Film Forming Apparatus, Film Forming Method, and Formed Film

Abstract

Provided is a film forming apparatus capable of stably supplying a large amount of ceramic raw material powder for a long time and forming a homogeneous and dense film. A film forming apparatus 1 for forming a film on a base material K includes an aerosol transport path 10 for ejecting an aerosol obtained by dispersing a ceramic raw material powder in a gas, from an ejection end 10a toward the base material K, in which a flow path cross-section at an ejection end 10a of the aerosol transport path 10 has a substantially circular shape with an area of 10 mm.sup.2 or more.

Claims

1. A film forming apparatus for forming a film on a base material, comprising: an aerosol transport path for ejecting an aerosol obtained by dispersing a ceramic raw material powder in a gas, from an ejection end toward the base material, and wherein a flow path cross-section at the ejection end of the aerosol transport path has a substantially circular shape with an area of 10 mm.sup.2 or more.

2. The film forming apparatus according to claim 1, wherein a distance from the ejection end of the aerosol transport path to the base material is 100 mm or less.

3. The film forming apparatus according to claim 1, wherein a value obtained by dividing the area of the flow path cross-section at the ejection end of the aerosol transport path by a square of a distance between the ejection end of the aerosol transport path and the base material is 0.001 or more.

4. The film forming apparatus according to claim 1, further comprising: a processing chamber with an inner space in which at least a portion on a side of the ejection end of the aerosol transport path and the base material are arranged, and wherein a flow path cross-section of the aerosol transport path at a processing chamber internal transport section located in the processing chamber has a substantially circular shape with an area of 10 mm.sup.2 or more.

5. The film forming apparatus according to claim 4, wherein the shape of the flow path cross-section at the processing chamber internal transport section corresponds to the shape of the flow path cross-section at the ejection end.

6. The film forming apparatus according to claim 4, wherein a pressure in the processing chamber is 0.6 kPa or less.

7. The film forming apparatus according to claim 1, wherein the aerosol transport path is a straight pipe member.

8. The film forming apparatus according to claim 1, wherein a density of particles of the ceramic raw material powder is 4.0 g/cm.sup.3 or more.

9. The film forming apparatus according to claim 1, wherein the ceramic raw material powder is stabilized zirconia.

10. A film forming method for forming a film on a base material comprising ejecting an aerosol obtained by dispersing a ceramic raw material powder in a gas, from an ejection end of an aerosol transport path toward the base material, and wherein ejecting the aerosol toward the base material from the ejection end has a flow path cross-section that has a substantially circular shape with an area of 10 mm.sup.2 or more.

11. The film forming method according to claim 10, wherein a distance from the ejection end of the aerosol transport path to the base material is 100 mm or less.

12. The film forming method according to claim 10, wherein a value obtained by dividing a flow path cross-sectional area at the ejection end of the aerosol transport path by a square of a distance between the ejection end of the aerosol transport path and the base material is 0.001 or more.

13. The film forming method according to claim 10, further comprising: arranging at least a portion on a side of the ejection end of the aerosol transport path and the base material in an inner space of a processing chamber, and ejecting the aerosol toward the base material from the ejection end of the aerosol transport path in which a flow path cross-section at a processing chamber internal transport section located in the processing chamber has a substantially circular shape with an area of 10 mm.sup.2 or more.

14. The film forming method according to claim 13, wherein the shape of the flow path cross-section at the processing chamber internal transport section corresponds to the shape of the flow path cross-section at the ejection end.

15. The film forming method according to claim 13, wherein a pressure in the processing chamber is 0.6 kPa or less.

16. The film forming method according to claim 10, wherein the aerosol transport path is a straight pipe member.

17. The film forming method according to claim 10, wherein a density of particles of the ceramic raw material powder is 4.0 g/cm.sup.3 or more.

18. The film forming method according to claim 10, wherein the ceramic raw material powder is stabilized zirconia.

19. A formed film formed by the film forming apparatus according to claim 1.

20. A formed film formed through the film forming method according to claim 10.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0036] FIG. 1 is a diagram showing a configuration of a film forming apparatus according to an embodiment.

[0037] FIG. 2 is a view of an aerosol transport pipe according to the present embodiment viewed from a side of an ejection end.

[0038] FIG. 3 is a diagram showing a positional relationship between the aerosol transport pipe and the base material.

[0039] FIG. 4 is a diagram showing the ejection end of the film forming apparatus used in Comparative Example 1.

[0040] FIG. 5 is a diagram showing the ejection end of the film forming apparatus used in Comparative Example 2.

[0041] FIG. 6 is a diagram schematically showing a base material after film formation processing in Comparative Example 1.

[0042] FIG. 7 is a diagram schematically showing a base material after film formation processing in Comparative Example 2.

DESCRIPTION OF THE INVENTION

[0043] 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.

[0044] Film Forming Apparatus

[0045] As shown in FIG. 1, the film forming apparatus according to this embodiment includes a processing chamber 2, an aerosol generating section 6, an aerosol transport pipe 10 (aerosol transport path), a carrier gas feeding means 15, and the like.

[0046] The processing chamber 2 is an airtight housing. The inside of the processing chamber 2 is depressurized to a predetermined pressure (e.g., about 0.6 kPa) or less by discharging gas by a mechanical booster pump 3 and a vacuum pump 4 serving as exhaust equipment. Also, in the inner space of the processing chamber 2, a holding section 5 for holding a base material K to be subjected to the film forming processing and part of the aerosol transport pipe 10 are arranged.

[0047] The aerosol generating section 6 is a device that generates an aerosol by dispersing ceramic raw material powder in gas. In this embodiment, the aerosol generating section 6 is connected to a raw material powder supply section 7 via a raw material supply pipe 51. Also, the aerosol generating section 6 is connected to a carrier gas feeding pipe S2 and the aerosol transport pipe 10, which will be described later. Also, in the aerosol generating section 6, an aerosol is generated by mixing the ceramic raw material powder supplied from the raw material powder supply section 7 at a constant speed and the carrier gas fed by the carrier gas feeding means 15. The generated aerosol is fed to the aerosol transport pipe 10. Note that the time it takes to form a film having a target thickness can be shortened by increasing the supply speed of the ceramic raw material powder supplied from the raw material powder supply section 7 to the aerosol generating section 6, but if the supply speed is too high, pulsation will occur in the supply amount of the raw material powder, making it difficult to obtain a homogeneous film. On the other hand, if the supply speed is too slow, the film quality is improved, but the time required to complete film formation increases, and thus the manufacturing cost increases. For this reason, the supply speed of the ceramic raw material powder is preferably 1.5 to 30 g/min.

[0048] As shown in FIGS. 1 to 3, the aerosol transport pipe 10 has an ejection end 10a and a processing chamber internal transport section 10b (at least a portion on a side of the ejection end), and the ejection end 10a is disposed in the processing chamber 2 in such a manner as to oppose the holding section 5 in the processing chamber 2. The aerosol transport pipe 10 in the present embodiment is a cylindrical straight pipe member having a flow path cross-sectional area A1 (shaded portion in FIG. 3) with a predetermined inner diameter, and the end portion opposite to the ejection end 10a is connected to the aerosol generating section 6. That is, in the aerosol transport pipe 10 of the present embodiment, the flow path cross-section in the processing chamber internal transport section 10b and the flow path cross-section at the ejection end 10a are both circular with the same flow path cross-sectional area A1. According to this aerosol transport pipe 10, the aerosol is fed from the aerosol generating section 6, and the fed aerosol is ejected from the opening of the ejection end 10a.

[0049] Next, the flow path cross-sectional area A1 at the ejection end 10a of the aerosol transport pipe 10, a distance Ia between the ejection end 10a of the aerosol transport pipe 10 and the base material K, and the relationship between the flow path cross-sectional area A1 and the distance Ia will be explained.

[0050] The flow path cross-sectional area A1 of the ejection end 10a of the aerosol transport pipe 10 is not particularly limited as long as it is 10 mm.sup.2 or more, but is preferably 20 mm.sup.2 or more, more preferably 30 mm.sup.2 or more, and even more preferably 95 mm.sup.2 or more. Note that in the present embodiment, the flow path cross-sectional area A1 is 95 mm.sup.2.

[0051] The distance Ia from the ejection end 10a of the aerosol transport pipe 10 to the base material K is not particularly limited, but is preferably 100 mm or less, more preferably 40 mm or less, and even more preferably 10 mm or less. On the other hand, if the distance between the ejection end 10a of the aerosol transport pipe 10 and the base material K is too small, when the base material K has a distorted shape, there is a risk that the ejection end 10a and the base material K will come into contact with each other when the aerosol transport pipe 10 and the base material K are moved relative to each other, and therefore it is preferable that the distance Ia between the ejection end 10a of the aerosol transport pipe 10 and the base material K is 2 mm or more. Note that in this embodiment, the distance Ia is 10 mm.

[0052] Also, with the film forming apparatus 1, the value obtained by dividing the flow path cross-sectional area A1 at the ejection end 10a of the aerosol transport pipe 10 by a square of the distance Ia between the ejection end 10a of the aerosol transport pipe 10 and the base material K (hereinafter referred to as “(A1/Ia.sup.2) value”) is set to be 0.001 or more (that is, 95/10.sup.2=0.95 in the present embodiment). Note that although there is no particular limitation on the (A1/Ia.sup.2) value, it is preferably 0.001 or more, more preferably 0.007 or more, and even more preferably 0.03 or more. Also, the (A1/Ia.sup.2) value is preferably 25 or less, and more preferably 1 or less.

[0053] The carrier gas feeding means 15 includes a gas supply section 16, a carrier gas pressure control unit 17, a carrier gas flow rate control unit 18, a carrier gas feeding pipe S2, and the like.

[0054] Specifically, a carrier gas feeding pipe S2 is connected to the gas supply section 16, and the gas supply section 16 supplies gases such as air, N.sub.2, He, and Ar to the carrier gas feeding pipe S2 using a compressor or a gas cylinder.

[0055] In this embodiment, the carrier gas feeding pipe S2 is for feeding the gas supplied from the gas supply section 16 to the aerosol generating section 6 as the carrier gas. Specifically, in the present embodiment, the gas sent from the gas supply section 16 is fed as the carrier gas to the aerosol generating section 6 via the carrier gas pressure control unit 17 and the carrier gas flow rate control unit 18 in the stated order, and the carrier gas feeding pipe S2 is constituted by a plurality of pipes connected between the gas supply section 16, the carrier gas pressure control unit 17, the carrier gas flow rate control unit 18, and the aerosol generating section 6.

Also, a pressure sensor P1 for detecting the pressure in the carrier gas feeding pipe S2 is provided between the carrier gas flow rate control unit 18 and the aerosol generating section 6 in the carrier gas feeding pipe S2.

[0056] The carrier gas pressure control unit 17 statically stabilizes the carrier gas flowing through the carrier gas feeding pipe S2 at an appropriate pressure, and the carrier gas flow rate control unit 18 controls the flow rate of the carrier gas flowing through the carrier gas feeding pipe S2. In this embodiment, the operations of the carrier gas pressure control unit 17 and the carrier gas flow rate control unit 18 are appropriately controlled based on the pressure detected by the pressure sensor P1 and the like.

[0057] Ceramic Raw Material Powder

[0058] Particles constituting the ceramic raw material powder used in the film forming apparatus 1 preferably have a density of 4.0 g/cm.sup.3 or more, and such particles include, for example, particles of stabilized zirconia in which yttrium, calcium, magnesium, hafnium, or the like is contained in zirconia. Note that in this embodiment, yttrium-containing zirconia (YSZ) is used as the ceramic raw material powder.

[0059] Film Formation Method

[0060] Next, the process of forming a film (formed film) on the base material K through the film forming method using the film forming apparatus 1 will be described. In the film forming method according to the present embodiment, the carrier gas is supplied from the gas supply section 16 to the aerosol generating section 6 while the carrier gas pressure control unit 17 and the carrier gas flow rate control unit 18 adjust the flow rate and pressure of the carrier gas flowing through the carrier gas feeding pipe S2. The aerosol generating section 6 generates an aerosol in which the fed carrier gas and the ceramic raw material powder supplied from the raw material powder supply section 7 are mixed. The generated aerosol is fed to the aerosol transport pipe 10.

[0061] The aerosol fed to the aerosol transport pipe 10 is ejected from the ejection end 10a of the aerosol transport pipe 10 toward the base material K, and the ejected aerosol collides with the base material K to form a film on the base material K.

[0062] Here, the aerosol ejected toward the base material K is ejected from the ejection end 10a having a circular flow path cross section, and the above (A1/Ia.sup.2) value is 0.95 (that is, 0.001 or more). Accordingly, the ejected aerosol has a uniform speed in the flow path cross section of the ejection end 10a, and variation in particle speed in the direction perpendicular to the base material K at the time of collision with the base material K is less likely to occur. For this reason, adhesion of a powder compact and formation of porosity are suppressed, and a homogeneous and dense film is formed. In particular, when the ceramic raw material powder is a stabilized zirconia such as YSZ, which has a relatively high density, a highly dense and homogeneous film can be formed. In addition, since the flow path cross-sectional area A1 of the ejection end 10a is 95 mm.sup.2 (i.e., 10 mm.sup.2 or more), the ceramic raw material powder is less likely to accumulate at the ejection end 10a, and a large amount of ceramic raw material powder can be stably supplied for a long time, and therefore it is possible to form a film on the base material K over a long period of time.

[0063] Working Examples 1 to 5 and Comparative Examples 1 to 4 will be described below. Film formation was performed for a predetermined time while moving the base material back and forth along a predetermined direction with different shapes of the flow path cross-section at the ejection end of the aerosol transport pipe, different flow path cross-sectional areas, and different distances between the ejection end and the base material. YSZ particles having a density of 5.9 g/cm.sup.3 and a median diameter of 1.01 μm were used as the raw ceramic powder in each of the working examples and comparative examples. Also, the flow rate of the carrier gas was set to 18 L/min, and the pressure in the processing chamber was set to 0.2 kPa in each working example and each comparative example.

[0064] Tables 1 to 3 are tables summarizing various conditions and results for Working Examples 1 to 5 and Comparative Examples 1 to 4, and “area of porous region” in Table 2 shows the area of a porous region with a low adhesive strength.

Also, FIG. 4 is a diagram showing the ejection end of the nozzle used in Comparative Example 1, and the area of the A3 portion indicated by shading in FIG. 4 is the flow path cross-sectional area. The shape of the nozzle used in Comparative Example 1 is a shape conventionally adopted as the shape of the nozzle of an apparatus for performing film formation processing through the AD method.
Furthermore, FIG. 5 is a diagram showing the ejection end of the nozzle used in Comparative Example 2, and the area of the A2 portion indicated by shading in FIG. 5 is the flow path cross-sectional area. FIG. 6 is a diagram schematically showing the base material after the film formation processing in Comparative Example 1, and the up-down direction in FIG. 6 is the movement direction of the base material. Also, FIG. 7 is a diagram schematically showing the base material after the film forming processing in Comparative Example 2, and, similarly to the above, the up-down direction in FIG. 7 is the movement direction of the base material. Note that in FIGS. 6 and 7, the dark shaded portions are the portions where a powder compact is adhered.

TABLE-US-00001 TABLE 1 Work. Work. Comp. Comp. Ex. 1 Ex. 2 Ex. 1 Ex. 2 Flow path cross- Circular Circular Slit-shaped Square sectional shape (11 mm φ) (11 mm φ) (10 mm × (10 mm 0.6 mm) square) Flow path cross- 95 95 6 100 sectional area (mm.sup.2) Distance between 10 40 10 10 ejection end and base material (mm) (A1/Ia.sup.2) value 0.950 0.059 0.060 1 Adhesion state of Not adhered Not adhered Adhered Adhered powder compact

TABLE-US-00002 TABLE 2 Work. Work. Work. Ex. 3 Ex. 4 Ex. 5 Flow path cross-sectional Circular Circular Circular shape (5.5 mm φ) (5.5 mm φ) (5.5 mm φ) Flow path cross-sectional area 23.75 23.75 23.75 (mm.sup.2) Distance between ejection end 10 40 60 and base material (mm) (A1/Ia.sup.2) value 0.237 0.015 0.007 Area of porous region (mm.sup.2) 56 336 364 Adhesion state of powder Not adhered Not adhered Not adhered compact

TABLE-US-00003 TABLE 3 Comp. Ex. 3 Comp. Ex. 4 Flow path cross-sectional shape Circular Circular (2.25 mm φ) (2.25 mm φ) Flow path cross-sectional shape (mm.sup.2) 3.97 3.97 Distance between ejection end and base 10 5 material (mm) (A1/Ia.sup.2) value 0.040 0.159 Adhesion state of powder compact Adhered Adhered

[0065] As can be understood from Table 1, when comparing Working Examples 1 and 2 with Comparative Examples 1 and 2, no adhesion of the powder compact was observed in Working Examples 1 and 2, whereas a large amount of powder compact was adhered in Comparative Examples 1 and 2 (see FIGS. 6 and 7). For example, as shown in FIG. 7, in Comparative Example 2, when the film formation processing is performed while the base material is moved back and forth, a large amount of the powder compact is adhered to the portion where the particles in the aerosol sprayed toward the base material from the corner portion where the flow of the aerosol is likely to be disturbed.

Based on these findings, it was confirmed that by making the cross-sectional shape of the ejection end of the aerosol transport path circular instead of square or slit-shaped as in the conventional technique, the flow speed of the aerosol becomes uniform within the flow path cross-section, and a uniform film can be formed on the base material.

[0066] Also, as shown in Table 2, even in Working Examples 3 to 5, in which the cross-sectional areas of the flow paths are slightly smaller than those in Working Examples 1 and 2, adhesion of the powder compact is not observed. On the other hand, regarding Working Examples 3 to 5, when the area of the porous region is focused on, it can be understood that the area of the porous region decreases and the uniformity of the film improves the higher the (A1/Ia.sup.2) value is.

[0067] Also, as shown in Table 3, in Comparative Examples 3 and 4, in which the cross-sectional areas of the flow paths are smaller than those of Working Examples 3 to 5, a large amount of the powder compact was adhered to the base material even though the cross-sectional shape of the flow path was circular. It is assumed that this is because even if the cross-sectional shape of the flow path is circular, the raw material powder will be clogged if the cross-sectional area of the flow path is too small. Due to this, it was confirmed that even if the channel cross-sectional shape is circular, a flow path cross-sectional area of a certain degree is required in order to suppress the formation of the powder compact and form a homogeneous film on the base material, and if the flow path cross-sectional area is too small, a homogeneous film cannot be formed on the base material.

[0068] Due to the above, it was confirmed that, as in the film forming apparatus 1 and the film forming method according to the present embodiment, by using an aerosol transport pipe 10 in which the flow path cross-section at the ejection end 10a is circular with an area of 10 mm.sup.2 or more, a large amount of ceramic raw material powder can be stably supplied for a long time, and a homogeneous film can be formed.

Other Embodiments

[0069] [1] In the above embodiment, the flow path cross-sectional area A1 at the ejection end 10a of the aerosol transport pipe 10 was 10 mm.sup.2 or more, and the (A1/Ia.sup.2) value was 0.001 or more, but there is no limitation to this. If the flow path cross-sectional area A1 is 10 mm.sup.2 or more, the (A1/Ia.sup.2) value does not need to be 0.001 or more.

[0070] [2] In the above embodiment, the distance from the ejection end 10a of the aerosol transport pipe 10 to the base material K was 100 mm or less, but there is no limitation to this as long as the flow path cross-sectional area A1 is 10 mm.sup.2 or more. In particular, if the cross-sectional area A1 of the flow path is 10 mm.sup.2 or more and the (A1/Ia.sup.2) value is 0.001 or more, variation in the particle speed in the direction perpendicular to the base material at the time of collision with the base material is less likely to occur, and therefore the effect of suppressing adhesion of a powder compact and formation of porosity is obtained.

[0071] [3] In the above embodiment, the aerosol transport pipe 10 was a cylindrical straight pipe member, but there is no limitation to this. Even if a crushing mechanism for crushing aggregated particles, a classifying mechanism for classifying particles, or the like is separately provided in the path of the straight pipe member, the flowability of the aerosol is not impaired, and therefore it is possible to stably supply a large amount of ceramic raw material powder for a long time. As long as the shape of the flow path cross-section at the ejection end 10a of the aerosol transport tube 10 is substantially circular, the straight tube member need not be used. Note that the substantially circular shape includes not only a perfect circle but also an elliptical shape. The substantially circular shape also includes triangles and polygons with curved corners, the polygons having a number of corners greater than or equal to that of a pentagon, and quadrilaterals with curved corners in which the ratio (r/R) of a radius r of a curved surface portion of a corner of the quadrilateral and the radius R of a circumscribing circle exceeds 0.3. In such a case as well, the flow speed of the aerosol at the ejection end becomes uniform within the cross section of the flow path, and therefore the effect of forming a homogeneous and dense film on the base material can be obtained.

[0072] [4] In the above embodiment, the flow path cross-section at the processing chamber internal transport section 10b of the aerosol transport pipe 10 and the flow path cross-section at the ejection end 10a were both circular with the same flow path cross-sectional area A1, but there is no limitation to this, and the shapes of both flow path cross-sections may be different from each other. For example, the shape of the flow path cross-section at the ejection end 10a may be circular, and the shape of the flow path cross-section at the processing chamber internal transport section 10b need not be circular, and the shapes of both flow path cross-sections may both be circular and have different areas. Note that the area of the flow path cross-section in the processing chamber internal transport section 10b of the aerosol transport pipe 10 is preferably 10 mm.sup.2 or more, more preferably 20 mm.sup.2 or more, more preferably 30 mm.sup.2 or more, and even more preferably 95 mm.sup.2 or more.

[0073] [5] In the above embodiment, the processing chamber was depressurized to 0.6 kPa or less, but the present invention is not limited to this.

[0074] The configurations disclosed in the above embodiments (including other embodiments) can be applied in combination with configurations disclosed in other embodiments as long as there is no contradiction, and the embodiment described in the present specification is an example, the embodiment of the present invention is not limited thereto, and can be modified as appropriate without departing from the object of the present invention.

INDUSTRIAL APPLICABILITY

[0075] The present invention can be applied to a film forming apparatus and film forming method for forming a film on a base material, and a formed film.

DESCRIPTION OF REFERENCE SIGNS

[0076] 1 Film forming apparatus [0077] 10 Aerosol transport pipe (aerosol transport path) [0078] 10a Ejection end [0079] 10b Processing chamber internal transport section [0080] K Base material