WO2005037732A1

WO2005037732A1 - Multilayer ceramic electronic component/film electronic component and its manufacturing method

Info

Publication number: WO2005037732A1
Application number: PCT/JP2004/015499
Authority: WO
Inventors: Yoshiaki Kinemuchi; Koji Watari; Shoji Uchimura; Hirohide Ishiguro; Hideki Morimitsu
Original assignee: National Institute Of Advanced Industrial Science And Technology; Sinto V-Cerax, Ltd
Priority date: 2003-10-21
Filing date: 2004-10-20
Publication date: 2005-04-28
Also published as: JP2005126255A

Abstract

The invention provides a baking method comprising a baking step for multilayer ceramic electronic components such as multilayer piezoelectric ceramic actuators and multilayer piezoelectric ceramic transformers and film-structure electronic components while suppressing cracking in layers and separation of layers due to contraction difference during heating. The inventions relates to a baking method including a baking step for baking a film or a multilayer structural body on a substrate, wherein a centrifugal force is exerted on the film or the interface of the multilayer in a vertical direction to effect pressure-sintering, and the contraction of the film or the interface between layers in a horizontal direction is significantly decreased so as to prevent defects. The intention further relates to a baking method improving the interface adhesion by matching the junction interface and to a film or multilayer structural body and a filmy or multilayer electronic member fabricated by the baking method. According to the invention, a multilayer ceramic electronic component and a film electronic component hardly causing defects such as cracking and delaminating can be manufactured and provided.

Description

Specification

Multilayer ceramic electronic components '' Membrane electronic components and manufacturing method thereof

Technical field

The present invention relates to a method for firing a film or a multilayer structure on a substrate and a fired product of the film or the multilayer structure. More specifically, the present invention relates to a method for firing a film or a multilayer structure on a substrate to fire them. And a new firing method capable of manufacturing a film or a laminated structure capable of suppressing generation of defects such as cracks and delamination due to a difference in shrinkage ratio. The present invention also relates to a film or a laminated structure in which shrinkage in a tangential direction with respect to a substrate manufactured by using the method is suppressed, and an applied product thereof.

The present invention relates to, for example, a technical field of a method for degreasing and firing a laminated structure without a film on a substrate, which is a material for a laminated electronic ceramic or a film electronic component having high functionality, Highly reliable film that suppresses the occurrence of defects such as cracks and delamination due to the difference in shrinkage, increases the adhesion of the film or layer, and does not peel off during use. In addition, the present invention is useful as a method for producing a new material suitable for a material of a film electronic component and a product thereof, which is capable of producing a multilayer structure. The present invention relates to a method for producing a multilayer ceramic electronic component such as a multilayer ceramic capacitor, a multilayer piezoelectric actuator, a multilayer piezoelectric transformer, and a film-shaped electronic member such as a membrane gas sensor and a solid fuel cell electrode, and a method for degreasing and firing. And their products.

Background art

[0003] A conventional general multilayer ceramic electronic component such as a multilayer piezoelectric ceramic unit and a multilayer piezoelectric ceramic transformer has a structure in which a plurality of ceramic sheets are stacked and an internal electrode is interposed between the ceramic sheets. It has the structure made to be. When these laminated structures are heated, each layer sinters, resulting in shrinkage and a dense product. However, since the temperature dependence of the shrinkage behavior differs depending on the material, when one material shrinks, the other material does not shrink, and thus a stress is generated due to the difference in shrinkage. Due to this stress, During the production of the laminated structure, cracks may occur in the layers or the layers may peel off.

[0004] Further, when the adhesive force at the layer interface is weak, the component may be peeled off at the interface during use of the component (this phenomenon is referred to as delamination). In the case where the element itself vibrates, such as a tutor-multilayer piezoelectric ceramic transformer, there is a possibility that delamination may occur during operation. A similar problem occurs when a film is formed on a substrate, and is a difficult problem to be solved in fabricating a film device.

[0005] In order to solve such a problem, for example, in the prior art document, a layer having a concavo-convex shape at an interface portion is added to enhance the adhesive force by mechanical engagement to suppress the separation of the interface. (Patent Document 1). In addition, other documents attempt to reduce the difference in shrinkage by adjusting the composition of the electrode material (Patent Documents 2, 3, and 4). In addition, other documents propose that the plasticity of the layer is increased by adjusting the atmosphere during the temperature increase, thereby alleviating the occurrence of stress and suppressing the occurrence of cracks. Licensing 5). Further, another document proposes to suppress generation of cracks by firing by microwave irradiation (Patent Document 6).

[0006] However, the method of imparting an uneven shape to the interface does not consider the sintering behavior at all, and does not contribute to the fundamental solution, that is, the relaxation of internal stress at all. On the other hand, reducing the mismatch in shrinkage by controlling the composition and adjusting the atmosphere is an essential solution and is subtle. However, when one material composition is changed for the purpose of improving characteristics, there is a problem that the other composition needs to be a new composition so that no stress is generated. Firing using microwave irradiation is characterized by maintaining the sample temperature uniformly and heating rapidly, but does not contribute to the relaxation of internal stress at all, and is not an essential solution.

Patent Document 1: Patent No. 3006518

Patent Document 2: JP-A-8-255509

Patent Document 3: JP-A-9-290985

Patent Document 4: Patent No. 3397753

Patent Document 5: JP-A-2003-17358 Patent Document 6: JP-A-6-267785

Disclosure of the invention

Problems to be solved by the invention

[0008] In such a situation, the present inventors, in view of the above-mentioned prior art, have developed a new multilayer structure electronic ceramic and a film that can drastically solve the problems in the above-mentioned prior art. As a result of intensive studies with the aim of developing a manufacturing technology for electronic components, it was found that the intended purpose could be achieved by applying a centrifugal force when heating the sample, and the present invention was completed. Was. The present invention relates to a method for firing a film or a laminated structure capable of suppressing the occurrence of defects such as cracks and layer separation occurring during firing, a film or a laminated structure manufactured using the method, And a film-shaped or laminated electronic member.

Means for solving the problem

[0009] The present invention for solving the above-mentioned problems is characterized in that, in a fired product of a film or a laminated structure on a substrate, the film has anisotropy in shrinkage and hardly shrinks in a tangential direction to the substrate. A fired product of the above-mentioned film or laminated structure, wherein generation of defects generated therein is suppressed. In the fired product, the generation of cracks and peeling of layers during firing is suppressed, the generation of cracks and peeling of layers due to the generation of gas during degreasing is suppressed, In a preferred embodiment, the adhesive strength of the laminated structure is improved, and the material of the film or the laminated structure is ceramics, metal, or a composite material containing these. Further, the present invention is a film-shaped or laminated electronic member comprising the film or the laminated structure in which the above-mentioned contraction in the tangential direction is suppressed. In a preferred embodiment, the member is a capacitor, a thermistor, a Nolister, an inductor, a piezoelectric actuator, a piezoelectric transformer, a sensor, or an electrode.

[0010] In the present invention, in a baking process of a film or a laminated structure on a substrate, a sample is placed in a rotating body, and a centrifugal force is applied to the film or the laminated structure by high-speed rotational movement of the rotating body, and simultaneously the heating is performed. A film or a laminated structure characterized by obtaining a fired product in which the occurrence of defects such as cracks and delamination during firing is suppressed by utilizing the anisotropy of shrinkage due to the action of centrifugal force. And a method for producing a fired product. The method comprises the steps of: The sample is placed in a rotating body during the degreasing process of the structure, and a centrifugal force is applied to the membrane or the laminated structure by the high-speed rotating motion of the rotating body, and at the same time, the sample is heated and the sample is pressurized by the action of the centrifugal force. As a result, a fired product that suppresses the occurrence of defects such as cracks and layer delamination due to the generation of gas during degreasing is obtained, and the sample is placed in the rotating body during the sintering process of the film or laminated structure on the substrate. Installed, applying a centrifugal force to the film or laminated structure by the high-speed rotation of the rotating body and simultaneously heating it to obtain a fired product with an increased adhesive strength of the film or layer. 500-100, OOOrpm, centrifugal force applied perpendicular to the membrane or laminated interface, pressure applied to the membrane or laminated interface should be 0.1 to 100 MPa, material of membrane or laminated structure Is ceramics, metal, or ceramics and gold And a composite material of the genus.

Next, the present invention will be described in more detail.

The present invention is characterized in that in a heating process of a laminated electronic ceramic or a film electronic component, a sample is pressurized by heating a centrifugal acceleration and simultaneously heated. That is, in the present invention, a sample of a laminated ceramic or a membrane electronic component is placed in a rotating body, and a centrifugal force is applied to the sample of the laminated ceramic or the membrane electronic component by high-speed motion of the rotating body to simultaneously heat the sample. When a binder for imparting moldability to the sample is used, a degreasing step is required. Generally, in the production of a laminated electronic ceramics or a membrane electronic component, a degreasing step is required. Delamination due to gas generation is the first problem. In the present invention, by applying a centrifugal pressure in a direction perpendicular to the interface in the sample during the degreasing process, it is possible to suppress the deformation of the sample due to the generation of gas, and thereby, during the degreasing process. Defect generation can be suppressed.

[0012] Further, when the temperature is increased in the sintering process, the sample starts sintering and the sample shrinks. In this case, in the case of a laminated electronic ceramic, since the sample is composed of a different material, a difference in shrinkage is essentially generated due to a difference in sinterability of the material. In the case of a film electronic component, the substrate does not shrink at all, while the film shrinks due to sintering. In either case, this difference in shrinkage causes stress in the layer or film, and in order to relieve this stress, cracks and delamination occur in the material, and coarse pores are formed. To solve such problems Requires that these samples be manufactured to essentially eliminate the difference in shrinkage.

[0013] In the present invention, by applying a centrifugal force in a direction perpendicular to the interface in the sample during the sintering process, it is possible to suppress the occurrence of these problems. By the way, the difference in the shrinkage rate that matters here is specifically the difference in the shrinkage rate in the direction parallel to the interface between the layers and the films. For example, in uniaxial pressure sintering, shrinkage occurs only in the pressing direction, and does not shrink at all in the direction perpendicular to the pressing direction. In the present invention, by performing sintering while applying pressure perpendicular to the layer or film interface, there is no difference in shrinkage in the direction parallel to the layer or film interface. Therefore, generation of cracks and delamination and formation of coarse pores do not occur.

[0014] Conventionally, the pressurizing method is a mechanical method, that is, in the case of force electronic materials that have been performed by a pressing method, there is a problem of deterioration of characteristics due to contamination of impurities. Pressurization is very disadvantageous in terms of impurity contamination. On the other hand, in the present invention, since pressurization by centrifugal force is used, solid contact for pressurization is unnecessary, which is very advantageous. If the material has magnetism or charge, it can be pressed in a non-contact manner by electromagnetic force. Generally, at high temperatures such as sintering, such force does not work effectively. This is disadvantageous because the possible materials are limited.

[0015] As described above, a device in which the element itself vibrates, such as a multi-layer piezoelectric ceramic actuator and a multi-layer piezoelectric ceramic transformer, has a problem in that the bonding force at the interface between layers or films is insufficient. Since delamination occurs during driving, it is necessary to improve the adhesive force at the interface. Diffusion bonding is a method of bonding (joining) ceramics together. In this method, mass transfer such as creep and diffusion is promoted by heating while applying pressure to achieve interface matching, and a method of obtaining a strong adhesive interface. Also in the present invention, since the pressurization by centrifugal force is performed during the heating of the sample, a physical phenomenon similar to that of diffusion bonding occurs, and strong adhesion at the interface is achieved.

Examples of the sample include LTCC ceramics composed of borosilicate glass and alumina, BaTiO, PbTiO—PbZrO, ferrite, anoremina, Ni—Cu—Al, Ag—Ag—Pd, A

3 3 3

u, Pt, RuO, glass, PZT, ZrO, CeO, but are limited to these

2 2 2

The present invention can be applied to any ceramics, metal materials, and composite materials of ceramics and metals. Further, as the substrate, alumina, aluminum nitride, silicon nitride, The force exemplified by PZT, silicon, quartz, glass, MgO, etc. The present invention is not limited to these.

[0017] In the present invention, a centrifugal force is applied to the sample layer or membrane interface in a vertical direction. Since the centrifugal force is proportional to the mass of the sample, it is necessary to adjust the number of rotations appropriately to control the pressure at the layer and at the interface, and the pressure needs to be applied perpendicular to the interface. In the present invention, it is important to fire the film or the laminated structure on the substrate under these specific conditions. In this case, the number of rotations is 500-100,000 rpm, and the pressure at the layer and the interface is preferably 0.1 to 100 MPa. The present invention is not limited to these. Also, depending on the sample, the strength of the molded body may be low.In such a case, it is necessary to adjust the pressure at a low temperature so that the molded body is not destroyed, and it is preferable to perform the operation at IMPa or lower. . However, the present invention is not limited to these.

In the present invention, the sample of the multilayer electronic ceramic or the film electronic component is heated under the centrifugal force. When the pressure is low, that is, when the pressure is lower than lOMPa, it is preferable to perform the heating at the same temperature as the normal sintering temperature. , The sintering temperature can be lowered. When the sintering temperature is lowered, the residual stress due to the difference in the coefficient of thermal expansion between the materials can be reduced, which is particularly effective when micro defects become a problem. For example, when a pressure of about 30 MPa is applied, the sintering temperature may be lowered by about 20%. Examples of the heating method include resistance heating, induction heating, microwave heating, infrared heating, and laser heating.

However, the present invention is not limited to these. Further, as the centrifugal sintering means, any apparatus having a means for applying a centrifugal force to the sample and a means for heating the sample by these heating methods can be used, and the type thereof is not limited. According to the present invention, it is possible to produce a laminated structure or a film material free of defects such as cracks and delamination due to a difference in shrinkage ratio, thereby producing a laminated structure free of those defects. And film electronic components can be manufactured and provided.

The invention's effect

[0020] In the multilayer electronic ceramic of the present invention, according to the method for manufacturing a sample of a film electronic component, (1) the sample is pressurized by the action of centrifugal force, and the sample is deformed due to generation of gas during degreasing. By suppressing the cracking, it is possible to suppress the occurrence of defects such as cracks and delaminations. (2) In the sintering process, the anisotropy of the shrinkage due to the action of centrifugal force is used. It is possible to suppress the occurrence of defects such as cracks and delaminations due to the difference in shrinkage. (3) Further, since the interface is weakened by the pressing action, the adhesive strength of the film and the layer is reduced. To produce and provide highly reliable multilayer electronic ceramics and membrane electronic components with high reliability without the layers and films peeling during use. .

BEST MODE FOR CARRYING OUT THE INVENTION

Next, the present invention will be specifically described based on examples, but the present invention is not limited by the following examples.

Example 1

In this example, a sintered body was manufactured by centrifugally sintering LTCC ceramics using the firing method of the present invention.

This LTCC was composed of 70 mass% and 30 mass% alumina of borosilicate glass, and the composition of the borosilicate glass was SiO: BO: K0 = 78: 20: 2. The centrifugal acceleration is

2 2 3 2

87 kmZs. As a comparative example, sintering was performed even at a centrifugal acceleration of Okm / s. FIG. 1 shows the relationship between the sintering temperature (T) and linear shrinkage (ΔΐΖΐο) when LTCC ceramics are centrifugally sintered using the firing method of the present invention. In the figure, r indicates the linear shrinkage in the rotational radius direction, and Θ indicates the shrinkage in the rotational tangential direction. It can be seen that due to the centrifugal force, the shrinkage occurs mainly in the radial direction of rotation and hardly shrinks in the tangential direction of rotation. On the other hand, in normal sintering, it shrinks uniformly. This indicates that centrifugal sintering by the firing method of the present invention is effective for viscous sintering.

Example 2

In this example, a sintered body was manufactured by centrifugally sintering BaTiO using the firing method of the present invention.

Three

did.

BaTiO was added with LiF and BaCO as sintering aids. The amount of these additives

3 3

O is 2mol% for BaTiO, LiF is 0.5mass% for BaTiO and BaCO mixture

3 3 3 3

And With this composition, a liquid phase forms at 610 ° C. Centrifugal acceleration was set 87kmZs ^2. As a comparative example, the centrifugal acceleration is also performed sintered at Okm / s ^2. Figure 2 shows BaTiO

3 shows the relationship between the sintering temperature (T) and the linear shrinkage (Δ 1/1 o) when centrifugal sintering is performed using the firing method of the present invention. In the figure, r indicates the linear shrinkage in the radial direction of rotation, and 示し indicates the shrinkage in the rotational tangential direction. Due to the centrifugal force, the contraction occurs mainly in the radial direction of rotation, and almost no contraction occurs in the tangential direction of rotation. On the other hand, in normal sintering, it shrinks uniformly. This shows that centrifugal sintering by the firing method of the present invention is also effective for liquid phase sintering.

Example 3

In this example, a sintered body was manufactured by centrifugally sintering the fly using the firing method of the present invention.

The ferrite composition was FeO: CuO: ZnO: NiO = 49: 6: 25: 20 in molar ratio. Centrifugation

twenty three

Acceleration, was 87kmZs ^2. As a comparative example, the centrifugal acceleration is also performed sintered at Okm / s ^2. FIG. 3 shows the relationship between the sintering temperature (T) and the linear shrinkage (ΔΐΖΐο) when ferrite is sintered by centrifugation using the sintering method of the present invention. In the figure, r indicates the linear shrinkage in the rotational radius direction, and Θ indicates the shrinkage in the rotational tangential direction. Due to the centrifugal force, the contraction occurs mainly in the radial direction of rotation, and almost no contraction occurs in the rotational tangential direction. On the other hand, in normal sintering, it shrinks uniformly. This shows that centrifugal sintering by the firing method of the present invention is also effective for solid phase sintering.

Example 4

In the present example, Ni was centrifugally sintered using the firing method of the present invention to produce a sintered body. The centrifugal acceleration was 87 km / s ² . As a comparative example, sintering was performed at a centrifugal acceleration of Okm / s ² . FIG. 4 shows the relationship between the sintering temperature (T) and the linear shrinkage (ΔΐΖΐο) when Ni is sintered by centrifugation using the sintering method of the present invention. In the figure, r indicates the linear shrinkage in the rotational radius direction, and Θ indicates the shrinkage in the rotational tangential direction. Due to the centrifugal force, the contraction occurs mainly in the radial direction of rotation, and almost no contraction occurs in the rotational tangential direction. On the other hand, in normal sintering, it shrinks uniformly. This shows that centrifugal sintering by the firing method of the present invention is also effective for metallurgy. Example 5

In the present embodiment, a laminated ceramic of BaTiO and Ni is laminated with these sheet compacts.

Three

It produced by doing. BaTiO was added with LiF and BaCO as sintering aids. Sheet

3 3

The thickness was about 60 m in each case, and after laminating them, the molded product was about 1.3 mm thick. The molded body was fired in a vacuum at a temperature of 1000 ° C. for a holding time of 20 minutes at a centrifugal acceleration of 87 kmZs ² using the firing method of the present invention. The molded body was fired without applying a centrifugal acceleration to obtain a comparative sample. FIG. 5 shows a cross-sectional structure of the sintered body. The pore structure is made uniform by centrifugal sintering using the firing method of the present invention. On the other hand, in normal sintering, a coarse pore connected structure that causes cracks is observed. This organizational feature is due to the fact that under centrifugal force, densification progresses due to radial contraction, and no contraction mismatch occurs in the tangential direction.

Example 6

[0027] Copper powder was screen-printed on a quartz substrate (film thickness 10 m) and centrifugally sintered using the firing method of the present invention. Centrifugal acceleration 0, 56, and was three conditions 87km / s ^2. The sintering temperature was 850 ° C and the holding time was 20 minutes. Figure 6 shows a photograph of the film surface after sintering. When no centrifugal force is applied, remarkable cracks and delamination are observed, but it can be seen that the cracks decrease and increase as the centrifugal port speed increases.

Example 7

[0028] Al O was bonded to stainless steel under centrifugal pressure using the firing method of the present invention. here

twenty three

Used aluminum for the intermediate layer. The bonding temperature was 650 ° C and the holding time was 2 hours. FIG. 7 shows the centrifugal pressure (Pc) dependence of the tensile strength (σ f) of the joined body. It can be seen that as the centrifugal pressure increases, the tensile strength, ie, the adhesive strength at the interface, increases. When no centrifugal force was applied, the sample did not adhere at all.

Example 8

[0029] Copper powder was screen-printed on a quartz substrate (film thickness 10 m) and centrifugally sintered using the firing method of the present invention. Centrifugal acceleration a 87kmZs ^2, sintering temperature 600 ° C, the retention time was 1 Omin. Thereafter, the film adhesion was evaluated by a scratch test. As a comparative example The sample was measured when no centrifugal acceleration was applied. Figure 8 shows the results. The horizontal axis shows the pressing force (Fn), and the vertical axis shows the tangential force (Ft). The higher the Ft, the higher the adhesive strength, but it can be seen that the adhesive strength is increased by centrifugal sintering using the firing method of the present invention.

Industrial applicability

As described in detail above, the present invention relates to a method for firing a film or a multilayer structure, a multilayer ceramic electronic component manufactured using the firing method, a film electronic component, and a method for manufacturing the same. According to the present invention, it is possible to suppress the deformation of the sample due to the generation of gas during degreasing in the degreasing process, and to suppress the occurrence of defects such as cracks and delamination due to the difference in shrinkage in the sintering process. can do. By using the sintering method of the present invention, the alignment of the interface of the layer or the film is enhanced, so that the adhesive force of the layer or the film is increased, and the layer or the film is not peeled during use, and high reliability is obtained. Electronic components can be manufactured. The present invention is intended to reduce defects, that is, to reduce the number of defects in the production of multilayer ceramic electronic components such as multilayer ceramic capacitors, multilayer piezoelectric actuators and multilayer piezoelectric transformers, and membrane electronic members such as membrane gas sensors and solid fuel cell electrodes. This is useful for improving the retention and, further, for realizing the production of highly reliable products.

Brief Description of Drawings

FIG. 1 is a view showing a linear shrinkage ratio of LTCC. The horizontal axis is the sintering temperature and the vertical axis is the linear shrinkage (Example 1).

FIG. 2 is a view showing a linear shrinkage ratio of BaTiO. The horizontal axis is the sintering temperature, and the vertical axis is the linear shrinkage.

Three

(Example 2).

FIG. 3 is a view showing a linear shrinkage ratio of a flight. The horizontal axis is the sintering temperature, and the vertical axis is the linear shrinkage (Example 3).

FIG. 4 is a view showing a linear shrinkage ratio of Ni. The horizontal axis is the sintering temperature, and the vertical axis is the linear shrinkage (Example 4).

FIG. 5 is a cross-sectional photograph of a laminated ceramic of BaTiO and Ni. Figure (a) is normal sintering, Figure (b) is

Three

It is centrifugal sintering using the firing method of the present invention. Figures (c) and (d) are enlarged views of Figures (a) and (b), respectively. Arrows in the figure (b) indicate the direction in which the centrifugal force is applied (Example 5). ) o

FIG. 6 is a photograph of the surface of a copper thick film after sintering. The numerical value at the top of the figure indicates the centrifugal acceleration (Example 6).

FIG. 7 shows the bonding strength of A1 O to stainless steel. The horizontal axis is the centrifugal pressure and the vertical axis is the tensile strength

twenty three

The degree is shown (Example 7).

FIG. 8 shows a scratch test result of a copper thick film. The horizontal axis shows the pressing force, the horizontal axis shows the pressing force, and the vertical axis shows the tangential force! /, (Example 8).

Claims

The scope of the claims

[1] A fired product of a film or a laminated structure on a substrate has anisotropy in shrinkage and suppresses generation of defects that occur during firing when shrinkage in the tangential direction to the substrate is almost negligible.

V. A fired product of the above film or laminated structure, characterized in that:

2. The fired product of the film or the laminated structure according to claim 1, wherein generation of cracks and delamination occurring during firing is suppressed.

[3] The fired product of the film or the multilayer structure according to claim 1, wherein generation of cracks and delamination due to generation of gas during degreasing is suppressed.

[4] The fired product of the film or the laminated structure according to claim 1, wherein the adhesive strength of the film or the laminated structure to the substrate is improved.

[5] The fired product of the film or the laminated structure according to claim 1, wherein the material of the film or the laminated structure is a ceramic, a metal, or a composite material containing these.

[6] A film-shaped or laminated electronic member comprising the film or the laminated structure in which shrinkage in the tangential direction is suppressed according to any one of claims 1 to 5.

7. The film-shaped or laminated electronic member according to claim 6, wherein the electronic member is a capacitor, a thermistor, a resistor, an inductor, a piezoelectric actuator, a piezoelectric transformer, a sensor, or an electrode.

[8] In the baking process of the film or the laminated structure on the substrate, the sample is placed in a rotating body, centrifugal force is applied to the film or the laminated structure by the high-speed rotation of the rotating body, and the centrifugal force is applied to the film or the laminated structure at the same time. By using the anisotropy of shrinkage due to the action, it is possible to obtain a fired product in which the occurrence of defects such as cracks and delamination during firing is suppressed, and a fired product of a film or multilayer structure is characterized. Manufacturing method.

[9] The sample is placed in a rotating body in the degreasing process of the film or laminated structure on the substrate, and centrifugal force is applied to the film or laminated structure by the high-speed rotation of the rotating body. 9. The method according to claim 8, wherein the sample is pressurized by the action of a cardiac force to obtain a fired product in which generation of cracks and delamination such as delamination due to generation of gas during degreasing is suppressed.

[10] In the sintering process of a film or a laminated structure on a substrate, a sample is placed in a rotating body, and centrifugal force is applied to the film or the laminated structure by high-speed rotation of the rotating body, and heating is performed simultaneously. 9. The method according to claim 8, wherein a fired product having an increased adhesive strength of the film or layer is obtained.

[11] The method according to claim 8, wherein the rotation speed of the rotating body is 500-100, OOOrpm.

[12] The method according to claim 8, wherein a centrifugal force is applied in a direction perpendicular to the interface of the film or the lamination.

[13] The method according to claim 8, wherein the pressure applied to the film or the lamination interface is 0.1 to 100 MPa.

14. The method according to claim 8, wherein the material of the film or the laminated structure is ceramic, metal, or a composite material of ceramic and metal.