JP6568535B2 - Powder feeder, film forming apparatus, and film forming method - Google Patents

Description

  The present invention relates to an article moving tool and a display shelf. This application claims priority based on Japanese Patent Application No. 2014-189134 for which it applied to Japan on September 17, 2014, and uses the content here.

  One method for forming a thin film on the surface of a substrate is an aerosol deposition method (hereinafter referred to as AD method). In the AD method, powder as a raw material is crushed into nano-sized fine particles, and the fine particles are aerosolized, and then the generated aerosol is sublimated using a carrier gas composed of an inert gas such as nitrogen. It is a method of accelerating from the speed of sound to about supersonic speed and physically spraying on the substrate. In the AD method, the raw material and the base material, or the raw materials are strongly bonded to each other due to the impact hardening phenomenon, so that a thin film is formed on the surface of the base material with a low temperature condition and a high film formation speed. The AD method has advantages such that film formation at room temperature is possible, and there are few restrictions on the characteristics of the substrate. For this reason, various electronic components including a thin film formed by using the AD method have been actively developed.

As described above, in the AD method, it is essential to aerosolize the raw material. Conventionally, a method has been employed in which a raw material that can be aerosolized prepared in advance is contained in a container, and an aerosol is generated by introducing a carrier gas into the container.
For example, Patent Document 1 discloses a composite structure formation including a storage mechanism that stores a raw material, and an aerosolization mechanism that forms an aerosol by dispersing the raw material stored in the storage mechanism in a carrier gas. A system is disclosed. In the system, a supply mechanism for supplying a raw material from the storage mechanism to the aerosol generation mechanism is provided between the storage mechanism and the aerosolization mechanism. Further, the supply mechanism is provided with a pressure blocking mechanism that provides a pressure difference between the pressure in the storage mechanism and the pressure in the aerosolization mechanism, and blocks the flow of carrier gas between the storage mechanism and the aerosolization mechanism. Yes. With this configuration, it is possible to replenish raw materials into the storage mechanism while the composite structure forming system is operating.

JP 2006-206976 A

However, in the composite structure forming system described in Patent Document 1, since a method of compressing the raw material between the accommodation mechanism and the aerosol generating mechanism is used as a means for blocking pressure, the raw material is aggregated and the aerosol is collected. There was a problem that the amount of the raw material derived to the crystallization mechanism varied and the aerosol became unstable.
Patent Document 1 discloses that the raw material extruded and compressed from the storage mechanism can be unraveled by the crushing means, but the raw material is sufficiently undissolved so that the aerosol is stably generated. There was a risk of not being unraveled.

  The present invention has been made in view of the above circumstances, and a powder feeder capable of suppressing reagglomeration and stably generating an aerosol stably without pressing the raw material, and the powder A film forming apparatus including a body supply device and a film forming method using the same are provided.

[1] An agitation unit for agitating a raw material, an aerosolization unit that takes in the agitated raw material and a carrier gas, aerosolizes the raw material to generate an aerosol, and a discharge port that discharges the aerosol; The partition is provided between the stirring unit and the aerosolization unit, and the partition is expanded from the stirring unit side toward the aerosolization unit side, and the stirred raw material is aerosolized A powder feeder in which a lead-out hole leading to the part is formed.
[2] The powder feeder according to [1], wherein a minimum opening width of the outlet hole on the stirring unit side is 100 times or more and 100000 times or less the average particle diameter of the stirred raw material.
[3] The powder feeder according to [1] or [2], wherein an enlargement ratio of the opening area of the outlet hole is 10 times or more and 1000 times or less.
[4] The stirring unit includes a stirring blade rotatable about an axis, and the stirring blade has a hole or a notch through which the raw material is passed. ] The powder feeder according to any one of the above.
[5] The powder feeder according to any one of [1] to [4], wherein a member having a large number of pores is provided between the partition wall and the discharge port.
[6] The powder feeder according to any one of [1] to [5], wherein a pulverizing medium is inserted on the stirring section side of the partition wall.
[7] One or more powder feeders according to any one of [1] to [6] above, a film forming chamber for storing a substrate to be a film forming target, and the powder feeder from the above A film forming apparatus comprising: an injection unit that injects the aerosol introduced into the film forming chamber toward the substrate.
[8] A thin film is formed on a substrate using the powder feeder according to any one of [1] to [6] or the film forming apparatus according to [7]. Membrane method.

  According to the present invention, a powder supplier capable of suppressing reagglomeration and generating an aerosol stably and efficiently without pressing and solidifying the raw material, and a film provided with the powder supplier An apparatus and a film forming method using them are provided.

It is sectional drawing which shows the powder feeder which is one Embodiment of this invention. It is sectional drawing which shows the 1st modification of the powder feeder which is one Embodiment of this invention. It is sectional drawing which shows the 2nd modification of the powder feeder which is one Embodiment of this invention. It is sectional drawing which shows the 3rd modification of the powder feeder which is one Embodiment of this invention. It is sectional drawing which shows the 4th modification of the powder feeder which is one Embodiment of this invention. It is sectional drawing which shows the 5th modification of the powder feeder which is one Embodiment of this invention. It is sectional drawing which shows the 6th modification of the powder feeder which is one Embodiment of this invention. It is sectional drawing which shows the 7th modification of the powder feeder which is one Embodiment of this invention. It is the schematic for demonstrating the usage method of the powder feeder which is one Embodiment of this invention. It is the schematic for demonstrating the usage method of the powder feeder which is one Embodiment of this invention. It is the schematic for demonstrating the usage method of the powder feeder which is one Embodiment of this invention. It is the schematic which shows the structure of the film-forming apparatus provided with the powder feeder which is one Embodiment of this invention. It is sectional drawing which shows the 8th modification of the powder feeder which is one Embodiment of this invention.

  Hereinafter, with reference to FIG. 1 to FIG. 8, a powder feeder as an embodiment to which the present invention is applied, a film forming apparatus including the powder feeder, and a film forming method using the same. I will explain. The drawings used in the following description are schematic, and ratios of length, width, and thickness are not necessarily the same as actual ones, and can be changed as appropriate. The materials and the like exemplified in the following description are examples, and the present invention is not limited to them, and can be appropriately modified and implemented without changing the gist thereof.

[Powder feeder]
1 to 7 are sectional views showing a powder feeder 1 according to a first embodiment of the present invention. As shown in FIGS. 1 to 7, the powder supply device 1 of the present embodiment includes at least a stirring unit 3, an aerosolization unit 4, and a discharge port 53. The powder feeder 1 of the present embodiment includes a generation container 5 that accommodates the agitation unit 3, the aerosolization unit 4, and the discharge port 53.

The generation container 5 is a casing of the powder supply device 1 and includes the stirring unit 3, the aerosolization unit 4, the discharge port 53, and the partition wall 8 in the same space. The generation container 5 is a container-like member that continuously generates the aerosol 62 and sends it out. The generation container 5 is formed in a substantially cylindrical shape so that the filled raw material can be easily stirred.
The generation container 5 is provided with an upper inlet 51 and a lower inlet 52 as two carrier gas inlets. Furthermore, a discharge port 53 for sending the generated aerosol 62 to the outside is provided at the bottom of the generation container 5 (on the downstream side of the aerosol generating unit 4). Although carrier gas is not specifically limited, For example, oxygen, nitrogen, a noble gas, air (atmosphere) etc. are used.

The stirring unit 3 is a place for crushing and stirring the raw material 6, and also serves as a place for storing the raw material 6 as a raw material of the aerosol 62. The stirring unit 3 is configured to communicate with the aerosol generating unit 4 via the outlet hole 8H of the partition wall 8 inside the generation container 5.
The structure for filling the raw material 6 in the stirring unit 3 is not particularly limited. Although detailed illustration is omitted, in order to fill the raw material 6 in the stirring unit 3, for example, a lid may be provided on the top of the generation container 5, and any one of the height directions of the generation container 5 may be provided. The inside of the production container 5 may be divided into upper and lower positions at the position and can be opened and closed.
Another container may be connected to the generation container 5 with a pipe or the like, and the raw material 6 may be filled in the container, and the raw material 6 may be supplied from the container to the generation container 5. It is not limited to the illustrated arrangement and configuration.

The agitation unit 3 is composed of a crushing and stirring means for crushing and stirring the raw material 6. As the crushing and stirring means, a means capable of crushing and stirring the raw material 6 by cutting the space forming the stirring unit 3 (hereinafter referred to as a stirring space) is preferable. Examples of such crushing and stirring means include a rotating body 3C shown in FIGS. 1 and 2, stirring rods 3D and 3E shown in FIGS. 3 and 4, a car 3J shown in FIG. 5, and a stirring member 3M shown in FIG. Etc.
An upper inlet 51 for introducing the carrier gas into the stirring unit 3 is disposed so as to open at a part of the upper side surface of the generation container 5. It is preferable that conditions for introducing the carrier gas into the stirring unit 3 are appropriately determined in consideration of the characteristics of the raw material 6 and the like. The flow rate of the carrier gas introduced into the agitation unit 3 is appropriately determined in consideration of the injection speed from the injection unit 19 in the film forming chamber 11 shown in FIG. 12, for example, from 0.1 L / min to 10.0 L It is sufficient that it is set within a range of about / min, and it is preferably within a range of 0.5 L / min to 5 L / min.

As shown in FIGS. 1 and 2, the rotating body 3 </ b> C includes a rotating shaft 3 </ b> A provided in the longitudinal direction of the stirring unit 3 and in the vicinity of the center when viewed from above the generation container 5, and a substantially rectangular shape in plan view. And a plate-like stirring blade 3B.
The rotating shaft 3 </ b> A rotates the stirring blade 3 </ b> B by being rotated by a motor (not shown) provided outside the generation container 5. The center of the rotating shaft 3A constitutes an axis J of rotation of the stirring blade 3B.
One long side end of the stirring blade 3B is connected to the rotating shaft 3A. The stirring blade 3B extends toward the inner peripheral surface of the generation container 5 with the long side end on the rotating shaft 3A side as a base end. With such a configuration, the stirring space is divided into a plurality of small spaces by the stirring blade 3 </ b> B when the generation container 5 is viewed from above.

It is preferable that the length of the rotating shaft 3A and the size of the stirring blade 3B are set in consideration of the diameter and length of the generation container 5. Part or all of the bottom end of the stirring blade 3B is preferably in contact with the stirring unit 3 side of the partition wall 8. With such a configuration, aggregation of the raw material 6 immediately above the partition wall 8 is further suppressed.
1 and 2 illustrate a rotating body 3C having two stirring blades 3B and 3B. However, the number of stirring blades 3B is not limited to two, so that stirring can be performed while cutting the stirring space. It is preferable to set as appropriate. Although the number of stirring blades is not particularly limited, the number of stirring blades 3B is preferably 2 or more and 8 or less from the viewpoint of increasing the crushing efficiency of the raw material 6 and the stability of the particle size distribution.

In the stirring blade 3 </ b> B shown in FIG. 1, a hole H that allows communication between the small spaces is formed. In the stirring blade 3 </ b> B shown in FIG. 2, a notch C that communicates the small spaces is formed. The size and shape of the hole H or the notch C are not particularly limited as long as the raw material 6 can be circulated between the small spaces.
In order to promote stirring of the raw material 6 between the small spaces, a baffle plate 3F may be provided inside the generation container 5 as shown in FIG. The baffle plate 3F is a so-called baffle plate, and is fixed to a side wall inside the generation container 5. According to such a configuration, the notch C sequentially passes through the baffle plate 3F when the rotating body 3C stirs the raw material 6 so as to cut the stirring space. Accordingly, the baffle plate 3F moves the raw material 6 in the vicinity of the notch C from the small space forward of the rotating body 3C in the rotating direction to the small space behind the rotating direction, and from the rotating direction front of the rotating body 3C to the rotating direction rearward. It becomes easy to move, and the stirring of the raw material 6 in the small spaces is promoted as described above.

FIG. 1 and FIG. 2 illustrate the stirring blade 3B in which three holes H, H, H or notches C, C, C are formed, but the hole H or each formed in each stirring blade 3B The number of notches C is not limited to three. The shape of the hole H or the notch C is not limited to a circle as in the illustrated example, and may be an ellipse, a triangle, a quadrangle, other polygons, a cross, a star, or other shapes. The number and shape of the holes H or notches C formed in each stirring blade 3B is such that the raw material 6 is stirred so that the rotating body 3C cuts the stirring space, and at that time, the raw material 6 flows between the small spaces. It is preferable to set appropriately so that it can do.
In the hole H or the notch C, a member having a large number of pores such as a mesh may be installed.

  The rotating body 3C is configured to crush and stir the raw material 6 by having the above shape. At that time, the raw material 6 flows through the plurality of small spaces through the holes H or the notches C, so that the raw material 6 is stirred without remaining in a part of the stirring space, and reaggregation is suppressed.

As shown in FIG. 3, the stirring rod 3 </ b> D is a rod-like member formed in a spiral shape with respect to the longitudinal direction of the stirring unit 3. As shown in FIG. 4, the stirring rod 3 </ b> E is a rod-shaped member having a plurality of refracting portions along the longitudinal direction of the stirring portion 3. The thickness and shape of the stirring rods 3D and 3E are preferably set in consideration of the diameter and length of the generation container 5. The bottom ends of the stirring bars 3D and 3E are preferably in contact with the stirring unit 3 side of the partition wall 8. With such a configuration, aggregation of the raw material 6 immediately above the partition wall 8 is further suppressed.
The spiral shape of the stirring bar 3D and the inner angle and number of the refracting portion of the stirring bar 3E are such that the stirring bar 3D, 3E cuts the stirring space and stirs the raw material 6 and the raw material 6 is in a small space between them. It is preferable to set appropriately so that it can be distributed.
The stirring rods 3D and 3E can be rotated in the direction of the arrow by a motor (not shown) provided outside the generation container 5. The stirring rods 3D and 3E may be connected to the rotating shaft 3A by a spring plate (not shown) without being connected to the motor (see FIG. 6).

  The stirring rods 3D and 3E are shaped as described above, thereby crushing and stirring the raw material 6. At that time, the raw material 6 passes through the gap between the stirring rods 3D and 3E, and is stirred without remaining in a part of the stirring space, thereby suppressing reaggregation.

As shown in FIG. 5, the car 3J is made of a material having pores such as metal processed into a mesh shape. The pore size of the material is not particularly limited as long as the raw material 6 can be crushed and stirred, but a pore size of about 0.01 mm mesh to 1 mm mesh is preferable. It is preferable that part or all of the bottom end of the car 3J is in contact with the stirring unit 3 side of the partition wall 8. With such a configuration, aggregation of the raw material 6 immediately above the partition wall 8 is further suppressed.
The car 3J is supported in the generation container 5 by a support member 3K or the like, and can be rotated in the direction of the arrow by a motor (not shown) provided outside the generation container 5.

  The cage 3J is shaped as described above, thereby crushing and stirring the raw material 6. At that time, the raw material 6 flows between the outside and the inside of the car 3J through the pores, so that the raw material 6 is stirred without staying at a fixed position in the stirring space, and reaggregation is suppressed.

As shown in FIG. 6, the stirring member 3M includes a rotating shaft 3A, a scraper 3N, and a spring plate 3P that connects the rotating shaft 3A and the scraper 3N.
The base end of the spring plate 3P is connected to the rotating shaft 3A. The tip of the spring plate 3P is connected to the scraper 3N.
The scraper 3 </ b> N extends along the axis J of the stirring unit 3 and is disposed in the vicinity of the inner peripheral surface of the generation container 5.
It is preferable that part or all of the bottom ends of the scraper 3N and the spring plate 3P provided at the lowermost part are in contact with the stirring unit 3 side of the partition wall 8. With such a configuration, aggregation of the raw material 6 immediately above the partition wall 8 is further suppressed.

  The stirring member 3M has the shape described above, thereby crushing and stirring the raw material 6. At that time, the raw material 6 passes through the space surrounded by the rotating shaft 3A, the scraper 3N, and the upper and lower spring plates 3P, 3P, thereby being stirred without staying in a part of the stirring space, and reaggregation is suppressed. The

The crushing and stirring means is not limited to the rotating body 3C, the stirring rods 3D and 3E, the cage 3J, and the stirring member 3M described above. The crushing and stirring means preferably employs a structure that allows the raw material 6 to move freely within the stirring space.
The crushing and stirring means may be a combination of two or more of the configuration examples described above, or may have other configurations. For example, the crushing and stirring means may be a stirring bar having a plurality of curved portions and refractive portions in the longitudinal direction.
From the viewpoint of suppressing the aggregation of the raw material 6 immediately above the partition wall 8, it is preferable that the crushing stirring means and the like are in contact with the stirring unit 3 side of the partition wall 8.
The structure of the rotating body 3C, the stirring rods 3D and 3E, the cage 3J, the stirring member 3M, and the other crushing stirring means described above that is in contact with the stirring unit 3 side of the partition wall 8 is not particularly limited. You may contact | connect with a structure like a scraper.

  The crushing and stirring means is preferably made of a material having a hardness higher than that of the raw material 6. For example, the Mohs hardness is more preferably 6 or more. Examples of the material having such hardness include various metal materials such as stainless steel (SUS), titanium, tungsten, silicon carbide, and aluminum oxide.

  The number of rotations of the crushing and stirring means when crushing and stirring the raw material 6 is not particularly limited, but is preferably in the range of 1 rpm to 1000 rpm, and more preferably in the range of 1 rpm to 10 rpm. preferable. By setting the number of rotations of the stirring unit 3 made of a rotating body within the above range, the raw material 6 is crushed and stirred well, and is led out toward the aerosolization unit 4. Thereby, the reaggregation of the raw material 6 is further effectively suppressed, and the aerosol 62 is stably and efficiently generated in the aerosolization unit 4.

The partition wall 8 is a partition member interposed between the stirring unit 3 and the aerosol-generating unit 4 below the stirring unit 3. The partition wall 8 is formed with a lead-out hole 8H. The outlet hole 8H is formed so as to expand from the stirring unit 3 side toward the aerosol-generating unit 4 side. The cross-sectional shape of the lead-out hole 8H is circular, but may be, for example, an ellipse, a polygon such as a triangle or a quadrangle, a star, or the like, and may be changed as appropriate.
The raw material 6 is collected in the outlet hole 8H and pushed out by the rotation operation of the crushing and stirring means. At this time, it passes through a narrower portion of the lead-out hole 8H and is discharged into the lead-out hole 8H that is enlarged immediately thereafter, thereby being moderately dispersed.

From the viewpoint of deriving the stirred raw material 6, the minimum opening width of the outlet hole 8H on the stirring unit 3 side is preferably 100 times or more and 100000 times or less the average particle diameter of the stirred raw material 6. More preferably, it is 100 times or more and 10,000 times or less. Here, the “opening width” refers to the diameter when the cross-sectional shape of the introduction hole 8H is circular, the short diameter when it is elliptical, and the shortest side length when it is a polygon such as a triangle or quadrangle. Refers to In addition, the “minimum opening width” being in the above range means that 80% or more, preferably 90% or more, of the total number of the plurality of introduction holes 8H is in the whole hole from the top to the bottom. It means that the minimum opening width is within the above range.
From the viewpoint of appropriately adjusting the degree of dispersion of the raw material 6 that passes through the outlet hole 8H, the enlargement ratio of the opening area of the outlet hole 8H is preferably not less than 10 times and not more than 1000 times. Here, the “opening area enlargement ratio” indicates the ratio of the maximum opening area to the minimum opening area for each lead-out hole 8H.
The opening area of the outlet hole 8H may be enlarged at a constant rate as shown in FIG. 1, or may be enlarged stepwise and discontinuously as shown in FIG.
The minimum opening width of the outlet hole 8H on the stirring unit 3 side is 100 times or more the average particle diameter of the stirred raw material 6, and the enlargement ratio of the opening area of the outlet hole 8H is 10 times or more. preferable.

As shown in FIGS. 1 to 7, grinding media such as beads and balls 20 are inserted on the side of the agitation unit 3 of the partition wall 8. By inserting grinding media such as beads and balls 20, the raw material 6 is crushed and easily stirred by the stirring unit 3, and is efficiently collected in the outlet hole 8H.
From the viewpoint of crushing the raw material 6, the average particle diameter of the grinding media such as beads and balls 20 should be not less than 2 times and not more than 200 times the minimum opening width of the outlet hole 8H on the stirring unit 3 side. Preferably, it is more preferably 2 times or more and 100 times or less from the viewpoint of the crushing effect. As a method for measuring the average particle size of the grinding media such as beads and balls 20, the same method as the method for measuring the average particle size of the stirred raw material 6 can be adopted, and a caliper or a ruler is used. May be.
As the grinding media such as beads and balls 20, a single particle size may be used, or different diameter particles may be used in combination.
Examples of materials such as grinding media such as beads and balls 20 include, but are not limited to, silica, aluminum oxide, silicon carbide, zirconia, glass, nylon, Teflon (registered trademark), and the like.

The aerosolization unit 4 is a space for generating an aerosol 62 by aerosolizing the raw material 6 stirred by the stirring unit 3 with a carrier gas introduced into the generation container 5.
In the vicinity of the aerosol generating unit 4, a lower introduction port 52 into which a carrier gas is taken is arranged so as to open at a part of the side surface of the production container 5. The raw material 6 led out from the partition wall 8 is dispersed in the carrier gas introduced from the lower inlet 52 and is aerosolized.

The aerosol 62 is discharged from the discharge port 53 provided at the bottom of the generation container 5.
As shown in FIGS. 1 to 7, a member 21 having a large number of pores is provided between the partition wall 8 and the discharge port 53. The minimum opening width of the pores of the member 21 is preferably 100 times or more and 100,000 times or less, more preferably 100 times or more and 10,000 times or less, and more preferably 100 times or more the average particle diameter of the stirred raw material 6. More preferably, it is 1000 times or less. By setting the minimum opening width of the pores of the member 21 within the above range, the agglomerated aerosol 62 and the like cannot pass through the member 21 and cannot reach the discharge port 53. Therefore, the aggregation of the aerosol 62 is suppressed by installing the member 21.

  In the powder feeder 1, first, a carrier gas is introduced from an upper inlet 51 provided in the upper part of the generation container 5, and the agitation unit 3 is operated. Next, when the carrier gas is introduced from the lower introduction port 52 provided in the lower part of the generation container 5, the raw material 6 is aerosolized in the aerosolization unit 4, and the generated aerosol 62 is outside the generation container 5. Is sent out. The aerosol 62 is transported from the discharge port 53 toward the injection unit 19 installed in the film forming chamber 11 of the film forming apparatus 10 shown in FIG.

The generation efficiency of the aerosol 62 depends on the flow rate of the carrier gas introduced into the aerosolization unit 4. Accordingly, the conditions such as the flow rate of the carrier gas introduced into the aerosolization unit 4 are preferably set in consideration of the characteristics of the raw material 6 and the generation efficiency of the aerosol 62.
The flow rate of the carrier gas introduced into the aerosolization unit 4 is appropriately determined in consideration of the injection speed from the injection unit 19 in the film forming chamber 11 shown in FIG. 12, and the raw material 6 is effectively contained in the carrier gas. the dispersing aerosolized, the flow rate that can be delivered from the discharge port 53 at high speed, for example, need only be set to be within a range from 0.1L / min · cm ² for about 1000L / min · cm ^2, It is preferably set to be in the range of 1 L / min · cm ² to 100 L / min · cm ² .

  The powder feeder 1 shown in FIGS. 1 to 7 is provided with two inlets, an upper inlet 51 and a lower inlet 52, as carrier gas inlets, but the present invention is not limited to this form. For example, the structure which made only one introduction port by optimizing arrangement | positioning of the introduction port in the production | generation container 5 may be sufficient.

From the viewpoint of efficiently sending the generated aerosol 62 to the outside, the discharge port 53 is preferably provided in the vicinity of the aerosol-generating unit 4 and on the bottom side of the generation container 5.
In the example of the powder feeder 1 shown in FIGS. 1 to 7, the opening area of the lower part of the production container 5 is reduced as it goes downward, and the aerosolization unit 4 is arranged in the lower part of the production container 5. However, as shown in FIG. 8, the lower part of the production container 5 (below the partition wall 8) may have substantially the same width as the upper part of the production container 5 (above the partition wall 8 or the stirring unit 3). Absent. When the opening width of the generation container 5 is substantially uniform as described above, a lower introduction port 52 may be provided at the bottom of the generation container 5 as shown in FIG. A discharge port 53 may be provided in a substantially central portion in the direction and in the vicinity of a portion immediately below the partition wall 8.

[How to use the powder feeder]
First, as shown in FIG. 9, the raw material 6 is filled above the partition wall 8 of the production vessel 5 until the height is about the same as the upper end of the stirring blade 3 </ b> B. For example, the powder supply device 1 can be filled with the raw material 6 by opening a lid (not shown) provided in the generation container 5 and storing the raw material 6 in the stirring unit 3. The upper inlet 51 is located above the filled raw material 6.
Thereafter, a carrier gas made of, for example, nitrogen is supplied toward the upper introduction port 51. As a result, the carrier gas is introduced into the powder feeder 1.
Then, the crushing stirring means of the stirring part 3 is operated. The raw material 6 loaded in the stirring unit 3 is crushed and stirred by introduction of the carrier gas and rotation of the stirring unit 3, and is guided to the outlet hole 8H together with the carrier gas. As the crushing and stirring means continues to rotate, the amount of the raw material 6 in the stirring unit 3 gradually decreases as shown in FIGS. When the raw material 6 is used up (see FIG. 11), the raw material 6 is loaded into the powder feeder 1.
The raw material 6 is led out to the aerosolization part 4 from the lead-out hole 8H with the introduction of the carrier gas into the stirring part 3 and the rotation of the crushing and stirring means.
In order to stir the raw material 6 satisfactorily in the agitation unit 3 and effectively lead it toward the aerosolization unit 4, the flow rate of the carrier gas and the crushing agitation means are taken into account in consideration of the height dimension of the production vessel 5 It is beneficial to adjust each of the rotation speeds appropriately.

  Subsequently, a carrier gas is supplied toward the lower introduction port 52. As a result, the carrier gas is introduced into the aerosolization unit 4. The raw material 6 led out to the aerosol-generating part 4 from the lead-out hole 8H is dispersed in the carrier gas introduced from the lower introduction port 52 to be aerosolized, and an aerosol 62 is generated. The aerosol 62 is sent out from the discharge port 53.

[Film deposition system]
FIG. 12 is a schematic diagram showing a film forming apparatus 10 that includes the powder feeder 1 and adopts the AD method. In FIG. 12, of the constituent elements of the powder feeder 1, illustration of the agitation unit 3, the crushing and agitation means, the aerosolization unit 4, the partition wall 8, the outlet hole 8H, and the like is omitted.
The film forming apparatus 10 includes at least one powder feeder 1 and can accommodate a base material 41 to be formed, and a film forming chamber 11 for forming a thin film (not shown) on one surface 41a thereof. The spray unit 19 sprays the aerosol 62 introduced from the powder feeder 1 into the film forming chamber 11 toward the substrate 41.

In the film forming chamber 11, a stage 12 having an arrangement surface 12a for arranging the base material 41 is provided. The stage 12 is movable in the horizontal direction with the base material 41 disposed.
A vacuum pump 13 is connected to the film forming chamber 11. By the suction of the vacuum pump 13, the inside of the film forming chamber 11 can be negatively pressured.
An injection unit 19 is disposed in the film forming chamber 11. The opening of the discharge port 19a of the injection unit 19 is provided so as to face one surface 41a of the base material 41 disposed on the arrangement surface 12a of the stage 12.

The injection unit 19 is connected to the gas cylinder 16 via the transport pipe 15.
In the path of the transport pipe 15, a mass flow controller 17 and a powder feeder 1 are provided in order from the gas cylinder 16 side. It is preferable that a crusher 25 and a classifier 18 are provided between the powder feeder 1 and the injection unit 19. Aggregation of the aerosol 62 is suppressed by providing the crusher 25 at the subsequent stage of the powder feeder 1. By providing the classifier 18 in the subsequent stage of the powder feeder 1, the particle size distribution of the aerosol 62 is suppressed within an appropriate range.

In the film forming apparatus 10, the above-described transport pipe 15, gas cylinder 16, mass flow controller 17, powder feeder 1, crusher 25, and classifier 18 constitute a powder transport mechanism.
The carrier gas is supplied from the gas cylinder 16 to the transport pipe 15. The flow rate of the carrier gas is adjusted by the mass flow controller 17. The carrier gas adjusted by the mass flow controller 17 is introduced into the powder feeder 1 through the two transport pipes 15.

Since the internal configuration of the powder feeder 1 is as described above, the description thereof is omitted.
Finally, the aerosol 62 is discharged and injected from the injection unit 19 toward the one surface 41a of the base material 41 at an injection speed of subsonic speed or higher and supersonic speed or lower.

[Film formation method]
Below, the process of producing | generating the aerosol 62 using the powder supply apparatus 1 of the said structure or the film-forming apparatus 10, and the production | generation of the aerosol 62 when the powder supply apparatus 1 is applied to the film-forming apparatus 10 are shown. The film forming process including this will be described. Hereinafter, a method of forming a photoelectrode of a dye-sensitized solar cell will be described as an example of forming a thin film by the AD method using the film forming apparatus 10.

  In the film forming method of the present embodiment, the raw material 6 such as an inorganic substance is aerosolized, and the obtained aerosol 62 is sprayed on the base material 41 to join the base material 41 and the raw material 6 together with the raw material 6. A thin film of an inorganic substance is formed on the base material 41 by bonding them together.

First, the base material 41 is arranged on the arrangement surface 12 a of the stage 12 in the film forming chamber 11.
Examples of the base material 41 include, but are not limited to, transparent substrates and plastics used in various electronic components such as photoelectrodes used in dye-sensitized solar cells.
Examples of the transparent substrate include a substrate made of glass or plastic, or a film. Examples of the glass that is a material of the base material 41 include soda lime glass, borosilicate glass, quartz glass, borosilicate glass, Vycor glass, alkali-free glass, blue plate glass, and white plate glass.
Examples of the plastic that is the material of the base material 41 include polyacrylic resin, polycarbonate resin, polyester resin, polyimide resin, polystyrene resin, polyvinyl chloride resin, and polyamide resin. Among these plastics, a polyester resin, in particular, polyethylene naphthalate (PEN) is suitable as a material for the substrate 41 from the viewpoint of being produced and used in large quantities as a transparent heat-resistant film. Furthermore, from the viewpoint of producing a thin, light and flexible dye-sensitized solar cell, in particular, a polyethylene terephthalate (PET) film is suitable as a material for the base material 41.

Next, the vacuum pump 13 is operated to evacuate the film forming chamber 11.
Thereafter, nitrogen is supplied from the gas cylinder 16 into the film forming chamber 11 through the transport pipe 15 to make the inside of the film forming chamber 11 a nitrogen atmosphere.

  Next, tin-doped indium oxide (ITO), fluorine-doped tin oxide (FTO), zinc oxide (ZnO), tin oxide, antimony-doped tin oxide (ATO), indium oxide / zinc oxide (IZO), gallium oxide / zinc oxide ( A conductive material such as GZO) is used as the raw material 6, and a conductive layer made of the conductive material is formed on one surface 41 a of the base material 41. You may use the base material 41 in which the conductive layer which consists of the said electrically conductive material in advance was formed.

Next, a photoelectric conversion layer made of a metal oxide such as titanium oxide (TiO ₂ ), zinc oxide (ZnO), tin oxide (SnO ₂ ) is formed on the conductive layer formed on one surface 41 a of the base material 41. Form. In order to form the photoelectric conversion layer, first, the raw material 6 made of the metal oxide is filled in the stirring unit 3 of the powder feeder 1.

Next, the crushing stirring means of the stirring unit 3 is rotated and the carrier gas is introduced into the stirring unit 3 from the upper inlet 51. The raw material 6 is crushed and stirred by the rotational force of the crushing and stirring means. Further, the raw material 6 is led out from the lead-out hole 8H by the rotation operation of the crushing and stirring means and the carrier gas, and is introduced into the aerosolization unit 4. The raw material 6 is dispersed in the carrier gas introduced into the aerosol generating unit 4 from the lower introduction port 52 to be aerosolized. Thereafter, the generated aerosol 62 is discharged from the discharge port 53 to the transport pipe 15 and conveyed to the crusher 25 and the classifier 18 in this order, and further to the injection unit 19 installed in the film forming chamber 11. Transport.
Then, the aerosol 62 is sprayed from the discharge port 19 a of the injection unit 19 onto the surface of the conductive layer formed on the one surface 41 a of the base material 41.

At least a part of the raw material 6 that collides with the surface of the conductive layer formed on the substrate 41 bites into the surface of the conductive layer and is not easily peeled off. Due to the collision between the conductive layer and the raw material 6, a new surface is formed on the surface of the conductive layer and the surface of the raw material 6. Mainly, the conductive layer and the raw material 6 are joined on this new surface.
By continuing the spraying of the aerosol 62, another raw material 6 collides with the raw material 6 that has digged into the surface of the conductive layer. By such collision of the raw materials 6, new surfaces are formed on the surfaces of the raw materials 6, and the raw materials 6 are joined mainly on the new surfaces. Such a collision between the raw materials 6 is not performed at such a high temperature that the raw materials 6 are melted, so that a temperature rise is unlikely to occur. There is substantially no grain boundary layer made of glass at the interface where the raw materials 6 are joined.
Furthermore, by continuing the spraying of the raw material 6, a thin film (not shown) is formed in which a large number of the raw materials 6 are gradually joined to the surface of the conductive layer formed on the base material 41. The formed thin film has sufficient strength as a conductive layer of the dye-sensitized solar cell. Furthermore, baking can be performed to increase the strength.

The above film forming method, on one surface 41a formed on the surface of the conductive layer of the substrate 41, by blowing TiO ₂ particles at high speed, with joining the conductive layer and the TiO ₂ particles, TiO ₂ particles are By bonding, a thin film photoelectrode made of TiO ₂ particles can be formed on the conductive layer.
Unlike the so-called green compact, the thin film obtained by the above procedure is stronger than the green compact and is more difficult to peel from the base material 41 than the green compact.

[Effects of Powder Feeder 1, Film Forming Apparatus 10, and Film Forming Method According to the Present Invention]
As described above, according to the powder feeder 1 according to the present invention, the partition wall 8 is provided between the stirring unit 3 and the aerosol generating unit 4. The partition wall 8 is formed with a lead-out hole 8 </ b> H that expands from the stirring unit 3 side toward the aerosolization unit 4 side and leads the raw material 6 to the aerosolization unit 4.
With the above configuration, the raw material 6 can be diffused in the outlet hole 8H immediately after being collected in the outlet hole 8H and pushed out from the stirring unit 3 side. Therefore, when deriving from the stirring unit 3 to the aerosol-generating unit 4, re-aggregation can be effectively suppressed without pressing the raw material 6 as before. In the aerosol generating unit 4, the aerosol 62 can be generated stably and efficiently.

According to the powder feeder 1 according to the present invention, the minimum opening width of the outlet hole 8H on the stirring unit 3 side is set to be 100 times or more and 100000 times or less the average particle diameter of the stirred raw material 6. Preferably, the enlargement ratio of the opening area of the outlet hole 8H is preferably 10 times or more and 1000 times or less.
With the above configuration, only the raw material 6 crushed and stirred from the stirring unit 3 can enter the outlet hole 8H, and the dispersity of the raw material 6 while passing through the outlet hole 8H is appropriately adjusted. Therefore, the aerosol 62 can be generated stably and efficiently while effectively suppressing reaggregation of the raw material 6.

According to the powder feeder 1 according to the present invention, the stirring unit 3 is provided with the stirring blade 3B that can rotate around the axis J, and the stirring blade 3B has a hole H or a notch C through which the raw material 6 passes. It is preferable that the stirrer 3 </ b> D formed in a spiral shape along the direction of the axis J is provided in the stirrer 3.
With the above configuration, when the rotating body 3C or the stirring rod 3D is rotated, the raw material 6 flows in the small space of the stirring unit 3 partitioned by the stirring blade 3B through the hole H or the notch C. The raw material 6 is agitated and does not stay in the fixed position of the agitating unit 3. Therefore, the aerosol 62 can be generated stably and efficiently while effectively suppressing reaggregation of the raw material 6.

According to the powder feeder 1 according to the present invention, the member 21 having a large number of pores is preferably provided between the partition wall 8 and the discharge port 53. The size of the pores of the member 21 is more preferably 100 times or more and 100000 times or less the average particle diameter of the raw material 6.
With the above configuration, only the crushed aerosol 62 can pass through the pores of the member 21 and reach the discharge port 53. Therefore, aggregation of the generated aerosol 62 can be effectively suppressed.

According to the powder feeder 1 according to the present invention, it is preferable that grinding media such as beads and balls 20 be inserted on the stirring unit 3 side of the partition wall 8.
With the above configuration, the raw material 6 loaded on the stirring unit 3 side of the partition wall 8 is crushed by a pulverizing medium such as beads and balls 20 and easily and quickly by an air flow by a carrier gas introduced from the upper introduction port 51. Then, it is carried to the aerosolization unit 4.

  According to the film forming apparatus 10 according to the present invention, since the powder feeder 1 is provided, reaggregation of the raw material 6 is suppressed in the apparatus, and a thin film having excellent characteristics on the base material 41. Can be formed with high productivity.

  According to the film forming method of the present invention, since the thin film is formed on the base material 41 using the powder feeder 1 or the film forming apparatus 10 described above, a thin film having excellent characteristics can be formed with high productivity. There is an effect that becomes possible.

The preferred embodiment of the present invention has been described in detail above. However, the present invention is not limited to the embodiment, and various modifications can be made within the scope of the gist of the present invention described in the claims.・ Change is possible.
For example, although detailed illustration is omitted, the film forming apparatus 10 may include a plurality of powder feeders 1. The plurality of powder feeders 1 may have different particle size distributions, and aerosol 62 having different average particle sizes may be generated and introduced into the film forming chamber 11. By adopting a configuration in which the aerosol 62 having a different particle size distribution is introduced into the film forming chamber 11, for example, the particle size distribution in the thin film formed on the substrate 41 is arbitrarily adjusted by adjusting the fraction of the aerosol 62. Can do. In addition to arbitrarily adjusting the particle size distribution, for example, the raw material 6 having a different particle size distribution can be sprayed onto the base material 41, and a thin film variation can be obtained.

  The present invention can be widely applied in the field related to thin film formation using a powder feeder, a film forming apparatus, and a film forming method.

DESCRIPTION OF SYMBOLS 1 ... Powder feeder 3 ... Stirring part 3B ... Stirring blade 3D ... Stirring rod 4 ... Aerosolization part 6 ... Raw material 8 ... Partition 8H ... Outlet 10 ... Film-forming apparatus 11 ... Film-forming chamber 20 ... Ball (for grinding | pulverization) media)
21 ... Member 41 ... Base 53 ... Discharge port 62 ... Aerosol C ... Notch H ... Hole J ... Axis

Claims (8)

A stirring unit for stirring the raw material,
An aerosolization unit that takes in the raw material and the carrier gas that have been stirred, and aerosolizes the raw material to generate an aerosol;
A discharge port for discharging the aerosol,
A partition wall is provided between the stirring unit and the aerosolizing unit,
A powder feeder in which an opening area is increased in the partition wall from the agitation unit side toward the aerosolization unit side, and a lead-out hole for leading the agitated raw material to the aerosolization unit is formed.
  2. The powder feeder according to claim 1, wherein a minimum opening width of the lead-out hole on the stirring unit side is 100 times or more and 100000 times or less the average particle diameter of the stirred raw material.   The powder feeder according to claim 1 or 2, wherein an enlargement ratio of the opening area of the lead-out hole is 10 times or more and 1000 times or less. The stirring unit includes a stirring blade that can rotate around an axis,
The powder feeder according to any one of claims 1 to 3, wherein a hole or a notch through which the raw material is passed is formed in the stirring blade.   The powder feeder according to any one of claims 1 to 4, wherein a member having a large number of pores is provided between the partition wall and the discharge port.   The powder feeder according to any one of claims 1 to 5, wherein a pulverization medium is inserted on the stirring section side of the partition wall. Comprising one or more powder feeders according to any one of claims 1 to 6,
A film forming chamber for storing a substrate to be formed;
A film forming apparatus comprising: an injection unit configured to inject the aerosol introduced from the powder supplier into the film forming chamber toward the substrate.   A film forming method for forming a thin film on a substrate using the powder feeder according to any one of claims 1 to 6 or the film forming apparatus according to claim 7.

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