Film deposition apparatus, film deposition method, and film deposition body

Abstract

To provide a film deposition apparatus capable of forming a homogeneous film while suppressing degradation of use efficiency of raw materials and increase of a production cost.SOLUTION: A film deposition apparatus 1 for forming a film on a substrate K is equipped with an aerosol transporting passage 10 for ejecting an aerosol formed by dispersing raw ceramic powder in a gas from the ejection end 10a toward the substrate K and plates 11 that have an opening and are installed between the ejection end 10a of the aerosol transporting passage 10 and the substrate K so that the opening is opposite to the ejection end 10a of the aerosol transporting passage 10. The plates 11 have a ratio of the area of the opening of 1 or more to the sectional area of the ejection end 10a of the aerosol transporting passage 10.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a film forming apparatus and a film forming method for forming a film on a substrate, and a formed film body.

Background Art

[0002] As a method of forming a film made of a metal oxide material on a substrate without undergoing heat treatment at a high temperature such as sintering, there is a technique called an aerosol deposition method (AD method). In this AD method, a raw material powder composed of fine particles such as metal oxide is jetted from a nozzle toward a substrate such as ceramics or plastic at about the speed of sound, and the fine particles are crushed and deformed by the energy when the raw material powder collides with the substrate, thereby forming a dense film on the substrate.

[0003] In the AD method, since the impact force of the fine particles colliding with the substrate has a great influence on the density of the film, in order to obtain a desired film quality uniformly, it is necessary to control the speed of the fine particles colliding with the substrate within an appropriate range. Among them, zirconia-based materials have high hardness and are difficult to show plastic deformation behavior when colliding with the substrate, and the process window for film formation is very narrow. Therefore, in order to form a uniform film, it is necessary to control the particle speed with high precision. On the other hand, the aerosol ejected from the nozzle has a slower speed at the time of collision as it is ejected from the inner wall side in the flow path cross section of the nozzle, and the distribution of the collision speed in the flow path cross section tends to be large. In addition, the aerosol ejected from the nozzle spreads as it moves away from the nozzle, and the particles in this spread part collide with the substrate obliquely. Therefore, compared with the particles at the center of the aerosol, the speed in the direction perpendicular to the substrate at the time of substrate collision is likely to decrease. Conventionally, it has been known that these factors cause problems in film quality uniformity and film adhesion strength.

[0004] Various methods have been proposed to address the above problem. For example, Patent Document 1 describes a method in which a mask integrated with the nozzle is placed between the nozzle and the substrate (base material), and the mask blocks the portion of the particle flow that is slower than a predetermined speed (the inner wall side portion of the nozzle's flow channel cross-section), thereby causing particles whose speed at the time of impact with the base material is greater than the predetermined speed to collide with the substrate.

[0005] Patent Document 2 describes a method in which a nozzle for ejecting an aerosol is provided with an outlet for ejecting a straightening gas, and by ejecting the straightening gas from this outlet around the aerosol, the spread of the aerosol is suppressed, causing the particles to collide perpendicularly with the substrate.

[0006] Furthermore, Patent Document 3 describes an adjustment device that selects specific particles from the particles blown out from the nozzle according to their density and adjusts the particle size distribution of the particles to be sprayed onto the substrate, thereby selecting particles other than aggregated particles to be sprayed onto the substrate. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] Japanese Patent Publication No. 2005-002461 [Patent Document 2] Japanese Patent Publication No. 2007-246937 [Patent Document 3] Japanese Patent Publication No. 2013-181234 [Overview of the project] [Problems that the invention aims to solve]

[0008] According to the methods described in Patent Documents 1 and 3 above, particles other than those with a speed above a predetermined speed or aggregated particles can be selectively made to collide with the substrate, thereby suppressing the adhesion of compacted powder to the substrate and improving the uniformity of the film quality. However, this may block the particle flow more than necessary, which could lead to a decrease in raw material utilization efficiency.

[0009] Furthermore, according to the method described in Patent Document 2, the spread of aerosols ejected from the nozzle can be suppressed, causing the particles to collide with the substrate, and the uniformity of the film quality can be improved in the same way as described above. However, it is necessary to flow an additional gas different from the gas used to generate the aerosols, which may necessitate the strengthening of the exhaust system, potentially leading to increased manufacturing costs.

[0010] This invention has been made in view of the above circumstances, and aims to provide a film deposition apparatus and method, as well as a film deposition product, that can form a homogeneous film while suppressing a decrease in raw material utilization efficiency and an increase in manufacturing costs. [Means for solving the problem]

[0011] The characteristic configuration of the film deposition apparatus according to the present invention for achieving the above objective is a film deposition apparatus for forming a film on a substrate, An aerosol transport path that ejects an aerosol, in which ceramic raw material powder is dispersed in gas, from an ejection end toward the substrate, The aerosol transport path comprises two or more plates disposed between the ejection end of the aerosol transport path and the substrate such that an opening is formed and the ejection end of the aerosol transport path faces the opening, The two or more plates are arranged parallel to each other and integrally with the aerosol transport path along the direction of aerosol ejection. The ejection end of the aerosol transport path and the substrate are relatively movable. The two or more plates follow the ejection end of the aerosol transport path, The ratio of the area of ​​the openings formed in each of the two or more plates to the cross-sectional area of ​​the flow path at the ejection end of the aerosol transport path is 1 or more. 2 or less And, When forming a film, The key feature is that the distance from the plate to the substrate is within 60 mm. Furthermore, a characteristic configuration of the film-forming method according to the present invention for achieving the above objective is a method in which a film is formed on a substrate by ejecting an aerosol in which ceramic raw material powder is dispersed in a gas from the ejection end of an aerosol transport path toward the substrate, The aerosol is ejected onto the substrate through the openings of two or more plates, which are disposed integrally with the aerosol transport path and parallel to each other along the direction of aerosol ejection, with the openings of the plates facing the ejection end of the aerosol transport path and positioned between the ejection end of the aerosol transport path and the substrate, respectively. With the two or more plates following the ejection end of the aerosol transport path, the aerosol is ejected onto the substrate while the ejection end of the aerosol transport path and the substrate are moved relative to each other. The ratio of the area of ​​the openings formed in each of the two or more plates to the cross-sectional area of ​​the flow path at the ejection end of the aerosol transport path is 1 or more. 2 or less And, When forming a film, The key feature is that the distance from the plate to the substrate is within 60 mm.

[0012] According to the above characteristic configuration, the ratio of the area of ​​the openings formed on each of the two or more plates to the flow path cross-sectional area at the ejection end in the aerosol transport path is 1 or more. 2 or less As a result, among the aerosols ejected from the ejection end of the aerosol transport path Because the aerosols in the expanded area can be shielded to a sufficient extent, a homogeneous film can be formed while suppressing a decrease in raw material utilization efficiency. This configuration allows for the shielding of aerosols incident on the substrate from an oblique direction, without shielding aerosols incident from a vertical direction. Therefore, it is less likely that aerosols will be shielded more than necessary, and only particles with a collision velocity sufficient to form a dense film upon impact with the substrate can be made to collide with the substrate. In other words, with the above-described configuration, the loss of ceramic raw material powder is minimized, reducing the decrease in raw material utilization efficiency, while suppressing the formation of porous materials due to the adhesion of compacted powder, and enabling the formation of a homogeneous film. Furthermore, since rectifying gases are not required, the increase in manufacturing costs can also be suppressed. Further, by the plate following the ejection end of the aerosol conveyance path, even if the ejection end of the aerosol conveyance path and the substrate are relatively moved, the aerosol ejected from the ejection end of the aerosol conveyance path always passes through the opening of the plate. Therefore, a film can be formed on the substrate in a state where the aerosol incident on the substrate from an oblique direction is shielded. Thus, according to the above characteristic configuration, a homogeneous film can be formed over a wide range on the substrate. Furthermore, since the aerosol ejected immediately after passing through the plate diffuses with a certain degree of spread, the film area formed on the substrate increases as the distance from the plate to the substrate increases. When the area formed on the substrate increases, when scanning the aerosol conveyance path or the substrate to obtain a homogeneous film, it is necessary to form a film over a wider area than the target film formation area. Then, the amount of raw material powder used increases, and there is a risk that the production cost will increase. According to the above characteristic configuration, When forming a film, by setting the distance from the plate to the substrate to be within 60 mm, it becomes easier to suppress an increase in production cost.

[0019] A further characteristic configuration of the film forming apparatus according to the present invention is that the two or more plates are arranged such that the distance between the plates is 0.1 mm or more. A further characteristic configuration of the film forming method according to the present invention is that the aerosol is ejected onto the substrate through the openings of the two or more plates arranged such that the distance between the plates is 0.1 mm or more.

[0020] When providing two or more plates, if the distance between the plates is too narrow, it becomes difficult for gas to flow between the plates. Therefore, there may be a case where the aerosol incident on the substrate from an oblique direction cannot be shielded. According to the above characteristic configuration, it becomes possible to shield the aerosol incident on the substrate from an oblique direction between the plates, and a homogeneous film can be formed.

[0023] A further characteristic configuration of the film forming apparatus and the film forming method according to the present invention is that the density of the particles constituting the ceramic raw material powder is 4.0 g / cm 3 or more.

[0024] According to the above characteristic configuration, a homogeneous film can be formed based on a ceramic raw material powder composed of particles with a density of 4.0 g / cm 3 or more.

[0025] A further characteristic configuration of the film forming apparatus and the film forming method according to the present invention is that the ceramic raw material powder is stabilized zirconia.

[0026] The inventor of the present application has confirmed by experiments that a homogeneous film can be formed when stabilized zirconia is used as the ceramic raw material powder.

Brief Description of the Drawings

[0029] [Figure 1] It is a diagram showing the configuration of the film forming apparatus according to this embodiment. [Figure 2] It is a diagram schematically showing the configuration near the aerosol transport pipe. [Figure 3] It is a view of the aerosol transport pipe seen from the ejection end side. [Figure 4] It is a top view of the plate. [Figure 5] It is a diagram for explaining the problem that occurs when there is no plate. [Figure 6] It is a diagram schematically showing the film formed when there is no plate.

Mode for Carrying Out the Invention

[0030] Hereinafter, a film forming apparatus and a film forming method according to an embodiment of the present invention will be described with reference to the drawings.

[0031] 〔Regarding the film forming apparatus〕 As shown in FIG. 1, the film forming apparatus 1 according to this embodiment includes a processing chamber 2, an aerosol generation unit 6, an aerosol transport pipe 10 (aerosol transport path), a plurality of plates 11, a carrier gas supply means 15, and the like.

[0032] Processing chamber 2 is an airtight enclosure. The pressure inside processing chamber 2 is reduced to a predetermined pressure (for example, about 0.5 kPa) or less by exhausting gas using a mechanical booster pump 3 and a vacuum pump 4, which serve as exhaust equipment. The processing chamber 2 also contains a holding section 5 for holding the substrate K to be subjected to film formation treatment, and the ejection end 10a of the aerosol transport pipe 10.

[0033] The aerosol generation unit 6 is a device that generates an aerosol by dispersing ceramic raw material powder in gas. In this embodiment, the raw material powder supply unit 7 is connected to the aerosol generation unit 6 via a raw material supply pipe S1. The aerosol generation unit 6 is also connected to a transport gas supply pipe S2 and an aerosol transport pipe 10, which will be described later. In the aerosol generation unit 6, an aerosol is generated by mixing the ceramic raw material powder supplied at a constant rate from the raw material powder supply unit 7 with the transport gas supplied by the transport gas supply means 15. This generated aerosol is then supplied to the aerosol transport pipe 10. The supply rate of ceramic raw material powder from the raw material powder supply unit 7 to the aerosol generation unit 6 can be increased to shorten the time required to form a film with the target thickness. However, if the supply rate is too high, pulsation occurs in the amount of raw material powder supplied, making it difficult to obtain a homogeneous film. On the other hand, if the supply rate is too low, the film quality is improved, but the time required to complete film formation increases, and manufacturing costs increase. Therefore, the supply rate of the ceramic raw material powder is preferably 1.5 to 30 g / min.

[0034] As shown in Figures 1 to 3, the aerosol transport pipe 10 is arranged in the processing chamber 2 such that its ejection end 10a faces the holding part 5 inside the processing chamber 2. In this embodiment, the aerosol transport pipe 10 is a cylindrical straight pipe member whose inner diameter of the ejection end 10a is a predetermined flow path cross-sectional area A1 (the shaded area in Figure 3), and the end opposite to the ejection end 10a is connected to the aerosol generating unit 6. With this aerosol transport pipe 10, aerosol is supplied from the aerosol generating unit 6, and this supplied aerosol is ejected from the opening of the ejection end 10a.

[0035] As shown in Figures 1, 2, and 4, the multiple plates 11 are annular plate-shaped members, each with an opening 11a of a predetermined area A2 (the shaded area in Figure 4), and each plate 11 has two through holes 11b drilled in its outer peripheral edge. The opening 11a of each plate 11 is circular and is formed in the center of each plate 11. The thickness of each plate 11 is not particularly limited, but in this embodiment, the thickness of each plate 11 is 0.6 mm.

[0036] In this embodiment, the multiple plates 11 are arranged between the ejection end 10a of the aerosol transport pipe 10 and the substrate K such that the opening 11a of each plate 11 faces the ejection end 10a of the aerosol transport pipe 10. Furthermore, the multiple plates 11 are arranged along the aerosol ejection direction such that each plate 11 is parallel to the other. In other words, the multiple plates 11 are arranged along the aerosol ejection direction such that each plate surface is perpendicular to the aerosol ejection direction. The distance Ia between each plate 11 is not particularly limited, but in this embodiment it is 0.8 mm or 1.6 mm. Note that if the distance Ia is too short, the aerosol will not flow easily. As a result, it may not be possible to shield aerosols that enter the substrate from an oblique direction, making it difficult to form a homogeneous film. Therefore, from the viewpoint of forming a homogeneous film over a long period of time, the distance Ia is preferably 0.1 mm or more, more preferably 0.6 mm or more, and even more preferably 0.8 mm or more. On the other hand, if the distance between each plate 11 is too long, the ceramic raw material powder is likely to clog. As a result, the gaps between the plates 11 become blocked, making it difficult to obtain the intended effect. Therefore, from the viewpoint of obtaining the intended effect sufficiently over a long period of time, the distance Ia is preferably 3 mm or less, and more preferably 1.6 mm or less. Also, although Figures 1 and 2 show a state in which seven plates 11 are installed, it is not limited to this. Furthermore, from the viewpoint of easily shielding aerosols that are incident on the substrate from an oblique direction, it is preferable to install 14 or more plates 11.

[0037] The distance Ib from the plate 11 (tip plate) located closest to the substrate K among the multiple plates 11 to the substrate K is not particularly limited, but in this embodiment, the distance Ib is 20 mm. Note that the greater the distance from the tip plate 11 to the substrate K, the larger the film area formed on the substrate K. When the area formed on the substrate K is large, it is necessary to form a film over a larger area than the target film area when moving the aerosol transport tube 10 relative to the substrate K to obtain a homogeneous film. This may increase the amount of ceramic raw material powder used, potentially raising production costs. From this viewpoint, the distance Ib is preferably 60 mm or less, more preferably 40 mm or less, and even more preferably 20 mm or less. On the other hand, if the distance from the tip plate 11 to the substrate K is too close, and the substrate K has a distorted shape, there is a risk that the plate 11 and the substrate K may come into contact when moving the aerosol transport tube 10 relative to the substrate K. From this viewpoint, the distance Ib is preferably 2 mm or more.

[0038] Furthermore, in this embodiment, the multiple plates 11 are supported by a support member 12 and are integrated with the aerosol transport pipe 10. Specifically, the support member 12 in this embodiment is a rod-shaped member with a circular cross-section, one end of which is fixed to the outer wall surface of the aerosol transport pipe 10, and is bent into an L-shape. The multiple plates 11 are integrated with the aerosol transport pipe 10 by inserting the support member 12 through two through holes 11b in each plate 11 and attaching a nut to the other end of the support member 12. Note that "integrated with the aerosol transport pipe" means that it follows the ejection end 10a of the aerosol transport pipe 10. In this embodiment, the aerosol transport pipe 10 and the base material K are relatively movable, and when the aerosol transport pipe 10 and the base material K move relative to each other, each plate 11 follows the aerosol transport pipe 10. For example, if the aerosol transport tube 10 is configured to be movable, each plate 11 will follow the movement of the aerosol transport tube 10. However, if the holding part 5 is configured to be movable (i.e., the base material K is configured to be movable), each plate 11 will not follow the holding part 5, and will remain in place together with the aerosol transport tube 10 if the aerosol transport tube 10 remains in place.

[0039] The conveying gas supply means 15 consists of a gas supply unit 16, a conveying gas pressure control unit 17, a conveying gas flow rate control unit 18, a conveying gas supply pipe S2, and the like.

[0040] Specifically, the gas supply unit 16 is connected to a transport gas supply pipe S2, and the gas supply unit 16 supplies gases such as air, N2, He, and Ar into the transport gas supply pipe S2 using a compressor or gas cylinder.

[0041] In this embodiment, the transport gas supply pipe S2 is for transporting the gas supplied from the gas supply unit 16 as transport gas to the aerosol generation unit 6. Specifically, in this embodiment, the gas sent from the gas supply unit 16 is transported as transport gas to the aerosol generation unit 6 via the transport gas pressure control unit 17 and the transport gas flow rate control unit 18 in sequence. The transport gas supply pipe S2 is composed of a plurality of pipes connected between the gas supply unit 16, the transport gas pressure control unit 17, the transport gas flow rate control unit 18 and the aerosol generation unit 6. Furthermore, a pressure sensor P1 for detecting the pressure inside the transport gas supply pipe S2 is provided between the transport gas flow rate control unit 18 and the aerosol generation unit 6 in the transport gas supply pipe S2.

[0042] The conveying gas pressure control unit 17 stabilizes the conveying gas flowing through the conveying gas supply pipe S2 to an appropriate pressure, and the conveying gas flow rate control unit 18 controls the flow rate of the conveying gas flowing through the conveying gas supply pipe S2. In this embodiment, the operation of the conveying gas pressure control unit 17 and the conveying gas flow rate control unit 18 is appropriately controlled based on the pressure detected by the pressure sensor P1.

[0043] Next, we will explain the relationship between the flow path cross-sectional area A1 at the ejection end 10a of the aerosol transport tube 10 and the area A2 of the opening 11a of each plate 11.

[0044] First, with reference to Figures 2, 5, and 6, the problems when plate 11 is not provided will be explained. As shown in Figure 5, when plate 11 is not provided, the aerosol ejected from the ejection end of the aerosol transport pipe 100 spreads out as it moves away from the aerosol transport pipe 100, and the particles contained in this spread-out portion of the aerosol collide with the substrate K1 at an oblique angle. Therefore, the particles contained in the spread-out portion of the aerosol have a slower velocity in the direction perpendicular to the substrate K1 when they collide with the substrate K1 compared to the particles contained in the center of the aerosol. Consequently, as shown in Figure 6, the film formed on the substrate K has a high-density region M1 in the area where the aerosol ejected from the center of the flow channel cross-section of the aerosol transport pipe 100 was sprayed, and a porous region M2 made of compacted powder or the like exists in the area where the aerosol ejected from the inner wall side and spread out was sprayed (the area enclosed by the dotted line in Figure 5). Therefore, when plate 11 is not provided, the uniformity of the film quality deteriorates. In addition, the porous region M2 has weaker adhesion strength compared to the high-density region M1. Therefore, when a film is formed over a wide area on the substrate K1 while the aerosol transport tube 100 and the substrate K1 are moved relative to each other, even if a dense film is formed on the porous region M2, if the porous region M2 peels off from the substrate K1, the dense film formed on it will also peel off. For this reason, the easier it is for the porous region M2 to form, the lower the overall strength of the film tends to be.

[0045] Therefore, in the film deposition apparatus 1 according to this embodiment, a configuration is adopted in which a plurality of plates 11 are provided, and the ratio of the opening area A2 of each plate 11 to the flow channel cross-sectional area A1 at the ejection end 10a of the aerosol transport pipe 10 (opening area A2 / flow channel cross-sectional area A1) is 1 or more. By providing a plurality of plates 11, as shown in Figure 2, aerosols that cause the formation of porous regions (aerosols incident on the substrate K from an oblique direction) can enter between the plates 11, preventing them from reaching the substrate K. Furthermore, by adopting a configuration in which the above ratio is 1 or more, only aerosols incident on the substrate K from an oblique direction are shielded, so that only aerosols that cause the formation of a porous film are shielded without unnecessarily shielding aerosols that contribute to the formation of a highly dense film.

[0046] Therefore, according to the film deposition apparatus 1 of this embodiment, situations that unnecessarily shield aerosols are unlikely to occur, and only particles with a collision velocity such that the energy at the time of impact with the substrate K is sufficient to form a highly dense film can be made to collide with the substrate K. Thus, the loss of ceramic raw material powder is minimized, suppressing a decrease in raw material utilization efficiency, while suppressing the formation of porous materials due to the adhesion of compacted powder, and enabling the formation of a homogeneous film. Furthermore, since rectifying gas and the like are not required, the increase in manufacturing costs can also be suppressed.

[0047] In particular, when the ceramic raw material powder is a stabilized zirconia such as YSZ, which has a relatively high density, only particles with a collision velocity such that the energy at the time of arrival at the substrate K is sufficient to form a highly dense film can be made to collide with the substrate K, thereby forming a homogeneous film with good adhesion.

[0048] Furthermore, if the above ratio is too large, that is, if the opening area A2 of each plate 11 is too large compared to the flow path cross-sectional area A1 at the ejection end 10a of the aerosol transport tube 10, aerosols incident on the substrate from an oblique direction cannot be properly shielded, and the aerosols are more likely to reach the substrate K and create porous regions. Therefore, the above ratio is preferably 2 or less, and more preferably 1.5 or less.

[0049] [Regarding ceramic raw material powder] The ceramic raw material powder used in the film deposition apparatus 1 consists of particles with a density of 4.0 g / cm³. 3 The above is preferable, and such particles include, for example, stabilized zirconia particles containing yttrium, calcium, magnesium, hafnium, etc. In this embodiment, yttrium-containing zirconia (YSZ) is used as the ceramic raw material powder.

[0050] [Regarding film deposition methods] Next, the process of forming a film (film-forming body) on a substrate K using the film-forming apparatus 1 described above will be explained. In the film-forming method according to this embodiment, the transport gas is supplied from the gas supply unit 16 to the aerosol generation unit 6 while adjusting the flow rate and pressure of the transport gas circulating in the transport gas supply pipe S2 by the transport gas pressure control unit 17 and the transport gas flow rate control unit 18. In the aerosol generation unit 6, an aerosol is generated by mixing the supplied transport gas with the ceramic raw material powder supplied from the raw material powder supply unit 7. The generated aerosol is supplied to the aerosol transport pipe 10.

[0051] The aerosol supplied to the aerosol transport pipe 10 is ejected from the ejection end 10a of the aerosol transport pipe 10 toward the substrate K, and a film is formed on the substrate K when the ejected aerosol collides with the substrate K. In this embodiment, the aerosol is ejected onto the substrate K through the opening 11a of a plate 11 disposed between the ejection end 10a of the aerosol transport pipe 10 and the substrate K, such that the opening 11a faces the ejection end 10a of the aerosol transport pipe 10. The ratio of the opening area A2 of the plate 11 to the flow path cross-sectional area A1 at the ejection end 10a of the aerosol transport pipe 10 is 1 or more.

[0052] Thus, in the film formation method of this embodiment, the plate 11 is positioned between the ejection end 10a of the aerosol transport pipe 10 and the substrate K such that the opening 11a faces the ejection end 10a of the aerosol transport pipe 10, and the ratio of the opening area A2 to the flow path cross-sectional area A1 at the ejection end 10a of the aerosol transport pipe 10 is 1 or more, allowing aerosol to be ejected onto the substrate K through the opening 11a of the plate 11. This minimizes the loss of ceramic raw material powder, suppresses a decrease in raw material utilization efficiency, suppresses the formation of porous materials due to the adhesion of compacted powder, and enables the formation of a homogeneous film. Furthermore, since no rectifying gas or the like is required, the increase in manufacturing costs can also be suppressed.

[0053] Examples 1-5 and the comparative example are described below. Film deposition treatment was performed on the substrate for a predetermined time while varying the inner diameter of the plate, the number of plates, the distance between plates, the distance between the plate and the substrate, and the distance between the ejection end and the substrate. In each film deposition apparatus used in Examples 1-5 and the comparative example, the aerosol transport tube had an inner diameter of 11 mmφ at the ejection end. In addition, in both Examples 1-5 and the comparative example, the ceramic raw material powder had a density of 5.9 g / cm³. 3 YSZ particles with a median diameter of 1.01 μm were used. In addition, the flow rate of the transport gas was set to 200 L / min in Examples 1 to 5 and the Comparative Example, and the pressure inside the processing chamber was set to 0.5 kPa.

[0054] Table 1 summarizes the various conditions and the area of ​​the porous region formed on the substrate after the film formation process for Examples 1-3 and the comparative example. Table 2 summarizes the various conditions and the relative density of the formed film for Examples 1, 4, 5 and the comparative example. In Example 5, 24 plates were installed, of which 4 plates with an inner diameter of 11 mmφ were used on the upstream side in the flow direction of the conveying gas, and 20 plates with an inner diameter of 15 mmφ were used on the downstream side in the flow direction. The "area of ​​the porous region" in Table 1 refers to the area of ​​the porous region with low adhesion strength, consisting of the compacted powder mentioned above. The "relative density" in Table 2 refers to the density of the film-formed portion (weight / volume of the film deposited on the substrate), which is calculated as the theoretical density value (5.9 g / cm³ for this material). 3 This is the value (%) obtained by dividing by ).

[0055] [Table 1]

[0056] [Table 2]

[0057] First, referring to Table 1, we can compare Examples 1-3 with the comparative example. Examples 1-3, which have plates installed, have a smaller area of ​​porous regions formed on the substrate than the comparative example, which does not have plates installed. Furthermore, regarding the distance between the ejection end and the substrate, the longer the distance between the ejection end and the substrate, the greater the spread of the ejected aerosol, and therefore the larger the porous region formed on the substrate. However, the comparative example has the shortest distance between the ejection end and the substrate, yet it still has a large area of ​​porous regions. These results indicate that by installing plates, the aerosols that cause porous regions to form are blocked by the plates, preventing them from reaching the substrate, thus making it difficult for porous regions to form.

[0058] Furthermore, comparing Examples 1 to 3, the area of ​​the porous region decreased as the number of installed plates increased. Example 1 had the smallest porous region despite having the longest distance between the ejection end and the substrate. From these results, it can be seen that even with a long distance between the ejection end and the substrate, increasing the number of installed plates makes it easier to shield the aerosols that cause the formation of porous regions, thus making it more difficult for porous regions to form.

[0059] Next, referring to Table 2, we can compare Example 1 and Example 4. Although there is a difference in the distance between the plates, there is no significant difference in relative density. In both cases, the relative density is very high, exceeding 90% (81% in the comparative example), and a denser film is formed compared to the comparative example where no plates were installed. Note that the relative density in Example 4 is slightly lower, which is thought to be due to the slightly longer distance between the ejection end and the substrate in Example 4 compared to Example 1.

[0060] Furthermore, referring to Table 2, a comparison between Example 1 and Example 5 shows that when a plate with an inner diameter larger than the inner diameter of the ejection end is used in part of the plate (Example 5), the relative density is lower than when only plates with the same inner diameter as the inner diameter of the ejection end are used (Example 1). However, in both cases, the relative density is higher than the comparative example where no plates are installed. From this, it can be seen that while it is preferable for the inner diameters of the installed plates to be uniform, even slight differences can improve the density by installing plates.

[0061] From the above, it was confirmed that, as in the film deposition apparatus 1 and film deposition method according to this embodiment, by arranging a plate 11 between the ejection end 10a of the aerosol transport pipe 10 and the substrate K such that the ejection end 10a of the aerosol transport pipe 10 and the opening 11a face each other, and by making the ratio of the opening area A2 of the plate 11 to the flow path cross-sectional area A1 of the ejection end 10a of the aerosol transport pipe 10 to 1 or more, a homogeneous film can be formed while suppressing a decrease in raw material utilization efficiency and an increase in manufacturing costs.

[0062] [Another embodiment] [1] In the above embodiment, the shape of the flow channel cross-section of the ejection end 10a of the aerosol transport tube 10 is circular, and the shape of the opening 11a of the plate 11 is circular, but it is not limited to this, and it may be square or slit-shaped. Also, the shape of the flow channel cross-section of the ejection end 10a and the shape of the opening 11a of the plate 11 may be different.

[0063] [2] In the above embodiment, a plurality of plates 11 are provided, but the invention is not limited to this, and the number of plates 11 may be one.

[0064] [3] In the above embodiment, the ejection end 10a of the aerosol transport pipe 10 and the base material K are configured to be relatively movable, but the embodiment is not limited to this, and the ejection end 10a of the aerosol transport pipe 10 and the base material K are not required to be relatively movable.

[0065] [4] In the above embodiment, an aerosol transport pipe composed of a straight pipe member was used as the aerosol transport path, but the embodiment is not limited to this. The aerosol transport path may also be an aerosol transport pipe composed of a straight pipe member with a nozzle attached to the tip of the aerosol transport pipe, in which case the tip of the nozzle becomes the ejection end of the aerosol transport path.

[0066] The configurations disclosed in the above embodiments (including other embodiments) can be applied in combination with configurations disclosed in other embodiments, provided that no inconsistencies arise. Furthermore, the embodiments disclosed herein are illustrative, and the embodiments of the present invention are not limited thereto and can be modified as appropriate without departing from the object of the present invention. [Industrial applicability]

[0067] The present invention can be applied to a film-forming apparatus and method for forming a film on a substrate, as well as to a film-forming body. [Explanation of Symbols]

[0068] 1 Film deposition equipment 10 Aerosol transport tube 10a Spout end 11 plates 11a opening K base material A1 Flow path cross-sectional area at the ejection end of the aerosol transport tube Area of ​​the opening formed in the A2 plate

Claims

1. A film deposition apparatus for forming a film on a substrate, An aerosol transport path that ejects an aerosol, in which ceramic raw material powder is dispersed in gas, from an ejection end toward the substrate, The aerosol transport path comprises two or more plates disposed between the ejection end of the aerosol transport path and the substrate such that an opening is formed and the ejection end of the aerosol transport path faces the opening, The two or more plates are arranged parallel to each other and integrally with the aerosol transport path along the direction of aerosol ejection. The ejection end of the aerosol transport path and the substrate are relatively movable. The two or more plates follow the ejection end of the aerosol transport path, The ratio of the area of ​​the openings formed in each of the two or more plates to the cross-sectional area of ​​the flow path at the ejection end of the aerosol transport path is 1 or more and 2 or less. A film deposition apparatus in which the distance from the plate to the substrate is 60 mm or less when depositing a film.

2. The film deposition apparatus according to claim 1, wherein the two or more plates are arranged such that the distance between them is 0.1 mm or more.

3. The density of the particles constituting the ceramic raw material powder is 4.0 g / cm³. ３ The film deposition apparatus according to claim 1 or 2, wherein the above conditions apply.

4. The film deposition apparatus according to any one of claims 1 to 3, wherein the ceramic raw material powder is stabilized zirconia.

5. In a method for forming a film on a substrate by ejecting an aerosol, in which ceramic raw material powder is dispersed in a gas, from the ejection end of an aerosol transport path toward the substrate, The aerosol is ejected onto the substrate through the openings of two or more plates, which are disposed integrally with the aerosol transport path and parallel to each other along the direction of aerosol ejection, with the openings of the plates facing the ejection end of the aerosol transport path and positioned between the ejection end of the aerosol transport path and the substrate, respectively. With the two or more plates following the ejection end of the aerosol transport path, the aerosol is ejected onto the substrate while the ejection end of the aerosol transport path and the substrate are moved relative to each other. The ratio of the area of ​​the openings formed in each of the two or more plates to the cross-sectional area of ​​the flow path at the ejection end of the aerosol transport path is 1 or more and 2 or less. A film deposition method wherein the distance from the plate to the substrate is 60 mm or less during film deposition.

6. The film-forming method according to claim 5, wherein the aerosol is ejected onto the substrate through the openings of the two or more plates arranged such that the distance between the plates is 0.1 mm or more.

7. The density of the particles constituting the ceramic raw material powder is 4.0 g / cm³. ３ The method for forming a film according to claim 5 or 6, wherein the above is true.

8. The method for forming a film according to any one of claims 5 to 7, wherein the ceramic raw material powder is stabilized zirconia.

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