities corresponding to a wave 4b having a low wave number as a large number of particles having a large particle size are contained. It is desirable that the median diameter of the powder containing the ceramic fine particles having the same particle size as λ _long is smaller than 3 μm because the yield may decrease and the base material and the film may be scraped.

Further, the ceramic laminate 1 is provided with unevenness (unevenness based on the wavelength range λ _long ) corresponding to the wave 4b having a low wave number by adjusting the surface texture of the base material 2 before film formation in advance, and the unevenness is formed. The ceramic film 3 may be formed while forming the unevenness corresponding to the wave 4a having a high wave number by using the aerosol deposition method so as not to be removed. Examples of the method for adjusting the surface texture of the base material before film formation include methods such as polishing, etching, blasting, and heat treatment, but it is important to perform the method under appropriate conditions and combinations.

For example, when blasting the surface of the base material 2, it is necessary to use a powder containing only fine particles in the same particle size range as the wavelength range λ _long of the target wave 4b having a low wave number. If blasting is performed using a powder containing fine particles having a particle size outside the wavelength range λ _long , the film forming phenomenon may be hindered during film formation or the bonding force may not be increased. Further, for example, when etching is performed, the crystal grain size of the base material 2 is made equal to the wavelength range λ _long of the target low wave number (long wavelength) wave 4b by heat treatment or the like, and then etching is performed, or the base material is performed. It may be necessary to scratch the surface at intervals equivalent to the wavelength range λ _long of the target low wave number (long wavelength) wave 4b, and then perform etching.

By using the above method, the average power spectral density P _high of the high wavenumber component of the curve z (x) is 2 × 10 ^-5 μm ³ or more, and the average power spectral density P _low of the low wavenumber component. It is possible to produce the ceramics laminate 1 of the present invention having a density of 0.5 × 10 ^-3 μm ³ or more, preferably 1 × 10 ^-3 μm ³ or more, and more preferably 3 × 10 ^-3 μm ³ or more.

(6) Action and Effect In the above configuration, in the ceramic laminate 1 of the present invention, the ceramic film 3 is laminated on the base material 2, and the ceramic film 3 and the base material 2 appearing on the cross section of the ceramic laminate 1. The interface (film / substrate interface 4) is represented by a curve z (x) containing a high wavenumber component and a low wavenumber component, the wavelength range λ _short of the high wavenumber component is 0.1 μm or more, and the crystal grains of the ceramic film 3 The wavelength range λ _long of the low wavenumber component is larger than the _{maximum value D max and} 10 μm or less, and the average power spectral density P of the high wavenumber component calculated from the curve z (x). The _high is 2 × 10 ^-5 μm ³ or more, and the average power spectral density P _low of the low wavenumber component calculated from the curve z (x) is 0.5 × 10 ^-3 μm ³ or more.

In the ceramics laminate 1 of the present invention, the average power spectral density Power of the _high wavenumber component is 2 × 10 ^-5 μm ³ or more, and the average power spectral density Power of the _low wavenumber component is 0.5 × 10 ^-3 μm. Since the number is ³ or more, the region of the film / base material interface where the unevenness exhibiting the anchor effect is present is large, and many irregularities exhibiting the anchor effect are present, so that it is possible to have an excellent bonding force.

(7) Verification test The ceramic laminate 1 of the present embodiment was produced, and the bonding force between the base material 2 of the ceramic laminate 1 and the ceramic film 3 was evaluated. Here, a pin with an epoxy adhesive having a diameter of φ4.1 mm is erected on the ceramic film 3 of the produced ceramic laminate 1, and the pin is adhered to the ceramic film 3 by heating at 150 ° C. for 1 hour to bond the pin to the ceramic laminate 1. The bonding force of the ceramic laminate 1 was evaluated by pulling the adhered pin in the film thickness direction with a tensile tester and measuring the stress at the time of breaking.

(Example 1)
In Example 1, as the ceramic powder 17, α _- Al ₂ O3 powder A having a minimum particle diameter of 0.1 μm, a maximum particle diameter of 0.4 μm, and a median diameter of 0.2 μm is used as a minimum particle diameter of 0.4 μm and a maximum particle diameter. A mixed powder (weight of α-Al ₂ O ₃ powder A: α-Al ₂ ) obtained by adding α-Al ₂ O ₃ powder B having a size of 10 μm and a median diameter of 2 μm so that the mixing amount of the powder B is 50 wt% of the total amount. Using the weight of O3 powder B = ₁ : 1) and using a pre-polished anoxic Cu base material as the base material 2, the above-mentioned "(5) Production of the ceramic laminate according to the embodiment of the present invention". The ceramic film 3 was formed on the base material 2 by the aerosol deposition apparatus 11 described in the above method, and the ceramic laminate 1 was produced.

At this time, N ₂ gas was used as the hoisting gas and the hoisting gas, and the total of the transport gas flow rate and the hoisting gas flow rate was set to 8 L / min. The nozzle opening at the tip of the aerosol transfer tube 14 is 5 x 0.3 mm, the angle between the normal of the base material 2 and the nozzle is 30 °, and the number of horizontal repeat drives of the stage 20 to which the base material 2 is fixed is 20 times (20 layers). ). The pressure in the film forming chamber 13 during the film forming was 70 Pa.

The ceramic laminate 1 of Example 1 thus produced was cut in the film thickness direction, the cross section in the film thickness direction that appeared was mirror-polished, and the ceramic film 3 was formed by FE-SEM (ULTRA 55, Carl Zeiss). The cross section was observed at a magnification of 50,000 to obtain an SEM image. When 100 crystal grains of the ceramic film 3 were randomly selected from the acquired SEM images and the maximum length of each crystal grain in the in-plane direction was measured, the maximum value D _max among them was D _max = 0.4 μm. Met. From this result, the wavelength range λ _short of the wave 4a having a high wave number is 0.1 μm ≤ λ _short ≤ 0.4 μm, and the wavelength range λ _long of the wave 4b having a low wave number is 0.4 μm < It was determined that λ _long ≤ 10 μm. Here, from the crystal grain size of the ceramic film 3, among the fine particles contained in the mixed powder of α-Al ₂ O ₃ powder A and α-Al ₂ O ₃ powder B, the fine particles derived from α-Al ₂ O ₃ powder B Most of the particles do not contribute to the film formation, and it can be said that the fine particles derived from a small part of the α _- Al ₂ O3 powder A and the powder B, which have the optimum particle size, contribute to the film formation and form a film.

Using FE-SEM, the film / substrate interface 4 appearing on the cross section of the ceramic laminate 1 of Example 1 was observed at a magnification of × 5000 to obtain an SEM image. In order to clarify the shape of the film / substrate interface 4, the acceleration voltage during observation was set as low as 5 kV. The acquired SEM image having a magnification of 5,000 has a length of 0.0212 μm per pixel and 1024 pixels in the in-plane direction (horizontal direction). For the SEM image, the film / substrate interface 4 is traced using image analysis software (Image-Pro Premier, Nippon Roper Co., Ltd.) at intervals of Δx = 0.0212 μm in the in-plane direction (horizontal direction). N = 1024 coordinate data (x, z) were acquired, and a curve z (x) was obtained. For the obtained curve z (x), the power spectral density P (k) was obtained by the method described in "(4) Method for calculating the average power spectral density". With respect to the obtained power spectrum density P (k), the wave number range of the high wave number wave 4a calculated from the wavelength range determined earlier is 1 / 0.4 = 2.5 μm ^-1 ≤ 1 / λ _short = k _high ≤ 1/0. .1 = 10 μm ^-1 , low wavenumber wavenumber 4b wavenumber range 1/10 = 0.1 μm ^-1 ≤ 1 / λ _long = k _low <1 / 0.4 = 2.5 μm ^-1 and high wavenumber The pre-average power spectral density P _{high (p)} of the components and the pre-average power spectral density P _{low (p)} of the low wavenumber components were calculated. These operations were also performed on two SEM images in different fields, a total of three sets of pre-average power spectral densities P _{high (p)} and P _{low (p)} were calculated, and they were averaged and performed. When the average power spectral density P _high and _Plow of Example 1 were obtained, the average power spectral density P _high = 4 × 10 ^-5 μm ³ and the average power spectral density P _low = 1 × 10 ^-3 μm ³ .

Further, in order to compare with the base material 2 before film formation, the average power spectral densities _High and _Plow were calculated in the same manner on the surface of the base material 2 in the place where the ceramic film 3 was not formed. The spectral density P _high = 0.4 × 10 ^-5 μm ³ and the average power spectral density P _low = 0.4 × 10 ^-3 μm ³ . From this, at the time of film formation, particles having a minimum particle diameter of 0.1 μm and a maximum particle diameter of 0.4 μm derived from α _- Al _{2 O3} powder A were formed into a film while being sunk into the substrate, so that the price was increased before the film formation. In addition, the mixed powder contains fine particles derived from α-Al ₂ O ₃ powder B that do not contribute to film formation, and the fine particles _dent the base material 2 to form a Plow. It is thought that it has increased from before.

As a result of evaluating the bonding force of the ceramic laminate 1 of Example 1, the ceramic film 3 of the ceramic laminate 1 was peeled off and the pin was removed, but the breaking stress was 50 MPa. Since the ceramic laminate 1 of Example 1 has a breaking stress of 50 MPa, the bonding force was evaluated as ◯.

(Example 2)
In Example 2, α _- Al ₂ O3 powder A having a minimum particle diameter of 0.1 μm, a maximum particle diameter of 0.4 μm, and a median diameter of 0.2 μm was used as the ceramic powder 17, and the base material 2 was previously heat-treated. Using the oxygen-free Cu base material on which the crystal grains on the surface were grown, the ceramic laminate 1 was produced by the same method as in Example 1.

Further, when the D _max was calculated for the ceramic laminate 1 of Example 2 produced by the same method as in Example 1, it was found that D _max = 0.4 μm. From this result, the wavelength range λ _short of the wave 4a having a high wave number is 0.1 μm ≤ λ _short ≤ 0.4 μm, and the wavelength range λ _long of the wave 4b having a low wave number is 0.4 μm < It was determined that λ _long ≤ 10 μm.

In the same manner as in Example 1, the power spectral density P (k) of the ceramic laminate 1 of Example 2 was determined. With respect to the obtained power spectrum density P (k), the wavenumber range of the high wavenumber wave 4a calculated from the wavelength range determined earlier is 1 / 0.4 = 2.5 μm ^-1 ≤ 1 / λ _short = k _high ≤ 1/0. .1 = 10 μm ^-1 , wavenumber range of low wavenumber 4b 1/10 = 0.1 μm ^-1 ≤ 1 / λ _long = k _low <1 / 0.4 = 2.5 μm ^-1 and average power When the spectral densities P _high and P _low were calculated, the average power spectral density P _high = 4 × 10 ^-5 μm ³ and the average power spectral density P _low = 1 × 10 ^-3 μm ³ .

Further, in order to compare with the base material 2 before film formation, the average power spectral densities P _high and P _low were calculated in the same manner on the surface of the base material 2 in the place where the ceramic film 3 was not formed _. = 0.4 × 10 ^-5 μm ³ and _Low = 1 × 10 ^-3 μm ³ . From this, the fine particles contained in the α-Al ₂ O ₃ powder A were formed into a film while being sunk into the base material at the time of film formation, so that the _Phi increased from before the film formation, but the _Plow changed from before the film formation. It turns out that it wasn't. As described above, it can be seen that the unevenness corresponding to the wave 4b having a low wave number is formed in advance.

As a result of evaluating the bonding force of the ceramic laminate 1 of Example 2, the ceramic film 3 of the ceramic laminate 1 was peeled off and the pin was removed, but the breaking stress was 50 MPa, which was equivalent to that of Example 1. Since the ceramic laminate 1 of Example 2 has a breaking stress of 50 MPa, the bonding force was evaluated as ◯.

(Example 3)
As Example 3, as the ceramic powder 17, a mixed powder of α-Al ₂ O ₃ powder A and α-Al ₂ O ₃ powder B (weight of α-Al ₂ O ₃ powder A: α) as in Example 1. -Al ₂ O ₃ powder B weight = 1: 1) was used, and as the base material 2, an oxygen-free Cu base material that had been scratched in advance and then etched was used, and ceramics were used in the same manner as in Example 1. The laminated body 1 was produced.

Further, when the D _max was calculated for the prepared ceramic laminate 1 of Example 3 by the same method as in Example 1, it was found that D _max = 0.4 μm. From this result, the wavelength range λ _short of the wave 4a having a high wave number is 0.1 μm ≤ λ _short ≤ 0.4 μm, and the wavelength range λ _long of the wave 4b having a low wave number is 0.4 μm < It was determined that λ _long ≤ 10 μm.

In the same manner as in Example 1, the power spectral density P (k) of the ceramic laminate 1 of Example 3 was determined. With respect to the obtained power spectrum density P (k), the wavenumber range of the high wavenumber wave 4a calculated from the wavelength range determined earlier is 1 / 0.4 = 2.5 μm ^-1 ≤ 1 / λ _short = k _high ≤ 1/0. .1 = 10 μm ^-1 , wavenumber range of low wavenumber 4b 1/10 = 0.1 μm ^-1 ≤ 1 / λ _long = k _low <1 / 0.4 = 2.5 μm ^-1 and average power When the spectral densities P _high and P _low were calculated, the average power spectral density P _high = 6 × 10 ^-5 μm ³ and the average power spectral density P _low = 3 × 10 ^-3 μm ³ .

Further, in order to compare with the base material 2 before film formation, the average power spectral densities _High and _Plow were calculated in the same manner on the surface of the base material 2 in the place where the ceramic film 3 was not formed. The spectral density P _high = 1 × 10 ^-5 μm ³ and the average power spectral density P _low = 1 × 10 ^-3 μm ³ . From this, at the time of film formation, particles having a minimum particle diameter of 0.1 μm and a maximum particle diameter of 0.4 μm derived from α-Al ₂ O ₃ powder A were formed into a film while being sunk into the substrate 2, so that the average power spectral density was _high . In addition, the mixed powder contains fine particles derived from α-Al ₂ O ₃ powder B that do not contribute to film formation, and the fine particles dent the base material 2. It is considered that the average power spectral density _Powder also increased from before the film formation.

As a result of evaluating the bonding force of the ceramic laminate 1 of Example 3, the ceramic film 3 of the ceramic laminate 1 was not peeled off and the pins were removed, the breaking stress was 60 MPa, and the bonding force was the same as that of Example 1. It was confirmed that it was larger than Example 2. Since the ceramic laminate 1 of Example 3 has a breaking stress of 60 MPa, the bonding force was evaluated as ⊚.

(Example 4)
In Example 4, the ceramic powder 17 has a minimum particle diameter of 0.05 μm, a maximum particle diameter of 0.3 μm, and a median diameter of 0.2 μm in β _- Si _3N4 powder C with a minimum particle diameter of 0.3 μm and a maximum particle diameter of 6 μm. , Β-Si ₃ N ₄ powder D having a median diameter of 1 μm added so that the mixing ratio is 80 wt% (weight of β-Si ₃ N ₄ powder C: weight of β-Si ₃ N ₄ powder D = 1: 4) was used, and an oxygen-free Cu base material that had been polished in advance was used as the base material 2, and the total of the conveyed gas flow rate and the hoisting gas flow rate was 10 L / min, in the film forming chamber 13 during film formation. The pressure was 360 Pa, and the ceramic laminate 1 was produced in the same manner as in Example 1 under other conditions.

Further, when D _max was calculated for the prepared ceramic laminate 1 of Example 4 by the same method as in Example 1, D _max = 0.3 μm. From this result, the wavelength range λ _short of the wave 4a having a high wave number is 0.1 μm ≤ λ _short ≤ 0.3 μm, and the wavelength range λ _long of the wave 4b having a low wave number is 0.3 μm < It was determined that λ _long ≤ 10 μm.

In the same manner as in Example 1, the power spectral density P (k) of the ceramic laminate 1 of Example 4 was determined. With respect to the obtained power spectrum density P (k), the wavenumber range of the _high wavenumber wave 4a calculated from the wavelength range determined earlier is 1 / 0.3 = 3.3 μm ^-1 ≤ 1 / λ _short = kHz ≤ 1/0. .1 = 10 μm ^-1 , wavenumber range of low wavenumber 4b 1/10 = 0.1 μm ^-1 ≤ 1 / λ _long = k _low <1 / 0.3 = 3.3 μm ^-1 and average power When the spectral densities P _high and P _low were calculated, the average power spectral density P _high = 2 × 10 ^-5 μm ³ and the average power spectral density P _low = 0.5 × 10 ^-3 μm ³ .

Further, in order to compare with the base material 2 before film formation, the average power spectral densities _High and _Plow were calculated in the same manner on the surface of the base material 2 in the place where the ceramic film 3 was not formed. The spectral density P _high = 0.4 × 10 ^-5 μm ³ and the average power spectral density P _low = 0.4 × 10 ^-3 μm ³ . From this, at the time of film formation, particles having a minimum particle diameter of 0.05 μm and a maximum particle diameter of 0.3 μm derived from β- _{Si 3} N ₄ powder C were formed into a film while being sunk into the base material 2, so that the price was before film formation. In addition, the mixed powder contains fine particles derived from β-Si ₃ N ₄ powder D that do not contribute to film formation, and the fine particles _dent the base material 2 to form a plow. It is considered that the amount increased from the front of the membrane.
As a result of evaluating the bonding force of the ceramic laminate 1 of Example 4, the ceramic film 3 of the ceramic laminate 1 was peeled off and the pin was removed, but the breaking stress was 40 MPa. Since the ceramic laminate 1 of Example 4 has a breaking stress of 40 MPa, the bonding force was evaluated as Δ.

(Example 5)
In Example 5, the minimum particle diameter of the ceramic powder 17 is 0.05 μm, the maximum particle diameter is 0.3 μm, and the minimum particle diameter of β-Si ₃ N ₄ powder C having a median diameter of 0.2 μm is 0.3 μm and the maximum particle diameter is 6 μm. Mixed powder (β-Si ₃ N ₄ powder C weight: β-Si ₃ N ₄ powder D weight = 1) to which β-Si ₃ N ₄ powder D having a median diameter of 1 μm is added so that the mixing ratio is 80 wt%. : 4) was used, and an oxygen-free Cu base material that had been polished in advance was used as the base material 2, and the total of the conveyed gas flow rate and the hoisting gas flow rate was 10 L / min in the film forming chamber 13 during film formation. The pressure was 36 Pa, and the other conditions were the same as in Example 1, so that the ceramic laminate 1 was produced.

Further, when D _max was calculated for the prepared ceramic laminate 1 of Example 5 by the same method as in Example 1, D _max = 0.3 μm. From this result, the wavelength range λ _short of the wave 4a having a high wave number is 0.1 μm ≤ λ _short ≤ 0.3 μm, and the wavelength range λ _long of the wave 4b having a low wave number is 0.3 μm < It was determined that λ _long ≤ 10 μm.

In the same manner as in Example 1, the power spectral density P (k) of the ceramic laminate 1 of Example 5 was determined. With respect to the obtained power spectrum density P (k), the wave number range of the high wave number wave 4a calculated from the wave number range determined earlier is 1 / 0.3 = 3.3 μm ^-1 ≤ 1 / λ _short = k _high ≤ 1/0. .1 = 10 μm ^-1 , low wavenumber wavenumber 4b wavenumber range 1/10 = 0.1 μm ^-1 ≤ 1 / λ _long = k _low <1 / 0.3 = 3.3 μm ^-1 and average power When the spectral density P _high and the average power spectral density P _low were calculated, the average power spectral density P _high = 4 × 10 ^-5 μm ³ and the average power spectral density P _low = 1 × 10 ^-3 μm ³ .

Further, in order to compare with the base material 2 before film formation, the average power spectral densities _High and _Plow were calculated in the same manner on the surface of the base material 2 in the place where the ceramic film 3 was not formed. The spectral density P _high = 0.4 × 10 ^-5 μm ³ and the average power spectral density P _low = 0.4 × 10 ^-3 μm ³ . From this, at the time of film formation, particles having a minimum particle diameter of 0.05 μm and a maximum particle diameter of 0.3 μm derived from β-Si ₃ N ₄ powder C were formed into a film while being embedded in the substrate, so that the average power spectral density P _high was increased. In addition, the mixed powder contains particles with a minimum particle diameter of 0.3 μm and a maximum particle diameter of 6 μm derived from β-Si ₃ N ₄ powder D, which increases from before the film formation and does not contribute to the film formation. It is considered that the powder also increased from before the film formation by _denting the base material 2.

As a result of evaluating the bonding force of the ceramic laminate 1 of Example 5, the ceramic film 3 of the ceramic laminate 1 was peeled off and the pin was removed, but the breaking stress was 50 MPa, which was about the same as that of Example 1. Since the ceramic laminate 1 of Example 5 has a breaking stress of 50 MPa, the bonding force was evaluated as ◯.

In order to compare with Examples 1 to 5, the ceramic laminate of Comparative Example 1 prepared so as not to form the unevenness corresponding to the wave 4b having a low wave number, and the unevenness corresponding to the wave 4a having a high wave number (exhibiting the anchor effect). The bonding force was also evaluated in the same manner as in Examples 1 to 5 with respect to the ceramic laminate of Comparative Example 2 produced so as not to form unevenness).

(Comparative Example 1)
In Comparative Example 1, α-Al ₂ O ₃ powder A having a minimum particle diameter of 0.1 μm, a maximum particle diameter of 0.4 μm, and a median diameter of 0.2 μm was used as the ceramic powder 17 and was pre-polished as the base material 2. A ceramic laminate was produced in the same manner as in Example 1 using the oxygen-free Cu base material subjected to the above. In Comparative Example 1, the base material is not treated in advance or the above-mentioned α-Al ₂ O ₃ powder B is not mixed, so that the unevenness corresponding to the wave 4b having a low wave number is not formed.

Further, when the D _max was calculated for the produced ceramic laminate of Comparative Example 1 by the same method as in Example 1, it was found that D _max = 0.4 μm. From this result, in the ceramic laminate of Comparative Example 1, the wavelength range λ _short of the wave 4a having a high wave number is 0.1 μm ≤ λ _short ≤ 0.4 μm, and the wavelength range λ _long of the wave 4b having a low wave number (long wavelength) is 0. It was determined that 4 μm <λ _long ≤ 10 μm.

In the same manner as in Example 1, the power spectral density P (k) of the ceramic laminate of Comparative Example 1 was determined. With respect to the obtained power spectrum density P (k), the wavenumber range of the high wavenumber wave 4a calculated from the wavelength range determined earlier is 1 / 0.4 = 2.5 μm ^-1 ≤ 1 / λ _short = k _high ≤ 1/0. .1 = 10 μm ^-1 , wavenumber range of low wavenumber 4b 1/10 = 0.1 μm ^-1 ≤ 1 / λ _long = k _low <1 / 0.4 = 2.5 μm ^-1 and average power When the spectral densities P _high and P _low were calculated, the average power spectral density P _high = 4 × 10 ^-5 μm ³ and the average power spectral density P _low = 0.4 × 10 ^-3 μm ³ .

Further, in order to compare with the base material 2 before film formation, the average power spectral densities _High and _Plow were calculated in the same manner on the surface of the base material 2 in the place where the ceramic film 3 was not formed. The spectral density P _high = 0.4 × 10 ^-5 μm ³ and the average power spectral density P _low = 0.4 × 10 ^-3 μm ³ . From this, the particles of α- _{Al 2} O ₃ powder A having a minimum particle diameter of 0.1 μm and a maximum particle diameter of 0.4 μm were formed into a film while being sunk into the substrate at the time of film formation, so that the value increased from before the film formation. However, it is considered that the _powder did not change from before the film formation.

As a result of evaluating the bonding force of the ceramic laminate of Comparative Example 1, the ceramic film 3 was peeled off and the pins were removed, and the breaking stress was 20 MPa, which was lower than that of Examples 1 to 5. Since the ceramic laminate of Comparative Example 1 had a breaking stress of 20 MPa, the bonding force was evaluated as x.

(Comparative Example 2)
In Comparative Example 2, α-Al ₂ O ₃ powder A having a minimum particle diameter of 0.1 μm, a maximum particle diameter of 0.4 μm, and a median diameter of 0.2 μm was used as the ceramic powder 17, and the base material 2 was scratched in advance. A ceramic laminate was produced by the same method as in Example 1 using a cemented carbide substrate that had been subjected to etching after being attached. In Comparative Example 2, by using a cemented carbide base material as the base material 2, the ceramic fine particles are less likely to sink into the base material 2 during film formation, and unevenness corresponding to the wave 4a having a high wave frequency is prevented from being formed. On the other hand, by scratching the base material 2 in advance and then etching the base material 2, unevenness corresponding to the wave 4b having a low wave number is formed on the base material 2.

Further, when the D _max was calculated for the produced ceramic laminate of Comparative Example 2 by the same method as in Example 1, it was found that D _max = 0.4 μm. From this result, the wavelength range λ _short of the high wave number wave 4a in the ceramic laminate of Comparative Example 2 is 0.1 μm ≤ λ _short ≤ 0.4 μm, and the wavelength range λ _long of the low wave number wave 4b is 0.4 μm <λ. It was determined that _long ≤ 10 μm.

In the same manner as in Example 1, the power spectral density P (k) of the ceramic laminate of Comparative Example 2 was determined. With respect to the obtained power spectrum density P (k), the wavenumber range of the high wavenumber wave 4a calculated from the wavelength range determined earlier is 1 / 0.4 = 2.5 μm ^-1 ≤ 1 / λ _short = k _high ≤ 1/0. .1 = 10 μm ^-1 , wavenumber range of low wavenumber 4b 1/10 = 0.1 μm ^-1 ≤ 1 / λ _long = k _low <1 / 0.4 = 2.5 μm ^-1 and average power When the spectral densities P _high and P _low were calculated, the average power spectral density P _high = 1 × 10 ^-5 μm ³ and the average power spectral density P _low = 1 × 10 ^-3 μm ³ .

Further, in order to compare with the base material 2 before film formation, the average power spectral densities _High and _Plow were calculated in the same manner on the surface of the base material 2 in the place where the ceramic film 3 was not formed. The spectral density P _high = 1 × 10 ^-5 μm ³ and the average power spectral density P _low = 1 × 10 ^-3 μm ³ . From this, the particles of α- _{Al 2} O ₃ powder A having a minimum particle diameter of 0.1 μm and a maximum particle diameter of 0.4 μm were formed into a film without being embedded in the substrate at the time of film formation. It is considered that there was no change from before, and that the _powder did not change from before the film formation.

As a result of evaluating the bonding force of the ceramic laminate of Comparative Example 2, the ceramic film was peeled off and the pin was removed, and the breaking stress was 20 MPa, which was lower than that of Examples 1 to 5. Since the ceramic laminate of Comparative Example 2 has a breaking stress of 20 MPa, the bonding force was evaluated as x.

Table 1 shows the average power spectral densities of the ceramic laminates of Examples 1 to 5 and the ceramic laminates of Comparative Examples 1 and 2 _High , _Plow , and the evaluation results of the bonding force.

As described above, it was confirmed that the ceramic laminates 1 of Examples 1 to 5 had better bonding strength than the ceramic laminates of Comparative Examples 1 and 2. Since the ceramic laminates 1 of Examples 1 to 5 have an average power spectral density P _high of 2 × 10 ^-5 μm ³ or more and an average power spectral density P _low of 0.5 × 10 ^-3 μm ³ or more. Since there are irregularities corresponding to the high wave number wave 4a that exerts the anchor effect and there are irregularities corresponding to the low wave number wave 4b, the total distance of the region where the unevenness exhibiting the anchor effect exists (total). It is considered that this is because the surface area) has increased. It was confirmed that the ceramic laminate 1 had a high bonding force regardless of whether the ceramic film was α-Al ₂ O ₃ or β-Si ₃ N ₄ .

The ceramic laminate 1 of Examples 1 to 3 and 5 has a better bonding force than the ceramic laminate 1 of Example 4. Since the ceramic laminates 1 of Examples 1 to 3 and 5 have an average power spectral density P _high of 2 × 10 ^-5 μm ³ or more and an average power spectral density P _low of 1 × 10 ^-3 μm ³ or more. Since there are irregularities corresponding to the high wave number wave 4a that exerts the anchor effect and the average power spectral density _Power is larger than that of Example 4, the total distance of the regions where the irregularities that exert the anchor effect exist (total). It is probable that the surface area) was larger than that of Example 4.

In particular, the ceramic laminate 1 of Example 3 is excellent in bonding strength as compared with other examples. Since the ceramic laminate 1 of Example 3 has an average power spectral density P _high of 2 × 10 ^-5 μm ³ or more and an average power spectral density P _low of 3 × 10 ^-3 μm ³ or more, it has an anchor effect. Since the wave 4a having a high wave number to exert is present and the average power spectral density _Plow is larger than that of the other examples, the total distance (total surface area) of the region where the unevenness exhibiting the anchor effect exists is further increased. it is conceivable that.

The ceramic laminate of Comparative Example 1 has an average power spectral density P _high of 2 × 10 ^-5 μm ³ or more, but an average power spectral density P _low of less than 0.5 × 10 ^-3 μm ³ and thus is an anchor. The total distance (total surface area) of the area where the unevenness that exerts the effect exists is small. Therefore, it is considered that the ceramic laminate of Comparative Example 1 has a lower bonding force than Examples 1 to 5.

The ceramic laminate of Comparative Example 2 has an average power spectral density P _low of 0.5 × 10 ^-3 μm ³ or more, but an average power spectral density P _high of less than 2 × 10 ^-5 μm ³ and is therefore an anchor. There are few irregularities that are effective. Therefore, it is considered that the ceramic laminate of Comparative Example 2 has a lower bonding force than Examples 1 to 5.

1 Ceramic laminate 2 Base material 3 Ceramic film 4 Film / substrate interface 4a High wavenumber (short wavelength) wave 4b Low wavenumber (long wavelength) wave 5 Ceramic film crystal grain λ _short High wavenumber (short wavelength) wave Wavelength range λ _long Wavenumber range of low wavenumber (long wavelength) D _max Maximum value of crystal grain size P (k) Power spectrum density k Wavenumber k _high Wavenumber range of high wavenumber (short wavelength) wave _low wavenumber Wavenumber range of (long wavelength) waves 11 Aerosol deposition device 12 Aerosolization container 13 Formation chamber 14 Aerosol transfer pipe 15 Vacuum pump 16 Gas supply system 17 Ceramic powder 18 Transfer gas pipe 19 Hoisting gas pipe 20 Stage 21 Horizontal drive mechanism

Claims (4)

In a ceramic laminate in which a ceramic film is laminated on a substrate,
The interface between the ceramic film and the base material appearing on the cross section of the ceramic laminate is represented by a curve including a high wave number component and a low wave number component.
The wavelength range λ _short of the high wave number component is 0.1 μm or more, and the maximum value D _max or less of the crystal grain size of the ceramic film.
The wavelength range λ _long of the low wavenumber component is larger than the maximum value D _max and 10 μm or less.
The average power spectral density P _high of the high frequency component calculated from the curve is 2 × 10 ^-5 μm ³ or more.
A ceramic laminate having an average power spectral density P _low of 0.5 × 10 ^-3 μm ³ or more of the low wavenumber component calculated from the curve. The ceramic laminate according to claim 1, wherein the average power spectral density P _low of the low wavenumber component is 1 × 10 ^-3 μm ³ or more. The ceramic laminate according to claim 1, wherein the average power spectral density Plow of the _low wavenumber component is 3 × 10 ^-3 μm ³ or more. The ceramic laminate according to any one of claims 1 to 3, wherein the base material is a metal material.

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