Film deposition method

Abstract

To provide a film deposition method capable of stably forming a ceramic film excellent in denseness and adhesion.SOLUTION: A film deposition method comprises: storing raw material particles obtained by mixing first ceramic particles having an average particle size of 3 μm or more and 7 μm or less with second ceramic particles pulverized powder consisting of ceramic particles formed of the same material as the first ceramic particles and including a particle size of 0.2 μm or more and 0.4 μm in a sealed container; forming the aerosol of the raw material particles by introducing gas into the sealed container; conveying the aerosol to a film deposition chamber maintained at a pressure lower than that of the sealed container through a conveying pipe connected to the sealed container to deposit an active species derived from the raw material fine particles on a base material stored in the film deposition chamber.SELECTED DRAWING: Figure 2

Description

[Technical field]

[0001] The present invention relates to a method for forming a ceramic film by utilizing an aerosol gas deposition method. [Background technology]

[0002] The aerosol gas deposition method (hereinafter also referred to as the AGD method) is a method in which raw material particles (aerosol raw material) contained in an aerosol container are stirred up by gas to become an aerosol, and then transported by a gas flow caused by the pressure difference between the aerosol container and the film-forming chamber, and collided with a substrate, forming a film at room temperature. In this method, the film formation speed is faster than other film-forming methods, and generally, it is possible to form a film with high density and high adhesion.

[0003] For example, Patent Documents 1 and 2 disclose a film formation method in which raw material particles contained in an aerosol-generating container are stirred up by a gas to become an aerosol, and the raw material particles are transported by a gas flow caused by a pressure difference between the aerosol-generating container and a film formation chamber, and are then collided with a substrate placed in the film formation chamber to be deposited.

[0004] Patent Document 3 also discloses a film formation method in which a gas is introduced into a sealed container containing electrically insulating raw material particles to generate an aerosol of the raw material particles, the aerosol is transported via a transport pipe connected to the sealed container to a film formation chamber which has a lower pressure than the sealed container, the aerosol is sprayed from a nozzle attached to the end of the transport pipe toward a target installed in the film formation chamber, the raw material particles are positively charged by colliding with the target, the charged raw material particles are discharged to generate fine particles of the raw material particles, and the generated fine particles are deposited on a substrate installed in the film formation chamber. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2014-9368 A [Patent Document 2] International Publication No. 2012 / 81053 [Patent Document 3] JP 2016-27185 A Summary of the Invention [Problem to be solved by the invention]

[0006] In recent years, there has been a demand for further improvements in the density and adhesion of ceramic films formed using the AGD method. The average particle size of the raw material particles that can be used to form films using the aerosol gas deposition method is generally considered to be optimal at around 0.5 μm, and films are formed using powders with particle sizes close to this size. On the other hand, if the particle size of the raw material particles is larger than this, it is thought that the density and adhesion of the film will be further improved, but it has been difficult to form a stable film.

[0007] In view of the above circumstances, an object of the present invention is to provide a film forming method capable of stably forming a ceramic film having excellent density and adhesion. [Means for solving the problem]

[0008] A film forming method according to one embodiment of the present invention includes the steps of: A raw material particle mixture of first ceramic particles having an average particle size of 3 μm or more and 7 μm or less and second ceramic particles which are pulverized powder of ceramic particles made of the same material as the first ceramic particles and have a particle size of 0.2 μm or more and 0.4 μm or less is placed in a sealed container; generating an aerosol of the raw material particles by introducing a gas into the sealed container; The aerosol is transported to a deposition chamber maintained at a lower pressure than the sealed container through a transport pipe connected to the sealed container; Active species derived from the raw material fine particles are deposited on a substrate accommodated in the film-forming chamber.

[0009] By mixing the first ceramic particles, which are relatively large in size, and the second ceramic particles, which are relatively small in size, as raw material particles, plasma is generated efficiently by the first ceramic particles, and the film formation efficiency is increased by the second ceramic particles, which have a larger specific surface area than the first ceramic particles. This makes it possible to stably form a dense, highly adhesive ceramic particle film.

[0010] The second ceramic particles may be formed by pulverizing ceramic particles having an average particle size smaller than that of the first ceramic particles.

[0011] The second ceramic particles may be formed by pulverizing the first ceramic particles.

[0012] During transport of the raw material particles from the sealed container to the film-forming chamber, the first ceramic particles may be charged, and surfaces of the second ceramic particles may be sputtered by discharges formed between the first ceramic particles and the substrate. Effect of the Invention

[0013] According to the present invention, a ceramic film having excellent density and adhesion can be stably formed. [Brief description of the drawings]

[0014] [Figure 1] FIG. 1 is a schematic diagram of an aerosolized gas deposition apparatus used in one embodiment of the present invention. [Diagram 2] 3 is a schematic diagram illustrating the operation of the aerosolized gas deposition apparatus. FIG. [Diagram 3] FIG. 13 is a diagram showing the particle size distribution of the PZT powder before the pulverization treatment used in Experimental Example 2. [Figure 4] FIG. 4 is a diagram showing an example of particle size distribution of the PZT powder after pulverization. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] Hereinafter, an embodiment of the present invention will be described with reference to the drawings.

[0016] FIG. 1 is a schematic diagram of an aerosolized gas deposition apparatus (hereinafter, also referred to as an AGD apparatus) 1 according to one embodiment of the present invention.

[0017] As shown in the figure, the AGD device 1 includes an aerosol-generating container 2 (sealed container), a film-forming chamber 3 (film-forming room), an exhaust system 4, a gas supply system 5, and a transfer pipe 6. The aerosol-generating container 2 and the film-forming chamber 3 each form an independent chamber, and the internal spaces of the chambers are connected to each other by the transfer pipe 6. The exhaust system 4 is connected to the aerosol-generating container 2 and the film-forming chamber 3. The gas supply system 5 is connected to the aerosol-generating container 2. The aerosol raw material P is stored in the aerosol-generating container 2. The substrate S is stored in the film-forming chamber 3.

[0018] The aerosol-generating container 2 contains the aerosol raw material P, and an aerosol is generated inside the aerosol-generating container 2. The aerosol-generating container 2 is connected to a ground potential, has a structure that can be sealed, and has a lid (not shown) for putting in and taking out the aerosol raw material P. The aerosol-generating container 2 is connected to an exhaust system 4 and a gas supply system 5. The AGD device 1 may be provided with a vibration mechanism that vibrates the aerosol-generating container 2 in order to agitate the aerosol raw material P, or a heating means that heats the aerosol raw material P in order to degas it (remove moisture, etc.).

[0019] The film formation chamber 3 accommodates the substrate S therein. The film formation chamber 3 is configured to be able to maintain the internal pressure. The film formation chamber 3 is connected to an exhaust system 4. The film formation chamber 3 is also provided with a stage 7 for holding the substrate S and a stage driving mechanism 8 for moving the stage 7 in two in-plane axial directions (X-axis and Y-axis). The stage 7 may have a heating means for heating the substrate S in order to degas the substrate S before film formation. The film formation chamber 3 may also be provided with a vacuum gauge that indicates the internal pressure. The film formation chamber 3 and the stage 7 are connected to ground potential.

[0020] The substrate S is typically a plate-shaped member. More specifically, the substrate S may be a metal substrate such as aluminum or stainless steel, a glass substrate such as quartz, or a ceramic substrate. The substrate S may have a surface layer such as a metal film or an insulating film formed thereon.

[0021] The exhaust system 4 evacuates the aerosol-generating container 2 and the deposition chamber 3. The exhaust system 4 includes a vacuum pipe 9, a first valve 10, a second valve 11, and a vacuum pump 12.

[0022] The vacuum pipe 9 connected to the vacuum pump 12 is branched and connected to the aerosol-generating container 2 and the deposition chamber 3. The first valve 10 is disposed on the vacuum pipe 9 between the branch point of the vacuum pipe 9 and the aerosol-generating container 2, and is configured to be capable of blocking the evacuation of the aerosol-generating container 2. The second valve 11 is disposed on the vacuum pipe 9 between the branch point of the vacuum pipe 9 and the deposition chamber 3, and is configured to be capable of blocking the evacuation of the deposition chamber 3. The configuration of the vacuum pump 12 is not particularly limited, and may be made up of a plurality of pump units. The vacuum pump 12 may be, for example, a mechanical booster pump and a rotary pump connected in series.

[0023] The gas supply system 5 supplies a carrier gas to the aerosol-generating container 2 for determining the pressure of the aerosol-generating container 2 and forming an aerosol. The carrier gas is, for example, N2, Ar, He, O2, dry air, etc. The gas supply system 5 includes a gas pipe 13, a gas source 14, a third valve 15, a gas flow meter 16, and a gas ejector 17.

[0024] The gas source 14 and the gas ejection body 17 are connected by a gas pipe 13, and a third valve 15 and a gas flow meter 16 are arranged on the gas pipe 13. The gas source 14 is, for example, a gas cylinder, and supplies a carrier gas. The gas ejection body 17 is arranged in the aerosol-generation container 2, and ejects the carrier gas supplied from the gas pipe 13 uniformly. The gas ejection body 17 can be, for example, a hollow body provided with a large number of gas ejection holes, and is arranged at a position covered by the aerosol raw material P, thereby enabling the aerosol raw material P to be effectively stirred up and aerosolized. The gas flow meter 16 indicates the flow rate of the carrier gas flowing through the gas pipe 13. The third valve 15 is configured to be capable of adjusting or cutting off the flow rate of the carrier gas flowing through the gas pipe 13.

[0025] The transport pipe 6 transports the aerosol formed in the aerosol-generating container 2 into the deposition chamber 3. One end of the transport pipe 6 is connected to the aerosol-generating container 2. The transport pipe 6 has a nozzle 18 provided at the other end. The nozzle 18 has a small round hole or a slit-shaped opening, and the ejection speed of the aerosol is determined by the opening diameter of the nozzle 18. The nozzle 18 is provided at a position facing the substrate S. The nozzle 18 is also connected to a nozzle movable mechanism (not shown) that determines the position and angle of the nozzle 18 to determine the ejection distance or ejection angle of the aerosol relative to the substrate S. The transport pipe 6 and the nozzle 18 are connected to a ground potential.

[0026] The inner surface of the transport pipe 6 may be made of a conductor. A straight metal pipe such as a stainless steel pipe may be used as the transport pipe 6. The length and inner diameter of the transport pipe 6 can be appropriately set, for example, the length is 300 mm to 1000 mm, and the inner diameter is 4.5 mm to 24 mm. In order to maintain the charge of the positively charged aerosol particles, an insulating fluororesin (for example, PTFE; polytetrafluoroethylene) pipe may be used.

[0027] The opening shape of the nozzle 18 may be circular or slot-shaped. In this embodiment, the opening shape of the nozzle 18 is slot-shaped, and the length is 10 times or more and 1000 times or less than the width. If the ratio of the length to the width of the opening is less than 10 times, it is difficult to effectively charge the particles inside the nozzle. If the ratio of the length to the width of the opening exceeds 1000 times, the charging efficiency of the particles is increased, but the amount of fine particles injected is limited and the film formation rate is significantly reduced. The ratio of the length to the width of the nozzle opening is preferably 20 times or more and 800 times or less, more preferably 30 times or more and 400 times or less.

[0028] The substrate S is made of a material such as glass, metal, or ceramic. As described above, the AGD method can form a film at room temperature and is a physical film formation method that does not involve a chemical process, so a wide range of materials can be selected as the substrate. In addition, the substrate S is not limited to a planar one, and may be a three-dimensional one.

[0029] The AGD device 1 is configured as described above. The configuration of the AGD device 1 is not limited to the above. For example, it is also possible to provide a gas supply mechanism connected to the aerosol-generating container 2 and separate from the gas supply system 5. In the above configuration, the pressure in the aerosol-generating container 2 is adjusted by the carrier gas supplied by the gas supply system 5, and the aerosol raw material P is stirred up to form an aerosol. By separately supplying a gas for adjusting the pressure from the gas supply means of the separate system, it is possible to adjust the pressure in the aerosol-generating container 2 independently of the aerosol formation state (formation amount, particle diameter mainly stirred up, etc.).

[0030] The aerosol raw material P is aerosolized in the aerosol-generating container 2 and formed into a film on the substrate S. The aerosol raw material P is made of fine particles having at least an insulating surface. As such fine particles, ceramic particles are used, and examples of the ceramic particles include insulating fine particles such as alumina fine particles, PZT (lead zirconate titanate) fine particles, zirconia fine particles, and yttria fine particles. In addition, examples of the fine particles include conductive fine particles such as metals whose surfaces are coated with an insulating film. The particle diameter of the aerosol raw material P is not particularly limited, but may be, for example, an average particle diameter (D 50 ) is applicable.

[0031] In this specification, unless otherwise specified, the term "average particle size" refers to the cumulative percentage of the particle size distribution measured by a laser diffraction particle size distribution measurement method at 50% (D 50 ) The average particle size was measured using a laser diffraction particle size distribution analyzer "SALD2000" manufactured by Shimadzu Corporation. The "specific surface area" is a value measured by gas adsorption method, and here the value measured using a Shimadzu Corporation "Flowsorb II2300" was used.

[0032] In this embodiment, raw material particles obtained by mixing first ceramic particles having an average particle size of 3 μm or more and 7 μm or less and second ceramic particles which are pulverized powder of ceramic particles made of the same material as the first ceramic particles are used as the aerosol raw material P. The second ceramic particles have a particle size of 0.2 μm or more and 0.4 μm or less.

[0033] As described later, by mixing first ceramic particles with a relatively large particle size and second ceramic particles with a relatively small particle size in the aerosol raw material P, plasma is generated efficiently by the first ceramic particles, and film formation efficiency is increased by the second ceramic particles, which have a larger specific surface area than the first ceramic particles. This makes it possible to stably form a dense, highly adhesive ceramic particle film.

[0034] The second ceramic particles may be formed by pulverizing ceramic particles having an average particle size smaller than that of the first ceramic particles. Alternatively, the second ceramic particles may be formed by pulverizing the first ceramic particles with a ball mill or the like. The pulverizing method is not particularly limited, and typically, a pulverizing means such as a ball mill is used.

[0035] Next, a film formation method of this embodiment will be described with reference to Fig. 2. Fig. 2 is a schematic diagram illustrating the operation of the AGD apparatus 1. A typical film formation method using the AGD apparatus 1 will be described below.

[0036] A predetermined amount of aerosol raw material P is placed in the aerosol-generating container 2. The aerosol raw material P may be heated and degassed in advance. The aerosol-generating container 2 may be heated in order to degas the aerosol raw material P while it is still contained therein. Degassing the aerosol raw material P can increase the charging probability and efficiency of the aerosol raw material P that induces plasma.

[0037] Next, the aerosol-generating container 2 and the film-forming chamber 3 are evacuated to a vacuum by the exhaust system 4 . While the vacuum pump 12 is operating, the first valve 10 and the second valve 11 are opened, and the aerosol-generating container 2 and the deposition chamber 3 are evacuated until the pressure is sufficiently reduced. When the pressure in the aerosol-generating container 2 is sufficiently reduced, the first valve 10 is closed. The deposition chamber 3 is evacuated during deposition.

[0038] Next, the carrier gas is introduced into the aerosol-generating container 2 by the gas supply system 5. The third valve 15 is opened, and the carrier gas is ejected from the gas ejection body 17 into the aerosol-generating container 2. The pressure in the aerosol-generating container 2 increases due to the carrier gas introduced into the aerosol-generating container 2. In addition, the aerosol raw material P is lifted up by the carrier gas ejected from the gas ejection body 17 as shown in FIG. 2, and floats in the aerosol-generating container, forming an aerosol (shown by A in FIG. 2) in which the aerosol raw material P is dispersed in the carrier gas. The generated aerosol flows into the transfer pipe 6 due to the pressure difference between the aerosol-generating container 2 and the deposition chamber 3, and is ejected from the nozzle 18. The pressure difference between the aerosol-generating container 2 and the deposition chamber 3 and the formation state of the aerosol are controlled by adjusting the opening degree of the third valve 15.

[0039] The aerosol (shown as A' in FIG. 2) is ejected from the nozzle 18 at a flow rate determined by the pressure difference between the aerosol-generating container 2 and the deposition chamber and the opening diameter of the nozzle 18. This aerosol reaches the surface of the substrate S or an existing film, and the aerosol raw material P contained in the aerosol, i.e., ceramic particles, collide with the surface of the substrate S or the existing film. In the process, a ceramic thin film is formed.

[0040] By moving the substrate S, a ceramic thin film (indicated by F in FIG. 2) is formed in a predetermined area on the substrate S. By moving the stage 7 by the stage driving mechanism 8, the relative position of the substrate S with respect to the nozzle 18 changes. By moving the stage 7 in one direction parallel to the substrate S surface to be coated, a thin film can be formed in a line shape having the same width as the opening diameter of the nozzle 18. By moving the stage 7 back and forth, a film can be further formed on the existing film, and thus a ceramic thin film can be formed with a predetermined film thickness. In addition, by moving the stage 7 two-dimensionally, a ceramic thin film is formed in a predetermined area. The angle of the nozzle 18 with respect to the substrate S surface to be coated may be a right angle or may be oblique. By obliquely orienting the nozzle 18 with respect to the substrate surface to be coated, even if aggregates of fine particles that deteriorate the quality of the coating are attached, the attached matter can be removed.

[0041] In the film forming method according to the present embodiment, when the aerosol A is generated and when the aerosol A is transported by the transport pipe 6, the fine particles constituting the raw material P collide with each other or with the inner surface of the transport pipe 6 and the nozzle 18, generating static electricity on the surfaces of the fine particles, and the charged fine particles are deposited on the substrate S. The greater the charge on the fine particles, the denser the film becomes, and the faster the film formation speed becomes. The excess charge of the deposited fine particles is released into the space within the film formation chamber, and depending on the amount of released charge, a noticeable light emission occurs. It is believed that this light emission phenomenon is mainly due to plasma, and contributes to the generation of active species.

[0042] More specifically, when the aerosol raw material P is aerosolized by the gas in the aerosol-generating container 2, the ceramic raw material powder that is positively charged by contact with the bottom wall of the aerosol-generating container 2 has a higher charging efficiency when the particle size is large. Small particles have a higher probability of being transported by the gas without colliding with anything, so the number of charged particles is reduced. When a positively charged particle flies near the earthed substrate S (stage 7), electrons are emitted from the earth side, which causes the gas near the particle to discharge. This can be seen with the naked eye as gas plasma, and large particle sizes are better for generating this plasma.

[0043] During this process, the surface of the raw material powder flying through the discharge is sputtered, knocking out atoms and molecules, and further merging and growing into fine nanoparticles (these are called active species) that contribute to film formation. The self-generated plasma region is spatially limited, and the probability of being sputtered within it increases the greater the specific surface area of ​​the particles being sputtered during the flight process. In other words, in order to create active species, it is necessary for small particles (with a large specific surface area) to fly through the plasma, and the greater the amount of these active species, the higher the film formation speed.

[0044] In this embodiment, a mixed powder of raw material particles, which is a mixture of first ceramic particles having an average particle size of 1 μm or more and second ceramic particles obtained by pulverizing the first ceramic particles, is used as the aerosol raw material P. Therefore, the raw material powder can be efficiently electrostatically charged and sputtered within the technology for producing a film by spraying ceramic powder at room temperature.

[0045] That is, when the raw powder is rubbed together during the gas transport process and becomes electrostatically charged, if the positively charged particles fly near the grounded substrate S, electrons are emitted from the ground side, which causes the gas near the particles to discharge and become plasma. As the particles fly through the plasma, the particle surface is sputtered, sputtered atoms and molecules are generated, and fine nanocrystalline particles (active species) are formed by coalescence and growth. It is thought that these active species contribute to the formation of a film by aerosol gas deposition. In other words, in order to stably form a dense and highly adhesive ceramic thin film, it is thought that an optimal mixed powder, etc. is required as the aerosol raw material P, because the particle shape (size) that efficiently electrostatically charges and generates plasma is different from the particle shape (size) that efficiently sputters in the plasma.

[0046] [Experimental Example 1] Hereinafter, a description will be given of an experimental example of a film forming method using the AGD apparatus 1 configured as above. Here, the description will be given of an experimental example in which alumina powder is used as the raw material powder.

[0047] (Experimental Example 1-1) 30 g of alumina powder (AL-160SG-3 manufactured by Showa Denko) with an average particle size of 0.52 μm was placed in an alumina crucible and subjected to heat treatment in the atmosphere at a temperature of 300° C. for 1 hour. After that, 30 g of the alumina powder was quickly transferred to a glass aerosol-generating container 2 and evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. by a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min, and the carrier gas was also supplied at 5 L / min to aerosolize the alumina powder in the aerosol-generating container 2 (pressure: about 30 kPa). The alumina powder was then sprayed and deposited on an aluminum substrate as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through a carrier pipe / nozzle (opening 30 mm×0.3 mm), forming an alumina film. The substrate was driven at a speed of 5 mm / s, and 40 layers were deposited over a length of 50 mm in the X-axis direction and 30 mm in the Y-axis direction. The deposition time was about 12 minutes, and an alumina film with a thickness of 7 μm and an area of ​​50 mm×30 mm was formed. The film was dense and had strong adhesion to the aluminum substrate (it did not peel off even when rubbed with an HB pencil). However, the film was a whitish gray color. In addition, the alumina film was conductive even when an applied voltage of 100V or less was applied, and it was not found to have any electrical insulation properties. The resistance was 1kΩ or less.

[0048] (Experimental Example 1-2) 30 g of alumina powder (AES-12, manufactured by Sumitomo Chemical) with an average particle size of 0.44 μm was placed in an alumina crucible and subjected to heat treatment in air at a temperature of 300° C. for 1 hour. After that, 30 g of the alumina powder was quickly transferred to a glass aerosol-generating container 2, and the container was evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. with a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min, and the carrier gas was also supplied at 5 L / min to aerosolize the alumina powder in the aerosol-generating container 2 (pressure: about 30 kPa). The alumina powder was then sprayed and deposited on an aluminum substrate as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through a carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an alumina film. The substrate was driven at a speed of 5 mm / s, and 40 layers were deposited over a length of 50 mm in the X-axis direction and 30 mm in the Y-axis direction. The deposition time was about 12 minutes, and an alumina film with an area of ​​50 mm x 30 mm was formed. The film was a green compact, not dense, and could be peeled off if rubbed. Based on the particle size distribution of the raw powder, it is believed that the presence of many particles with sizes of 0.1 μm to 0.2 μm caused the film to become a green compact.

[0049] (Experimental Example 1-3) 150 g of alumina powder (AL-160SG-3 manufactured by Showa Denko) with an average particle size of 0.52 μm was ground for 3 hours in a planetary ball mill, and 30 g of the ground powder was placed in an alumina crucible and heated for 1 hour at a temperature of 300° C. in the atmosphere. After that, the 30 g of alumina powder was quickly transferred to a glass aerosol-generating container 2, and the container was evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. with a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min, and the carrier gas was also supplied at 5 L / min to aerosolize the alumina powder in the aerosol-generating container 2 (pressure: about 30 kPa). The alumina powder was then sprayed and deposited on an aluminum substrate as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through a carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an alumina film. The substrate was driven at a speed of 5 mm / s, and 40 layers were deposited over a length of 50 mm in the X-axis direction and 30 mm in the Y-axis direction. The deposition time was about 12 minutes, and an alumina film with a thickness of 7 μm and an area of ​​50 mm x 30 mm was formed. The film was dense and had strong adhesion to the aluminum substrate (it did not peel off even when rubbed with an HB pencil). Compared to the film formed using alumina powder that had not been milled (Experimental Example 1-1), the film was less whitish and had a transparent gray-black color. This alumina film was found to be conductive in many places even with an applied voltage of 100V or less, and had no electrical insulation properties. The resistance was 1kΩ or less.

[0050] (Experimental Example 1-4) 150 g of alumina powder (AES-12, manufactured by Sumitomo Chemical) with an average particle size of 0.44 μm was ground for 3 hours in a planetary ball mill, and 30 g of the ground powder was placed in an alumina crucible and heated for 1 hour at a temperature of 300° C. in the atmosphere. After that, the 30 g of alumina powder was quickly transferred to a glass aerosol-generating container 2, and the container was evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. with a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas being stirred up was adjusted with a flow meter and supplied at 8 L / min. Also, the carrier gas was supplied at 5 L / min. The alumina powder in the aerosol-generating container 2 (pressure: about 30 kPa) was aerosolized, and the alumina powder was sprayed and deposited on the aluminum substrate as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through the carrier pipe / nozzle (opening 30 mm×0.3 mm), forming an alumina film. The drive speed of the substrate was set to 5 mm / s, and 40 layers were deposited with a length of 50 mm in the X-axis direction and 30 mm in the Y-axis direction. The deposition time was about 12 minutes, and an alumina film with an area of ​​50 mm×30 mm was formed, but the film was not dense and could be peeled off if rubbed.

[0051] (Experimental Example 1-5) 30 g of alumina powder (ALM-43 manufactured by Sumitomo Chemical) with an average particle size of 3.7 μm was placed in an alumina crucible and subjected to heat treatment in the atmosphere at a temperature of 300° C. for 1 hour. After that, the 30 g of alumina powder was quickly transferred to a glass aerosol-generating container 2, and the container was evacuated to a pressure of 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. with a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas being stirred up was adjusted with a flow meter to be supplied at 8 L / min, and the carrier gas was also supplied at 5 L / min to aerosolize the alumina powder in the aerosol-generating container 2 (pressure: about 30 kPa), which was then sprayed and deposited on an aluminum substrate as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through a carrier pipe / nozzle (opening 30 mm x 0.3 mm) to form an alumina film. The substrate was driven at a speed of 5 mm / s, and 40 layers were deposited over a length of 50 mm in the X-axis direction and 30 mm in the Y-axis direction. The deposition time was about 12 minutes. The film thickness was less than 1 μm, and although there was a discharge mark measuring 50 mm x 30 mm, the film was not thick, and even when the number of layers was 100, the film thickness did not exceed 1 μm. There were no traces of the compact, and although reddish purple discharge was observed during film formation, no film was formed. The particle size distribution of the raw material powder showed that there were no particles with a size of 0.4 μm or less, which is thought to be the reason why the film thickness did not increase.

[0052] (Experimental Example 1-6) 150 g of alumina powder (AL-160SG-3 manufactured by Showa Denko) with an average particle size of 0.52 μm was ground for 3 hours in a planetary ball mill to produce alumina powder (second ceramic particles) with a particle size of 0.2 μm or more and 0.4 μm or less. 60 g of the ground powder was mixed with 20 g of alumina powder (first ceramic particles) (ALK-43 manufactured by Sumitomo Chemical) with an average particle size of 3.7 μm, placed in an alumina crucible, and heated at a temperature of 300 ° C. in air for 1 hour. Then, 30 g of the alumina powder was quickly transferred to a glass aerosolization container 2 and evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosolization container 2 was heated to 150 ° C. by a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas being stirred up was adjusted with a flow meter and supplied at 8 L / min. Also, the carrier gas was supplied at 5 L / min. By this, the alumina powder in the aerosol-generating container 2 (pressure: about 30 kPa) was aerosolized, and the alumina powder was sprayed and deposited on the aluminum substrate as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through the carrier pipe / nozzle (opening 30 mm×0.3 mm), to form an alumina film. The drive speed of the substrate was set to 5 mm / s, and 200 layers were deposited over a length of 50 mm in the X-axis direction and 30 mm in the Y-axis direction. The deposition time was about 108 minutes, and an alumina film with a thickness of 4 μm and an area of ​​50 mm×30 mm was formed. The film was dense and had strong adhesion to the aluminum substrate (it did not peel off even when rubbed with an HB pencil). The film was a glossy black color. The resistance of this alumina film was 40 MΩ or more over the entire surface, demonstrating a high level of electrical insulation. In this experimental example, the data was for a case where the mixing ratio of large 3.7 μm particles to small powder was 25%. When this mixing ratio was increased to 50%, it was confirmed that a black alumina film could be formed, but the film had uneven surface gloss.

[0053] As described above, in the film formation examples (Experimental Examples 1-1 to 1-5) using raw material powder of a single particle size, it was difficult to form an alumina film that was dense, had high adhesion, and had excellent electrical insulation. However, in the film formation example (Experimental Example 1-6) using two types of raw material powder with different particle sizes, it was possible to stably form an alumina film that was dense, had high adhesion, and had excellent electrical insulation.

[0054] [Experimental Example 2] Next, the raw material powder PZT(Pb(Zr 0.52 Ti 0.48 )O3) We will explain an experimental example using powder.

[0055] (Experimental Example 2-1) 50 g of PZT powder (manufactured by Kojundo Chemical Laboratory) with an average particle size of 2.9 μm was placed in an alumina crucible and heat-treated in air at a temperature of 300° C. for 1 hour. After that, the 50 g of PZT powder was quickly transferred to a glass aerosol-generating container 2, and the container was evacuated to a pressure of 10 Pa or less. To promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. with a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min, and the carrier gas was supplied at 5 L / min to aerosolize the PZT powder in the aerosol-generating container 2 (pressure: about 30 kPa). The aerosol was then sprayed and deposited on a quartz substrate as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through a carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming a PZT film. The substrate was driven at a speed of 5 mm / s, and 60 layers were deposited over a length of 50 mm in the X-axis direction and 30 mm in the Y-axis direction. The deposition time was about 10 minutes, but the film thickness was less than 1 μm, and although there was a thin deposition mark with an area of ​​50 mm x 30 mm, the film thickness was not thick, and even if the number of layers was 100, the film thickness did not exceed 1 μm.

[0056] (Experimental Example 2-2) 150 g of PZT powder (manufactured by Kojundo Kagaku Kenkyusho) with an average particle size of 2.9 μm was ground for 3 hours in a planetary ball mill to produce PZT powder (second ceramic particles) with a particle size of 0.2 μm or more and 0.4 μm or less. 15 g of the ground powder and 45 g of the PZT powder (first ceramic particles) with an average particle size of 2.9 μm were mixed and placed in an alumina crucible, and heat-treated at a temperature of 300° C. in air for 1 hour. Then, 60 g of the PZT powder was quickly transferred to a glass aerosolization container 2 and evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosolization container 2 was heated to 150° C. by a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min. Also, the carrier gas was supplied at 5 L / min to aerosolize the alumina powder in the aerosol-generating container 2 (pressure: about 30 kPa). The alumina powder was then sprayed and deposited on the ITO-coated quartz substrate as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through the carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming a PZT film. The substrate was driven at a speed of 5 mm / s, and 50 layers were deposited over a length of 50 mm in the X-axis direction and 30 mm in the Y-axis direction. The deposition time was about 27 minutes, and a PZT film with a thickness of 2 μm and an area of ​​50 mm x 30 mm was formed. The film was dense and had strong adhesion to the quartz substrate (it did not peel off even when rubbed with an HB pencil). The film was a transparent, yellowish-black glossy film. The weight of the film was about 6 mg.

[0057] Figure 3 shows the particle size distribution of the PZT powder before pulverization, and Figure 4 shows the particle size distribution of the PZT powder after pulverization. As shown in the figures, the PZT powder after pulverization is refined, and it was confirmed that the PZT powder after pulverization contains a large amount of raw material powder (second ceramic particles) with a particle size of 0.2 μm to 0.4 μm.

[0058] (Experimental Example 2-3) 150g of PZT powder (manufactured by Kojundo Kagaku Kenkyusho) with an average particle size of 2.9μm was ground for 3 hours in a planetary ball mill to produce PZT powder (second ceramic particles) with a particle size of 0.2μ or more and 0.4μm or less. 30g of the ground powder and 30g of the PZT powder (first ceramic particles) with an average particle size of 2.9μm were mixed and placed in an alumina crucible, and heat-treated at a temperature of 300℃ in air for 1 hour. After that, 60g of the PZT powder was quickly transferred to a glass aerosolization container 2 and evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosolization container 2 was heated to 150℃ using a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min. Also, the carrier gas was supplied at 5 L / min to aerosolize the alumina powder in the aerosol-generating container 2 (pressure: about 30 kPa). The alumina powder was then sprayed and deposited on the ITO-coated quartz substrate as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through the carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming a PZT film. The substrate was driven at a speed of 5 mm / s, and 50 layers were deposited over a length of 50 mm in the X-axis direction and 30 mm in the Y-axis direction. The deposition time was about 27 minutes, and a PZT film with a thickness of 2 μm and an area of ​​50 mm x 30 mm was formed. The film was dense and had strong adhesion to the quartz substrate (it did not peel off even when rubbed with an HB pencil). However, protruding film was observed in places. The film was a yellowish blackish color. The weight of the film was about 29 mg.

[0059] [Experimental Example 3] Next, an experimental example in which yttria-stabilized zirconia powder was used as the raw material powder will be described.

[0060] (Experimental Example 3-1) 50 g of 8 mol% yttria-stabilized zirconia powder (powder produced by wet process by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) with an average particle size of 2.5 μm was placed in an alumina crucible and subjected to heat treatment in air at a temperature of 300° C. for 1 hour. After that, 50 g of the yttria-stabilized zirconia powder was quickly transferred to a glass aerosol-generating container 2 and evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. by a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 6 L / min. Also, the carrier gas was supplied at 7 L / min. The yttria-stabilized zirconia powder in the aerosol-generating container 2 (pressure: about 32 kPa) was aerosolized, and the aerosol was sprayed and deposited on a SUS substrate of φ25 mm as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through a carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an yttria-stabilized zirconia film. The substrate was driven at a speed of 5 mm / s, and 44 layers were deposited over a length of 30 mm only in the X-axis direction. The deposition time was about 4.5 minutes, and an yttria-stabilized zirconia film with a central thickness of 14 μm and an area of ​​φ25 mm was formed. The film was dense and had strong adhesion to the SUS substrate (it did not peel off even when rubbed with an HB pencil). The film was gray in color. The weight of the film was about 25 mg.

[0061] (Experimental Example 3-2) 50 g of 8 mol% yttria-stabilized zirconia powder (powder produced by wet process by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) with an average particle size of 6.3 μm was placed in an alumina crucible and subjected to heat treatment in air at a temperature of 300° C. for 1 hour. After that, 50 g of the yttria-stabilized zirconia powder was quickly transferred to a glass aerosol-generating container 2, and the container was evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. by a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas being stirred up was adjusted with a flow meter and supplied at 8 L / min. Also, the carrier gas was supplied at 5 L / min. The yttria-stabilized zirconia powder in the aerosol-generating container 2 (pressure: about 29 kPa) was aerosolized, and the aerosol was sprayed and deposited on a SUS substrate of φ25 mm as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through a carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an yttria-stabilized zirconia film. The substrate was driven at a speed of 5 mm / s, and 240 layers were deposited over a length of 30 mm only in the X-axis direction. The deposition time was about 24 minutes, and an yttria-stabilized zirconia film having a central thickness of 2.6 μm and an area of ​​φ25 mm was formed. The film was dense and had strong adhesion to the SUS substrate (it did not peel off even when rubbed with an HB pencil). The film was glossy black in color. The weight of the film was approximately 9.8 mg. The density is high, but the film formation speed tends to be slow. From the particle size distribution of the raw powder, it is thought that there is little powder below 1 μm, and although plasma is generated, there is a tendency for little powder to be sputtered. Here, since dry powder is produced by crushing large lumps, it is speculated that the powder sprayed onto the substrate during the film formation process is crushed, and the crushed small powder below 1 μm is sputtered. In other words, it is thought that film formation requires the generation of crushed powder by spraying it onto the substrate. In the worst case, it is thought that the blasting effect could cause cutting of the base material, but cutting did not occur on the hard SUS substrate.

[0062] (Experimental Example 3-3) 50 g of 8 mol% yttria-stabilized zirconia powder (powder produced by wet process by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) with an average particle size of 5.4 μm was placed in an alumina crucible and subjected to heat treatment in air at a temperature of 300° C. for 1 hour. After that, 50 g of the yttria-stabilized zirconia powder was quickly transferred to a glass aerosol-generating container 2 and evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. by a mantle heater. The exhaust valve (first valve 10) of the aerosolization container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min. Also, the carrier gas was supplied at 5 L / min. The yttria-stabilized zirconia powder in the aerosolization container 2 (pressure: about 32 kPa) was aerosolized, and the aerosol was sprayed and deposited on a SUS substrate of φ25 mm as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through a carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an yttria-stabilized zirconia film. The substrate was driven at a speed of 5 mm / s, and 80 layers were deposited over a length of 30 mm only in the X-axis direction. The deposition time was about 8 minutes, and an yttria-stabilized zirconia film with a central thickness of 11 μm and an area of ​​φ25 mm was formed. The film was dense and had strong adhesion to the SUS substrate (it did not peel off even when rubbed with an HB pencil). The film was black in color. The weight of the film was about 22 mg.

[0063] (Experimental Example 3-4) 50 g of 8 mol% yttria-stabilized zirconia powder (powder produced by wet process by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) with an average particle size of 1.4 μm was placed in an alumina crucible and subjected to heat treatment in air at a temperature of 300° C. for 1 hour. After that, 50 g of the yttria-stabilized zirconia powder was quickly transferred to a glass aerosol-generating container 2 and evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. by a mantle heater. The exhaust valve (first valve 10) of the aerosol-generating container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 6 L / min, and the carrier gas was also supplied at 7 L / min to aerosolize the yttria-stabilized zirconia powder in the aerosol-generating container 2 (pressure: about 30 kPa). The aerosol was then sprayed and deposited on a SUS substrate of φ25 mm as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through a carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an yttria-stabilized zirconia film. The substrate was driven at a speed of 5 mm / s, and 64 layers were deposited over a length of 30 mm only in the X-axis direction. The deposition time was about 6.5 minutes, and an yttria-stabilized zirconia film with a central thickness of 14 μm and an area of ​​φ25 mm was formed. The film was dense and had strong adhesion to the SUS substrate (it did not peel off even when rubbed with an HB pencil). The film was gray in color. The weight of the film was about 17.5 mg.

[0064] From the above results, it can be seen that in the film formation using 8 mol% yttria-stabilized zirconia powder, the density increases in the following order according to the particle size of the powder used: Therefore, it is found that to form a film with high density, it is better to use the larger particle size of 6.3 μm. 1. Average particle size 6.3μm (dry type) High density approx. 5.7g / cm 3 2.Average particle size 5.4μm (dry method) approximately 4.1g / cm 3 3.Average particle size 2.5μm (wet) approx. 3.7g / cm 3 4. Average particle size 1.4μm (dry type) Low density approx. 2.5g / cm 3

[0065] (Experimental Example 3-5) 50 g of 8 mol% yttria-stabilized zirconia powder (powder produced by wet process by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) with an average particle size of 6.3 μm was placed in an alumina crucible and subjected to heat treatment in air at a temperature of 300° C. for 1 hour. After that, 50 g of the yttria-stabilized zirconia powder was quickly transferred to a glass aerosol-generating container 2, and the container was evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. by a mantle heater. The exhaust valve (first valve 10) of the aerosolization container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min. In addition, the carrier gas was supplied at 5 L / min. The yttria-stabilized zirconia powder in the aerosolization container 2 (pressure: about 29 kPa) was aerosolized, and the powder was sprayed and deposited on the porous ceramic undercoat film on the SUS substrate of φ25 mm as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through the carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an yttria-stabilized zirconia film. The substrate was driven at a speed of 5 mm / s, and 240 layers were deposited over a length of 30 mm only in the X-axis direction. The deposition time was about 24 minutes, and as a result, 50% (25% to 75%) of the porous ceramic undercoat film was peeled off from the entire film. Plasma was confirmed during deposition.

[0066] (Experimental Example 3-6) 50 g of 8 mol% yttria-stabilized zirconia powder (powder produced by wet process by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) with an average particle size of 5.4 μm was placed in an alumina crucible and subjected to heat treatment in air at a temperature of 300° C. for 1 hour. After that, 50 g of the yttria-stabilized zirconia powder was quickly transferred to a glass aerosol-generating container 2 and evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. by a mantle heater. The exhaust valve (first valve 10) of the aerosolization container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min. In addition, the carrier gas was supplied at 5 L / min. The yttria-stabilized zirconia powder in the aerosolization container 2 (pressure: about 29 kPa) was aerosolized, and the powder was sprayed and deposited on the porous ceramic undercoat film on the SUS substrate of φ25 mm as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through the carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an yttria-stabilized zirconia film. The substrate was driven at a speed of 5 mm / s, and 240 layers were deposited over a length of 30 mm only in the X-axis direction. The deposition time was about 24 minutes, and as a result, 50% (25% to 75%) of the porous ceramic undercoat film was peeled off from the entire film. Plasma was confirmed during deposition.

[0067] (Experimental Example 3-7) 150 g of 8 mol% yttria-stabilized zirconia powder (powder produced by wet method, manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd.) with an average particle size of 2.5 μm was ground for 3 hours in a planetary ball mill, and 50 g of the ground powder was placed in an alumina crucible and heat-treated at a temperature of 300° C. in the atmosphere for 1 hour. After that, 50 g of the yttria-stabilized zirconia powder was quickly transferred to a glass aerosol-generating container 2, and the container was evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosol-generating container 2 was heated to 150° C. with a mantle heater. The exhaust valve (first valve 10) of the aerosolization container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min. Also, the carrier gas was supplied at 5 L / min. The yttria-stabilized zirconia powder in the aerosolization container 2 (pressure: about 30 kPa) was aerosolized, and the powder was sprayed and deposited on the porous ceramic undercoat film on the SUS substrate of φ25 mm as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through the carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an yttria-stabilized zirconia film. The substrate was driven at a speed of 5 mm / s, and 8 layers of 30 mm in length were deposited only in the X-axis direction. The deposition time was about 1 minute, and an yttria-stabilized zirconia film with a thickness of 4 μm and an area of ​​φ25 mm was deposited. There was no peeling between the porous ceramic undercoat and the film, which was whitish in color. The weight of the film was approximately 4.5 mg.

[0068] (Experimental Example 3-8) 150g of 8mol% yttria-stabilized zirconia powder (powder manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. using a wet method) with an average particle size of 2.5μm was ground for 3 hours in a planetary ball mill to produce yttria-stabilized zirconia powder (second ceramic particles) with a particle size of 0.2μ or more and 0.4μm or less. 15g of the powder after the grinding process and 35g of 8mol% yttria-stabilized zirconia powder (first ceramic particles) (powder manufactured by Daiichi Kigenso Kagaku Kogyo Co., Ltd. using a dry method) with an average particle size of 6.3μm were placed in an alumina crucible and subjected to a heat treatment at a temperature of 300°C in the atmosphere for 1 hour. Then, 50g of the yttria-stabilized zirconia powder was quickly transferred to a glass aerosolization container 2 and evacuated to 10 Pa or less. In order to promote degassing of the powder, the aerosolization container 2 was heated to 150°C using a mantle heater. The exhaust valve (first valve 10) of the aerosolization container 2 was closed, and the nitrogen gas was adjusted with a flow meter to be supplied at 8 L / min, and the carrier gas was also supplied at 5 L / min to aerosolize the yttria-stabilized zirconia powder in the aerosolization container 2 (pressure: about 30 kPa). The powder was then sprayed and deposited on the porous ceramic undercoat film on the SUS substrate of φ25 mm as the substrate S attached to the stage 7 in the deposition chamber 3 (pressure: about 200 Pa) through the carrier pipe / nozzle (opening 30 mm x 0.3 mm), forming an yttria-stabilized zirconia film. The substrate was driven at a speed of 5 mm / s, and 120 layers were deposited over a length of 30 mm only in the X-axis direction. The deposition time was about 9 minutes, and an yttria-stabilized zirconia film with a thickness of 7.8 μm and an area of ​​φ25 mm was formed. There was no peeling between the porous ceramic base film and the film was black in color. The weight of the film formed was about 14.2 mg. Compared to Experimental Example 3-7, it was possible to form a film with increased density. [Explanation of symbols]

[0069] 1...Aerosolized gas deposition device (AGD device) 2. Aerosol container 3…Deposition chamber 6...Transport pipe 18…Nozzle S...Base material

Claims

1. A raw material particle mixture of first ceramic particles having an average particle size of 3 μm or more and 7 μm or less and second ceramic particles which are pulverized powder of ceramic particles made of the same material as the first ceramic particles and have a particle size of 0.2 μm or more and 0.4 μm or less is placed in a sealed container; generating an aerosol of the raw material particles by introducing a gas into the sealed container; The aerosol is transported to a deposition chamber maintained at a lower pressure than the sealed container via a transport pipe connected to the sealed container; The raw material fine particles are deposited on a substrate accommodated in the film-forming chamber. Film formation method.

2. The film forming method according to claim 1, The second ceramic particles are formed by pulverizing ceramic particles having an average particle size smaller than that of the first ceramic particles. Film formation method.

3. The film forming method according to claim 1, The second ceramic particles are formed by pulverizing the first ceramic particles. Film formation method.

4. The film forming method according to claim 1, During the transport of the raw material particles from the sealed container to the film-forming chamber, the first ceramic particles are charged, and surfaces of the second ceramic particles are sputtered by discharge generated between the first ceramic particles and the substrate. Film formation method.

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