Mist generating device, thin film manufacturing device, and thin film manufacturing method

Abstract

To provide a compact and inexpensive mist generator which performs film deposition on a substrate.SOLUTION: The mist generator comprises: a container 91 for storing a liquid; a gas supply unit for supplying a first gas from a gas supply port 70A into the container 91; and a plasma generation unit which includes an electrode 78A for generating plasma between itself and a liquid surface of the liquid and includes a hollow body surrounding the electrode 78A. One tip of the hollow body is positioned below the liquid surface of the liquid.SELECTED DRAWING: Figure 1

Description

[Technical field]

[0001] The present invention relates to a mist generating device, a thin film manufacturing device, and a thin film manufacturing method. [Background technology]

[0002] Conventionally, a deposition method as shown in Patent Document 1 has been used as a technique for forming a thin film on a substrate. In general, in addition to the deposition method, a method that requires a vacuum or reduced pressure environment, such as a sputtering method, is used in the film formation process. Therefore, the problem is that the equipment becomes large and expensive. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication 2010-265508 Summary of the Invention

[0004] A first aspect of the present invention is a mist generating device comprising: a container for containing a liquid; a gas supply unit for supplying a first gas into the container from a gas supply port; a plasma generating unit having an electrode for generating plasma between the electrode and the liquid surface; and a hollow body surrounding the electrode, one tip of the hollow body being positioned below the liquid surface of the liquid.

[0005] A second aspect of the present invention is a thin-film manufacturing apparatus for forming a film on a substrate, comprising the apparatus of the first aspect and a mist supplying section for supplying the liquid in a mist form onto a predetermined substrate.

[0006] A third aspect of the present invention is a thin film manufacturing method for forming a film on a substrate, comprising the steps of: turning a liquid into a mist using the apparatus of the first aspect; and supplying the mist of the liquid to a specified substrate. [Brief description of the drawings]

[0007] [Figure 1]1 is a schematic diagram illustrating an example of a mist generating device according to a first embodiment. [Diagram 2] 2A and 2B are schematic diagrams showing an example of a tip 79 of an electrode 78 in the first embodiment. Fig. 2A is an example of an electrode 78A in which a tip 79A has a needle-like shape, Fig. 2B is an example of an electrode 78A in which a tip 79B has a plurality of needle-like portions, and Fig. 2C is an example of an electrode 78C in which a tip 79C has a spherical shape. [Diagram 3] FIG. 3A is a schematic diagram showing an example of a gas supply unit according to the first embodiment, illustrating the supply direction; FIG. 3B is a schematic diagram illustrating the supply direction of gas supply unit 70B; and FIG. 3C is a diagram illustrating the angle θ in FIG. 3A. [Figure 4] Fig. 4A is a schematic diagram showing an example of a discharge direction and an angle α between the discharge direction and the direction of gravity. Fig. 4A is a schematic diagram showing an example of a discharge section 74A of the first embodiment and explaining the discharge direction. Fig. 4B is a schematic diagram explaining the discharge direction of a discharge section 74B. Fig. 4C is a diagram for explaining the angle α. [Diagram 5] Fig. 5A is a schematic diagram of a gas supply unit 70C and a discharge unit 74C according to the first embodiment, and Fig. 5B is a diagram for explaining the angle β between the supply direction and the discharge direction. [Figure 6] 1 is a schematic diagram showing an example of a mist generating device according to a first modified example of the first embodiment. FIG. [Figure 7] 10 is a schematic diagram showing an example of a mist generating device according to a second modified example of the first embodiment. FIG. [Figure 8] FIG. 11 is a schematic diagram showing an example of a mist generating device according to a third modified example of the first embodiment. [Figure 9] FIG. 11 is a schematic diagram showing an example of a mist generating device according to a fourth modified example of the first embodiment. [Figure 10] FIG. 13 is a schematic diagram showing an example of a mist generating device according to a fifth modified example of the first embodiment. [Figure 11] FIG. 11 is a schematic diagram showing an example of a mist generating device according to a second embodiment. [Figure 12] FIG. 11 is a schematic diagram showing an example of a mist generating device according to a third embodiment. [Figure 13] FIG. 11 is a schematic diagram showing a modification of the mist generating device according to the third embodiment. [Figure 14] FIG. 13 is a schematic diagram showing an example of a mist generating device according to a fourth embodiment. [Figure 15] FIG. 13 is a schematic diagram showing an example of a mist generating device according to a fifth embodiment. [Figure 16] FIG. 13 is a schematic diagram showing a modification of the mist generating device according to the fifth embodiment. [Figure 17] FIG. 13 is a schematic diagram showing an example of a mist generating device according to a sixth embodiment. [Figure 18] FIG. 13 is a schematic diagram showing a modification of the mist generating device according to the sixth embodiment. [Figure 19] FIG. 13 is a diagram showing an example of the configuration of a thin-film manufacturing apparatus according to a seventh embodiment. [Figure 20] 13 is an example of a perspective view of a mist supply unit as viewed from the substrate side. FIG. [Figure 21] 13 is an example of a cross-sectional view of the tip portion of the mist supply portion and a pair of electrodes as viewed from the Y-axis direction. [Figure 22] FIG. 2 is a block diagram showing an example of a schematic configuration of a high-voltage pulse power supply unit. [Diagram 23] FIG. 4 is a diagram showing an example of waveform characteristics of an inter-electrode voltage obtained by a high-voltage pulse power supply unit. [Figure 24] FIG. 2 is a cross-sectional view showing an example of a configuration of a substrate temperature control unit. [Diagram 25] FIG. 13 is a schematic diagram showing an example of a mist generating device according to an eighth embodiment. [Figure 26] 26A is a diagram for explaining an outline of a plasma generating unit, Fig. 26A is an example of the appearance of the tip portion of the plasma generating unit, Fig. 26B is an example (part 1) of a cross-sectional view (top view) of the plasma generating unit, and Fig. 26C is an example (part 2) of a cross-sectional view (top view) of the plasma generating unit. [Figure 27] FIG. 23 is a schematic diagram showing an example of a mist generating device according to a first modified example of the eighth embodiment. [Figure 28] FIG. 23 is a schematic diagram showing an example of a mist generating device according to a second modified example of the eighth embodiment. [Figure 29] FIG. 23 is a schematic diagram showing an example of a mist generating device in a third modified example of the eighth embodiment. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] A mist generating device 90 according to a mode for carrying out the present invention (hereinafter referred to as the "present embodiment"), a thin film manufacturing apparatus 1 equipped with the mist generating device 90, and a thin film manufacturing method for manufacturing a thin film using the mist generating device 90 will be described in detail below with reference to the accompanying drawings as preferred embodiments. The following present embodiment is for the purpose of explaining the present invention, and is not intended to limit the present invention to the following content. In the drawings, the positional relationships such as up, down, left, and right are based on the positional relationships shown in the drawings, unless otherwise specified. Furthermore, the dimensional ratios of the drawings are not limited to those shown.

[0009] [First embodiment] 1 is a schematic diagram showing an example of a mist generating device 90 that generates mist in the first embodiment. In the following description, an XYZ orthogonal coordinate system is set, and the arrows in the figure indicate the X-axis, Y-axis, and Z-axis directions.

[0010] <Mist generating device> 1 includes a container 62 (62A), a gas supply unit 70 (70A), an exhaust unit 74 (74A), an electrode 78 (78A), and a mist generating unit 80 inside an external container 91. The container 62A includes a container unit 60A and a lid unit 61A. A liquid is contained in the container unit 60A. The liquid is not particularly limited, and is preferably a dispersion liquid 63 containing a dispersion medium 64 and particles 66.

[0011] The flow of mist generation using the mist generator 90 will be described. First, the gas supply unit 70A supplies gas to the storage unit 60A. A voltage is applied to the electrode 78A from a power supply unit (not shown), and the above-mentioned gas is plasmatized between the electrode 78A and the liquid surface of the dispersion liquid 63 (hereinafter, sometimes simply referred to as the "liquid surface"). Next, the mist generating unit 80 turns the dispersion liquid 63 in the storage unit 60A into mist. One example of the mist generating unit 80 is an ultrasonic vibrator. The space between the container 62A and the external container 91 is filled with liquid, and the vibration of the ultrasonic vibrator is transmitted to the dispersion liquid 63 in the container 62A through the liquid. As a result, the dispersion liquid 63 is turned into mist. The dispersion liquid 63 may be turned into mist while the plasma is being generated, or may be turned into mist after the plasma is generated. The dispersion liquid 63 may be turned into mist after the plasma is irradiated to prevent the particles 66 from agglomerating, but it is preferable to turn the dispersion liquid 63 into mist during the plasma irradiation to improve the dispersibility of the particles 66. The mist of dispersion liquid 63 (hereinafter, sometimes simply referred to as "mist") is discharged to the outside from exhaust section 74 together with the gas supplied from gas supply section .

[0012] The plasma in this embodiment is plasma above the water surface. Plasma above the water surface refers to plasma generated between one or more electrodes arranged facing the liquid surface and the liquid surface. In FIG. 1, an electrode 78 is provided facing the liquid surface along the Z-axis direction. In addition, the number of electrodes is not limited to one, and may be two or more electrodes in order to generate plasma uniformly in the storage section 60A. The distance between the liquid surface of the stationary liquid and the electrode 78 is preferably 30 mm or less, more preferably 5 nm to 10 mm. In addition, a ground (G) electrode (not shown) may be provided under the container 62A to make it easier for the generated plasma to hit the liquid surface of the dispersion liquid.

[0013] When the plasma comes into contact with the dispersion liquid 63, OH radicals are generated. These OH radicals modify the surfaces of the particles and increase the repulsion between the particles, thereby improving the dispersibility of the particles.

[0014] In order to efficiently disperse the particles 66 in the dispersion medium 64, it is preferable to apply a voltage at a frequency of 0.1 Hz to 50 kHz. The lower limit is preferably 1 Hz, and more preferably 30 Hz. The upper limit is preferably 5 kHz, and more preferably 1 kHz. The voltage applied to the electrodes is 21 kV (electric field is 1.1×10 6 It is preferable that the axial length of the conductor is equal to or larger than the axial length of the conductor.

[0015] The material of the electrode 78A is not particularly limited, but may be copper, iron, titanium, or the like.

[0016] FIG. 2 is a schematic diagram showing an example of the tip 79 of the electrode 78 in the first embodiment. FIG. 2A is an example of the electrode 78A in which the tip 79A has a needle-like shape, FIG. 2B is an example of the electrode 78A in which the tip 79B has a plurality of needle-like portions, and FIG. 2C is an example of the electrode 78C in which the tip 79C has a spherical shape. The electrodes 78B and 78C are modified examples of the electrode 78A. The electrode 78A has a tip 79A. When the tip 79A is viewed from the -Z axis direction, it is preferable that the area of ​​the part of the tip 79A closest to the liquid surface is small from the viewpoint of plasma generation efficiency. Therefore, the shape of the tip 79A is needle-like (FIG. 2A). The shape of the tip of the electrode is not limited to this. The electrode 78B has a tip 79B in a shape having a plurality of needle-like portions (FIG. 2B). The electrode 78C has a spherical tip 79C (FIG. 2C). However, the dimensions and shape of the tip are not limited to those shown in this figure.

[0017] Furthermore, although the electrodes 78 shown in FIGS. 1 and 2 are linear, they may each be bent.

[0018] In the mist generating device 90 according to the present embodiment, it is preferable to cool the dispersion liquid 63. The cooling here includes gradual cooling. The temperature of the dispersion liquid 63 may increase due to contact with plasma. If the temperature of the dispersion liquid 63 increases, the particles 66 aggregate and settle in the dispersion liquid 63, so that the dispersion liquid 63 may not be able to maintain its dispersibility. For example, a cooling pipe (not shown) may be inserted into the container 62A and a refrigerant may be circulated to suppress the temperature increase of the dispersion liquid 63. In addition, in order to prevent impurities from being mixed into the dispersion liquid 63, a cooling pipe may be inserted into the container 62A and the external container 91, and the refrigerant may be circulated through the cooling pipe (not shown) to adjust the temperature of the dispersion liquid. In addition, the temperature of the dispersion liquid 63 is preferably 40 degrees or less, and more preferably 30 degrees or less. In addition, the temperature of the dispersion liquid 63 is preferably 0 degrees or more, and more preferably 10 degrees or more in order to facilitate the function of the ultrasonic vibrator 80. The cooling may be performed during or after the generation of plasma, but it is more preferable to perform the cooling during the generation from the viewpoint of suppressing the temperature increase.

[0019] In FIG. 1, an example in which the mist generating unit 80 is disposed at a distance from the container 62A has been described, but the mist generating unit 80 may be in direct contact with the container 62A. In order to prevent the heat generated in the mist generating unit 80 from being directly thermally conducted to the container 62A, it is preferable to dispose the mist generating unit 80 at a distance from the container 62A. In addition, when disposing the mist generating unit 80 at a distance from the container 62A, as described above, it is preferable to fill the space between the container 62A and the external container 91 with liquid. By configuring in this way, the vibration generated in the mist generating unit 80 can be propagated to the container 62A. In addition, the heat generated in the mist generating unit 80 due to the vibration can be cooled. The liquid may be any liquid that can propagate vibration, and water is preferable.

[0020] The mist obtained by the apparatus according to this embodiment can be suitably used in a film forming apparatus and a film forming method, which will be described later.

[0021] The lid portion 61A is a lid for the storage portion 60A. The lid portion 61A may or may not be present. In the mist generator 90 shown in FIG. 1, the gas supply portion 70A, the exhaust portion 74A, and the electrode 78A are inserted into the lid portion 61A. The lid portion 61A may or may not have a structure that seals the container 62A. If the lid portion 61A has a structure that seals the container 62A, the container 62A can be easily filled with gas, and the plasma generation efficiency can be improved.

[0022] The container 60A is a container that contains the dispersion liquid 63. The material of the container is not particularly limited, but in order to efficiently propagate the vibrations generated in the mist-generating section 80 to the dispersion liquid 63, the material may be plastic or metal.

[0023] The particles 66 are preferably inorganic oxides. Although there are no particular limitations on the inorganic oxide, silicon dioxide, zirconium oxide, indium oxide, zinc oxide, tin oxide, titanium oxide, indium tin oxide, potassium tantalate, tantalum oxide, aluminum oxide, magnesium oxide, hafnium oxide, tungsten oxide, etc. may be used alone or in any combination of two or more kinds.

[0024] The average particle size of the particles 66 is not particularly limited, but may be 5 nm to 1000 nm. The lower limit is preferably 10 nm, more preferably 15 nm, further preferably 20 nm, and even more preferably 25 nm. The upper limit is preferably 800 nm, more preferably 100 nm, and further preferably 50 nm. In this specification, the average particle size is the median diameter of scattering intensity determined by dynamic light scattering spectroscopy.

[0025] The type of the dispersion medium 64 is not particularly limited, and may be any type that can disperse particles. Examples of the dispersion medium that can be used include water, alcohols such as isopropyl alcohol (IPA), ethanol, and methanol, acetone, dimethylformamide (DMF), dimethylsulfoxide (DMSO), ethyl acetate, acetic acid, tetrahydrofuran (THF), diethyl ether (DME), toluene, carbon tetrachloride, n-hexane, and mixtures thereof. Among these, the dispersion medium preferably contains water as the dispersion medium, and is more preferably an aqueous solvent, from the viewpoints of particle dispersibility and dielectric constant.

[0026] The concentration of the particles 66 in the dispersion liquid 63 is not particularly limited, but may be set to 0.001% by mass to 80% by mass or less from the viewpoint of the dispersion effect to be obtained. The upper limit is preferably 50% by mass, more preferably 25% by mass, and still more preferably 10% by mass. The lower limit is preferably 1% by mass, more preferably 2% by mass, and still more preferably 3% by mass.

[0027] The type of gas that serves as the plasma source for generating plasma is not particularly limited, and any known gas can be used. Specific examples of the gas include helium, argon, xenon, oxygen, nitrogen, and air. Among these, helium, argon, and xenon, which are highly stable, are preferred.

[0028] The plasma generation time is not particularly limited, but from the viewpoint of dispersing the particles 66 well, the total generation time can be 25 to 1800 seconds. The lower limit is preferably 25 seconds. The upper limit is preferably 1800 seconds, more preferably 900 seconds, and even more preferably 600 seconds. The plasma may be generated continuously (one time) or intermittently. Even in the case of intermittent generation, the total generation time is preferably the above-mentioned irradiation time.

[0029] The gas supply unit 70A introduces gas supplied from outside the mist generating device 90 into the container 62A. The shape of the gas supply unit 70A is not limited to a cylindrical shape. The gas supply port 72A of the gas supply unit 70A is installed inside the storage unit 60A. The shape of the gas supply port 72A is not limited to a circular shape.

[0030] Fig. 3 is a schematic diagram showing an example of a supply direction and an angle θ between the supply direction and the direction of gravity. Fig. 3A is a schematic diagram showing an example of a gas supply unit 70A of the first embodiment and explaining the supply direction. Fig. 3B is a schematic diagram explaining the supply direction of gas supply unit 70B. Fig. 3C is a diagram for explaining the angle θ in Fig. 3A.

[0031] 3A and 3B, the supply direction of gas supplied from gas supply port 72A and gas supply port 72B in gas supply unit 70A and gas supply unit 70B will be described. The supply direction refers to the direction in which gas supply unit 70 extends from gas supply port 72 (extension direction). In the case of FIG. 3A, the extension direction of gas supply unit 70A is the +X axis direction, and the supply direction is the +X axis direction as shown by arrow (a). In the case of FIG. 3B, the extension direction of gas supply unit 70B is the gravity direction, and the supply direction is the gravity direction (-Z axis direction) as shown by arrow (a). Note that arrow (a) is a line drawn from the center of gravity of gas supply port 72 in the supply direction.

[0032] Next, the angle θ between the supply direction and the direction of gravity (g) will be described with reference to Fig. 3C (the gas supply unit of Fig. 3A is used in Fig. 3C). The smaller angle between the supply direction and the direction of gravity is called the angle θ between the supply direction and the direction of gravity. For example, in the case of this embodiment, θ is 90 degrees.

[0033] In the case of the mist generator shown in FIG. 1, the first intersection of the arrow (a) (a line drawn from the center of gravity of the gas supply port 72 in the supply direction) is the side of the container 62A, and the momentum of the supplied gas is weakened. In other words, the first intersection of the line drawn from the center of gravity of the gas supply port 72 in the supply direction is configured not to be the liquid surface of the dispersion liquid 63. This makes it possible to stably generate plasma without the liquid surface rippling significantly. If the gas hits the liquid surface directly, the liquid surface will ripple significantly. As a result, the electrode 78A comes into contact with the liquid surface of the dispersion liquid 63, and plasma is not generated between the electrode 78A and the dispersion liquid 63.

[0034] In this embodiment, it is preferable that the gas supply port 72 and the liquid level of the dispersion liquid 63 do not face each other. Here, in this specification, "the gas supply port and the liquid level of the dispersion liquid do not face each other" means that the portion where a line drawn from the center of gravity of the gas supply port 72 in the supply direction first intersects is a portion other than the liquid level of the dispersion liquid.

[0035] The exhaust part 74A exhausts the mist and gas generated in the storage part 60A to the outside of the container 62A. The shape of the exhaust part 74A is not limited to a cylindrical shape. The exhaust outlet 76A of the exhaust part is installed in the storage part 60A and exhausts the mist and gas from the storage part 60A to the outside of the mist generating device 90. The shape of the exhaust outlet 76A is not limited to a circular shape.

[0036] Fig. 4 is a schematic diagram showing an example of a discharge direction and an angle α between the discharge direction and the direction of gravity. Fig. 4A is a schematic diagram showing an example of a discharge section 74A of the first embodiment and explaining the discharge direction. Fig. 4B is a schematic diagram explaining the discharge direction of a discharge section 74B. Fig. 4C is a diagram for explaining the angle α in Fig. 4A.

[0037] 4A and 4B, the discharge direction of the mist and gas discharged from the discharge port 76A and the discharge port 76B in the discharge portion 74A and the discharge portion 74B will be described. The discharge direction refers to the opposite direction to the direction in which the discharge portion 74 extends from the discharge port 76 (extension direction). In the case of FIG. 4A, the opposite direction to the extension direction of the discharge portion 74A is the +Z axis direction, and the discharge direction is the +Z axis direction as shown by the arrow (b). In the case of FIG. 4B, the opposite direction to the extension direction of the discharge portion 74B is the -X axis direction, and the discharge direction is the -X axis direction. Here, the arrow (b) is drawn from the center of gravity of the discharge port 76 in the discharge direction.

[0038] Next, the angle α between the discharge direction and the direction of gravity (g) will be described with reference to FIG. 4C (FIG. 4C uses the discharge unit of FIG. 4A). As shown in FIG. 4C, the smaller angle between the discharge direction and the direction of gravity is called the angle α between the discharge direction and the direction of gravity. When the two directions are opposite to each other as in this embodiment, there are two angles that are 180 degrees, and in this case, one of the angles is set as α. In FIG. 4C, 180 degrees is defined using a counterclockwise angle as viewed from the direction of gravity, but 180 degrees may also be defined using a clockwise angle.

[0039] When α=180 degrees, the liquid surface and the outlet 76A face each other, so the generated mist is efficiently discharged to the outside of the container 62A.

[0040] The gas supply port 72A may be located above or below the exhaust port 76A. However, in order to make it easier to mix the supplied gas and to discharge a uniform mist to the outside of the container 62A, it is preferable that the gas supply port 72A be located below the exhaust port 76A.

[0041] FIG. 5 is an explanatory diagram showing an example of an angle β between the supply direction and the exhaust direction. FIG. 5A is a schematic diagram of the gas supply unit 70C and the exhaust unit 74C of the first embodiment. FIG. 5B is a diagram for explaining the angle β. The supply direction (represented by an arrow (a) here) and the exhaust direction (represented by an arrow (b) here) shown in FIG. 5A are illustrated in FIG. 5B. In FIG. 5B, the smaller angle of the angles formed by the two directions is called the angle β formed by the supply direction and the exhaust direction. It is desirable that the angle β is set to an angle such that the gas exhausted from the exhaust unit 74C contains mist. Therefore, the angle β may be 30 degrees to 150 degrees. The upper limit may be 135 degrees or 120 degrees. The lower limit may be 60 degrees, and 90 degrees is more preferable.

[0042] 3A and 4A show the case where θ=90 degrees and α=180 degrees, but the present embodiment is not limited to this.

[0043] [First embodiment: Modification 1] Fig. 6 is a schematic diagram showing an example of a mist generating device 90 in Modification 1 of the first embodiment. Differences from the above-described embodiment will be described below. Note that the mist generating device 90 in the embodiment and modifications shown in Figs. 6 to 18 includes an external container 91 and mist generating section 80 similar to those in the above-described embodiment. Therefore, in the example shown below, the mist generating section 80 and external container 91 are omitted from illustration.

[0044] The mist generator 90 shown in FIG. 6 has a gas supply unit 70D. The gas supply unit 70D has a gas supply port 72D, and θ<90 degrees. In this modification, the first intersection of the arrow (a) (a line drawn from the center of gravity of the gas supply port 72D in the supply direction) is the side of the container 60A. When the gas collides with the side of the container, the momentum of the gas being supplied weakens, and the gas can be supplied into the container 62A without disturbing the liquid surface. In this modification, the first intersection of the arrow (a) is not limited to the side of the container 60A, but may be the discharge unit 74A or the electrode 78A.

[0045] [First embodiment: Modification 2] FIG. 7 is a schematic diagram showing an example of a mist generator 90 in the second modified example of the first embodiment. In the mist generator 90 shown in FIG. 7, a plate-shaped member 81 is installed under the gas supply unit 70E (θ=0 degrees). That is, the plate-shaped member 81 is disposed between the gas supply unit 70E and the liquid surface of the dispersion liquid 63. The portion where the arrow (a) (a line drawn from the center of gravity of the gas supply port 72E in the supply direction) first intersects is the plate-shaped member 81, so the momentum of the gas to be supplied is weakened, and the gas can be supplied into the container 62A without disturbing the liquid surface. In addition, the angle of θ is not limited to 0 degrees, and it is sufficient that the portion where the arrow (a) first contacts is the plate-shaped member.

[0046] [First embodiment: Modification 3] Fig. 8 is a schematic diagram showing an example of a mist generator 90 in Modification 3 of the first embodiment. In the mist generator 90 shown in Fig. 8, the gas supply unit 70F is inserted from the side of the storage unit 60A. In this modification, the portion where the arrow (a) (a line drawn from the center of gravity of the gas supply port 72F in the supply direction) first intersects is the electrode 78A. The portion where the arrow (a) first intersects is not limited to the electrode 78A, and may be the exhaust unit 74A, the side of the storage unit 60A, or the lid unit 61A.

[0047] [First embodiment: Modification 4] FIG. 9 is a schematic diagram showing an example of a mist generator 90 in a fourth modified example of the first embodiment. The mist generator 90 shown in FIG. 9 has a gas supply unit 70G in which the angle α between the discharge direction and the direction of gravity is set to 180 degrees, and the angle θ between the supply direction and the direction of gravity is set to be greater than 90 degrees. It is desirable that the first intersection of the arrow (a) (a line drawn from the center of gravity of the gas supply port 72G in the supply direction) does not intersect with the liquid surface, and the gas supplied from the gas supply port 72G is not directly sprayed onto the liquid surface, thereby preventing the liquid surface from shaking significantly. The angle θ may be 90 degrees to 150 degrees. The upper limit may be 135 degrees or 120 degrees. The lower limit may be 100 degrees or 105 degrees.

[0048] [First embodiment: Modification 5] Fig. 10 is a schematic diagram showing an example of a mist generator 90 in a fifth modified example of the first embodiment. The mist generator 90 shown in Fig. 10 has a discharge section 74D in which the angle α between the discharge direction and the direction of gravity is smaller than 180 degrees while the angle θ between the supply direction and the direction of gravity is kept at 90 degrees. The angle α may be set to 120 degrees to 180 degrees in order to efficiently collect the generated mist. The upper limit may be set to 165 degrees or 150 degrees. The lower limit may be set to 130 degrees or 135 degrees.

[0049] [Second embodiment] The second embodiment will be described with reference to Fig. 11. Differences from the above-mentioned embodiment will be described below. Each configuration in the second embodiment is the same as that in the above-mentioned first embodiment unless otherwise specified.

[0050] Fig. 11 is a schematic diagram showing an example of a mist generator 90 according to the second embodiment. The mist generator 90 according to this embodiment has two or more gas supply units 70A. Fig. 11 shows the arrangement of a container 62A, two gas supply units 70A, an exhaust unit 74A, and an electrode 78A in the mist generator 90 according to the second embodiment. Note that the mist generating unit 80 is not shown in Fig. 11.

[0051] The mist generator 90 shown in FIG. 11 has two gas supply units 70A. By increasing the number of gas supply units 70A, a large amount of gas can be supplied into the container 62A at one time. When attempting to supply a large amount of gas into the container 62A with one gas supply unit 70A, even if the gas is not directly supplied to the liquid surface of the dispersion liquid 63, gas with a high flow rate is supplied locally, which may cause the airflow in the container 62A to be significantly disturbed and the liquid surface to be significantly ruffled. By increasing the number of gas supply units 70A, the amount of gas supplied can be increased while suppressing an increase in the flow rate of the gas supplied from one gas supply unit 70A, and therefore, the liquid surface of the dispersion liquid 63 can be prevented from being significantly ruffled.

[0052] The number of gas supply units 70A is not limited to two, and may be three or more. In addition, in this embodiment, the configuration shown in Fig. 11 has been described, but the present invention is not limited to this, and the gas supply units 70A to 70G described in the first embodiment above may be used in combination.

[0053] [Third embodiment] The third embodiment will be described with reference to Fig. 12. Each configuration in the third embodiment is the same as that in the first embodiment unless otherwise specified.

[0054] Fig. 12 is a schematic diagram showing an example of a mist generator 90 according to the third embodiment. The mist generator 90 according to this embodiment has two or more gas supply ports 72H. Fig. 12 shows the arrangement of a container 62A, a gas supply unit 70H, an exhaust unit 74A, and an electrode 78A in the mist generator 90 according to the third embodiment. Note that the mist generating unit 80 is not shown in Fig. 12.

[0055] The mist generator 90 shown in FIG. 12 has one gas supply unit 70H and two gas supply ports 72H1 and H2. When a large amount of gas is supplied into the container 62A through one gas supply port 72H1 (H2), the flow rate per unit time per gas supply port 72H1 (H2) becomes large. As a result, even if the gas is not directly supplied to the liquid surface, gas with a high flow rate is supplied locally in the container 62A, so that the air flow in the container 62A may be greatly disturbed and the liquid surface of the dispersion liquid 63 may be greatly wavy. By providing multiple gas supply ports 72H1 (H2) for one gas supply unit 70H, the flow rate per unit time per gas supply port 72H1 (H2) is reduced. As a result, even when a large amount of gas is supplied into the container 62A, the liquid surface of the dispersion liquid 63 may be prevented from being greatly wavy.

[0056] The number of gas supply ports 72H1 (H2) is not limited to 2, and may be 3 or more. Note that this embodiment is not limited to this, and the gas supply ports 72 described in the first embodiment above may be combined.

[0057] [Third embodiment: modified example] Fig. 13 is a schematic diagram showing a modification of the mist generator 90 in the third embodiment. The gas supply unit 70I shown in Fig. 13 has two gas supply ports 72I1 and I2 with different inclinations. Note that the gas supply unit 70I in this modification may have a plurality of gas supply ports 72I with different inclinations, and the plurality of gas supply ports 72I may satisfy the above-mentioned angles θ and β with respect to the respective supply directions. Furthermore, as described in the second embodiment, a plurality of gas supply units 70 may be combined.

[0058] [Fourth embodiment] The fourth embodiment will be described with reference to Fig. 14. Unless otherwise specified, each configuration in the fourth embodiment is the same as that in the first embodiment. A mist generating device 90 in this embodiment has two or more exhaust units 74A.

[0059] Fig. 14 is a schematic diagram showing an example of a mist generator 90 according to the fourth embodiment. Fig. 14 shows the arrangement of a container 62A, a gas supply unit 70A, two exhaust units 74A, and an electrode 78A in the mist generator 90 according to the fourth embodiment. Note that the mist generating unit 80 is not shown in Fig. 14.

[0060] 14 is configured to have two exhaust parts 74A. By increasing the number of exhaust parts 74A, a large amount of gas can be exhausted from inside the container 62A at one time. Also, the mist generated inside the container 62A can be exhausted evenly.

[0061] The number of discharge sections 74A is not limited to two, and may be three or more. In this embodiment, the configuration shown in Fig. 14 has been described, but the present invention is not limited to this, and two or more discharge sections 74 may be provided in the first to third embodiments described above.

[0062] [Fifth embodiment] The fifth embodiment will be described with reference to Fig. 15. Unless otherwise specified, each configuration in the fifth embodiment is the same as that in the first embodiment.

[0063] Fig. 15 is a schematic diagram showing an example of a mist generator 90 according to the fifth embodiment. The mist generator 90 according to this embodiment has two or more exhaust ports 76E. Fig. 15 shows the arrangement of a container 62A, a gas supply unit 70A, an exhaust unit 74E, and an electrode 78A in the mist generator 90 according to the fifth embodiment. Note that the mist generating unit 80 is not shown in Fig. 15.

[0064] The mist generator 90 shown in FIG. 15 has two outlets 76E1, E2 for one exhaust section 74E. When a large amount of gas and mist is exhausted from the container 62A using one exhaust section 74E, the flow rate per unit time per outlet 76E1 (E2) becomes large. This may cause the liquid surface to ripple significantly. By providing multiple outlets 76E1 (E2) for one exhaust section 74E, the flow rate per unit time per outlet 76E1 (E2) is reduced. As a result, it is possible to prevent the liquid surface from rippling significantly. In addition, since the outlets 76E1 (E2) are located at different positions, the mist generated in the container 62A can be exhausted evenly and uniformly.

[0065] The number of discharge openings 76E1 (E2) is not limited to 2, and may be 3 or more. The configuration of the discharge section 74E is not limited to the configuration shown in FIG.

[0066] [Fifth embodiment: modified example] Fig. 16 is a schematic diagram showing a modification of the mist generator 90 in the fifth embodiment. The discharge section 74E shown in Fig. 16 has two discharge ports 76E1 and E2 with different inclinations. Note that the discharge section 74E in this modification may have a plurality of discharge ports 76E with different inclinations, and each of the discharge ports 76E may satisfy the above-mentioned angles α and β with respect to the respective discharge directions as described in the first embodiment. Also, as described in the fourth embodiment, the mist generator 90 may use a combination of a plurality of discharge sections 74.

[0067] [Sixth embodiment] The sixth embodiment will be described with reference to Fig. 17. Unless otherwise specified, each configuration in the sixth embodiment is the same as that in the first embodiment.

[0068] Fig. 17 is a schematic diagram showing an example of a mist generator 90 according to the sixth embodiment. Fig. 17 is a diagram showing the arrangement of a container 62B, a gas supply unit 70J, an exhaust unit 74A, and an electrode 78A in the mist generator according to the sixth embodiment. Note that the mist generating unit 80 is not shown in Fig. 17.

[0069] 17, a partition 94 is provided in a storage section 60B. There are two spaces in the storage section 60B. The space in which the dispersion liquid is stored is a storage space 96. The space in which the dispersion liquid 63 is not stored is an empty space 98. The number of storage spaces 96 and empty spaces 98 is not limited to one, and there may be multiple spaces. A gas supply port 72J is provided in the empty space 98.

[0070] In order to discharge the gas supplied from the gas supply port 72J into the container 62B from the discharge portion 74A, the partition 94 does not have a height that reaches the lid portion 61B of the container 62B, and the storage space 96 and the empty space 98 are open to each other at the top of the storage portion 60B. In other words, the space partitioned by the partition 94, which contains the dispersion liquid 63 and extends upward until it reaches the lid portion 61B, is the storage space 96, and the space partitioned by the partition 94, which does not contain the dispersion liquid and extends upward until it reaches the lid portion 61B, is the empty space 98.

[0071] By providing the gas supply port 72J in the empty space 98, the gas can be filled into the container 62B without directly spraying the gas onto the dispersion liquid 63. Also, the exhaust part 74A is located inside the accommodation space 96. As a result, the mist can be efficiently exhausted to the outside of the container 62B. Note that this embodiment is not limited to the example shown in this figure.

[0072] [Sixth embodiment: Modification] Fig. 18 is a schematic diagram showing a modification of the mist generator 90 in the sixth embodiment. The container 62C shown in Fig. 18 has a step. The dispersion liquid 63 is contained up to the height of the step. The number of steps is not limited to one, and there may be multiple steps.

[0073] The gas supply port 72J is disposed at a position not facing the liquid surface. This allows the container 62C to be filled with gas without directly supplying gas to the liquid surface. The exhaust port 76A is disposed at a position facing the liquid surface, allowing the generated mist to be efficiently exhausted to the outside of the container 62C. This embodiment is not limited to this, and the gas supply unit 70 and exhaust unit 74 of the first to fifth embodiments described above may be used in combination.

[0074] [Seventh embodiment] <Thin film manufacturing equipment and manufacturing method> According to the mist generating device 90 of this embodiment of the present invention, for example, a thin film can be formed by the following device. The following will be explained with reference to FIG.

[0075] 19 is a diagram showing an example of the configuration of a thin-film manufacturing apparatus 1 in the seventh embodiment, which is one of the configurations of an electronic device manufacturing apparatus. The mist generating unit 20A and the mist generating unit 20B in this embodiment correspond to the mist generating device 90 described above. Moreover, the ducts 21A and 21B correspond to the exhaust unit 74 described above.

[0076] The thin-film manufacturing apparatus 1 in this embodiment continuously forms a thin film made of particles 66 on the surface of a flexible long sheet substrate FS by a roll-to-roll method.

[0077] (Outline of the device) In Fig. 19, the floor of the factory where the main body of the apparatus is installed is defined as the XY plane, and the direction perpendicular to the floor is defined as the Z axis direction in the Cartesian coordinate system XYZ. In addition, in the thin-film manufacturing apparatus 1 in Fig. 19, the sheet substrate FS is transported in the longitudinal direction in a state where the surface of the sheet substrate FS is always perpendicular to the XZ plane.

[0078] A long sheet substrate FS (hereinafter simply referred to as substrate FS) is wound over a predetermined length as a processing object on a supply roll RL1 mounted on a stand EQ1. A roller CR1 is provided on the stand EQ1 for wrapping the sheet substrate FS pulled out from the supply roll RL1, and the rollers CR1 and CR1 are arranged to extend in the Y-axis direction (perpendicular to the paper surface of FIG. 19) so that the central axis of rotation of the supply roll RL1 and the central axis of rotation of the roller CR1 are parallel to each other. The substrate FS bent in the -Z-axis direction (gravity direction) by the roller CR1 is turned back in the Z-axis direction by the air turn bar TB1, and is bent obliquely upward (within the range of 45 degrees ±15 degrees with respect to the XY plane) by the roller CR2. The air turn bar TB1 bends the substrate FS in the conveying direction while slightly floating it by an air bearing (gas layer), as described in WO2013 / 105317, for example. The air turn bar TB1 can move in the Z-axis direction by being driven by a pressure adjusting unit (not shown), and applies tension to the substrate FS in a non-contact manner.

[0079] After passing through the rollers CR2, the substrate FS passes through a slit-shaped air seal portion 10A of the first chamber 10, and then passes through a slit-shaped air seal portion 12A of the second chamber 12 that houses the film formation main body, and is conveyed diagonally upwards and linearly into the second chamber 12 (film formation main body). When the substrate FS is conveyed at a constant speed through the second chamber 12, a film of particles 66 is formed to a predetermined thickness on the surface of the substrate FS by a mist deposition method assisted by atmospheric pressure plasma or a mist CVD (Chemical Vapor Deposition) method.

[0080] The substrate FS that has been subjected to the film forming process in the second chamber 12 exits the second chamber through the slit-shaped air seal section 12B, is folded back in the -Z-axis direction by the roller CR3, is then folded by the roller CR4 provided on the stand EQ2, and is wound up on the recovery roll RL2. The recovery roll RL2 and the roller CR4 are provided on the stand EQ2, extending in the Y-axis direction (direction perpendicular to the paper surface of FIG. 19) so that their central rotation axes are parallel to each other. If necessary, a drying section (heating section) 50 for drying unnecessary water components adhering to or impregnated in the substrate FS may be provided in the transport path from the air seal section 10B to the air turn bar TB2.

[0081] As disclosed in WO2012 / 115143, for example, the air seal parts 10A, 10B, 12A, and 12B shown in Fig. 19 are provided with slit-shaped openings that allow the sheet substrate FS to be carried in and out in the longitudinal direction while preventing the flow of gas (air, etc.) between the inner space and the outer space of the outer wall of the first chamber 10 or the second chamber 12. A vacuum pressurized air bearing (static pressure gas layer) is formed between the upper end of the opening and the upper surface (surface to be processed) of the sheet substrate FS, and between the lower end of the opening and the lower surface (rear surface) of the sheet substrate FS. Therefore, the mist gas for film formation remains in the second chamber 12 and the first chamber 10, and is prevented from leaking out to the outside.

[0082] In the present embodiment, the transport control and tension control in the longitudinal direction of the substrate FS are performed by a servo motor provided on the stand EQ2 to rotate the recovery roll RL2, and a servo motor provided on the stand EQ1 to rotate the supply roll RL1. Although not shown in FIG. 19, the stand EQ2 and each servo motor provided on the stand EQ2 are controlled by a motor control unit so that a predetermined tension (longitudinal direction) is applied to the substrate FS at least between the rollers CR2 and CR3 while the transport speed of the substrate FS is set to a target value. The tension of the sheet substrate FS can be obtained, for example, by providing a load cell or the like that measures the force pushing up the air turn bars TB1 and TB2 in the Z-axis direction.

[0083] In addition, the stand EQ1 (and the supply roll RL1 and roller CR1) has a function of finely moving in the Y-axis direction within a range of about ± several mm by a servo motor or the like in response to the detection result from an edge sensor ES1 that measures the fluctuation in the Y-axis direction (the width direction perpendicular to the long dimension of the sheet substrate FS) of the edges (ends) on both sides of the sheet substrate FS just before it reaches the air turn bar TB1, that is, an EPC (edge ​​position control) function. As a result, even if there is unevenness in the Y-axis direction of the sheet substrate wound around the supply roll RL1, the fluctuation of the center position in the Y-axis direction of the sheet substrate FS passing through the roller CR2 is always suppressed within a certain range (for example, ±0.5 mm). Therefore, the sheet substrate FS is transported into the film formation main body (second chamber 12) in a state where it is accurately positioned in the width direction.

[0084] Similarly, the stand EQ2 (and roll RL2, roller CR4) has an EPC function that moves slightly in the Y-axis direction within a range of about ± several meters using a servo motor or the like in response to the detection results from an edge sensor ES2 that measures the Y-axis direction fluctuation of the edge (end) positions on both sides of the sheet substrate FS immediately after it has passed through the air turn bar TB2. As a result, the sheet substrate FS after film formation is wound up on the recovery roll RL2 while preventing uneven winding in the Y-axis direction. The stand EQ1 and EQ2, supply roll RL1, recovery roll RL2, air turn bars TB1 and TB2, and rollers CR1, CR2, CR3, and CR4 function as a transport section that guides the substrate FS to the mist supply section 22 (22A / 22B).

[0085] In the apparatus of FIG. 19, rollers CR2 and CR3 are arranged so that the linear transport path of the sheet substrate FS in the film formation main body (second chamber 12) is elevated at an inclination of about 45 degrees ± 15 degrees (here, 45 degrees) along the transport direction of the substrate FS. This inclination of the transport path allows the mist of the dispersion liquid 63 sprayed on the sheet substrate FS by the mist deposition method or the mist CVD method to be appropriately retained on the surface of the sheet substrate FS, thereby improving the deposition efficiency (also called the film formation rate or film formation speed) of the particles 66. The configuration of the film formation main body will be described later, but since the substrate FS is inclined in the longitudinal direction in the second chamber 12, an orthogonal coordinate system Xt·Y·Zt is set, in which the plane parallel to the processed surface of the substrate FS is the Y·Xt plane and the direction perpendicular to the Y·Xt plane is the Zt plane.

[0086] In this embodiment, two mist supply parts 22A, 22B are provided in the second chamber 12 at a fixed interval along the transport direction (Xt direction) of the substrate FS. The mist supply parts 22A, 22B are formed in a cylindrical shape, and a slit-shaped opening extending in the Y-axis direction is provided at the tip side facing the substrate FS for ejecting mist gas (mixture of gas and mist) Mgs toward the substrate FS. Furthermore, a pair of parallel wire-shaped electrodes 24A, 24B for generating atmospheric pressure plasma in a non-thermal equilibrium state is provided near the opening of the mist supply parts 22A, 22B. A pulse voltage is applied to each of the pair of electrodes 24A, 24B from a high-voltage pulse power supply unit 40 at a predetermined frequency.

[0087] The type of gas that serves as the plasma source for generating plasma in the mist supply parts 22A and 22B is not particularly limited, and known gases can be used. Specific examples of gases include helium, argon (xenon), oxygen, and nitrogen. Among these, helium, argon, and xenon, which are highly stable, are preferred. The gas used to generate plasma in the mist generation parts 20A and 20B may be used as it is to generate plasma in the mist supply parts 22A and 22B. This makes it possible to reduce the amount of gas used in the entire film formation apparatus, thereby reducing costs.

[0088] In addition, temperature adjustment units 23A and 23B for maintaining the internal spaces of the mist supply units 22A and 22B at a set temperature are provided on the outer periphery of the mist supply units 22A and 22B. The temperature adjustment units 23A and 23B are controlled by a temperature adjustment control unit 28 to be at the set temperature.

[0089] The mist gas Mgs of the dispersion liquid 63 generated in the first mist generating unit 20A and the second mist generating unit 20B is supplied to the mist supply units 22A and 22B at a predetermined flow rate through the ducts 21A and 21B. The mist gas Mgs of the dispersion liquid 63 ejected from the slit-shaped openings of the mist supply units 22A and 22B in the -Zt axis direction is sprayed onto the upper surface of the substrate FS at a predetermined flow rate, so that it immediately tends to flow downward (in the -Z axis direction) if left as is. In order to extend the residence time of the mist gas of the dispersion liquid 63 on the upper surface of the substrate FS, the gas in the second chamber 12 is sucked by the exhaust control unit 30 through the duct 12C. That is, by creating a gas flow from the slit-shaped openings of the mist supply units 22A and 22B toward the duct 12C in the second chamber 12, the mist gas Mgs of the dispersion liquid 63 is controlled to immediately flow downward (in the -Z axis direction) from the upper surface of the substrate FS.

[0090] The exhaust control unit 30 removes particles 66 or gas contained in the gas sucked into the second chamber 12, converts it into normal gas (air), and releases it into the environment through the duct 30A. In Fig. 19, the mist generating units 20A and 20B are provided outside the second chamber 12 (inside the first chamber 10), but this is to reduce the volume of the second chamber 12 and make it easier to control the flow of gas (flow rate, flow velocity, flow path, etc.) in the second chamber 12 when the exhaust control unit 30 sucks in the gas. Of course, the mist generating units 20A and 20B may be provided inside the second chamber 12.

[0091] When depositing a film on a substrate FS by mist CVD using mist gas Mgs of the dispersion liquid 63 from each of the mist supply parts 22A and 22B, it is necessary to set the substrate FS to a temperature higher than room temperature, for example, about 200°C. Therefore, in this embodiment, substrate temperature control parts 27A and 27B are provided at positions (on the back side of the substrate FS) facing the slit-shaped openings of each of the mist supply parts 22A and 22B across the substrate FS, and the temperature of the region on the substrate FS where the mist gas Mgs of the dispersion liquid 63 is sprayed is controlled by the temperature adjustment control part 28 so that it becomes a set value. On the other hand, in the case of film formation by the mist deposition method, room temperature is sufficient, so there is no need to operate the substrate temperature control parts 27A and 27B, but when it is desired to set the substrate FS to a temperature lower than room temperature (for example, 40°C or lower), the substrate temperature control parts 27A and 27B can be operated as appropriate.

[0092] The mist generating units 20A, 20B, temperature adjustment control unit 28, exhaust control unit 30, high-voltage pulse power supply unit 40, and motor control unit (control system for the servo motors that rotate the supply roll RL1 and the recovery roll RL2), etc. described above, are centrally controlled by a main control unit 100 including a computer.

[0093] (Sheet substrate) Next, the sheet substrate FS as the processing target will be described. As described above, the substrate FS is, for example, a resin film, a foil made of a metal such as stainless steel or an alloy, or the like. The resin film may be made of one or more of polyethylene resin, polypropylene resin, polyester resin, ethylene-vinyl copolymer resin, polyvinyl chloride resin, cellulose resin, polyamide resin, polyimide resin, polycarbonate resin, polystyrene resin, and vinyl acetate resin. The thickness and rigidity (Young's modulus) of the substrate FS may be within a range that does not cause folds or irreversible wrinkles due to buckling when the substrate FS is transported. When manufacturing electronic devices such as flexible display panels, touch panels, color filters, and electromagnetic wave protection filters, inexpensive resin sheets such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate) having a thickness of about 25 μm to 200 μm are used.

[0094] It is desirable to select a substrate FS that does not have a significantly large thermal expansion coefficient so that the amount of deformation caused by heat in various processes performed on the substrate FS can be substantially negligible. In addition, the thermal expansion coefficient can be reduced by mixing an inorganic filler such as titanium oxide, zinc oxide, alumina, or silicon oxide with a base resin film. The substrate FS may be a single layer of ultra-thin glass having a thickness of about 100 μm manufactured by a float method or a single layer of a metal sheet obtained by rolling a metal such as stainless steel into a thin film shape, or may be a laminate obtained by bonding the above-mentioned resin film or a metal layer (foil) such as aluminum or copper to the ultra-thin glass or metal sheet. Furthermore, when forming a film by a mist deposition method using the thin-film manufacturing apparatus 1 of this embodiment, the temperature of the substrate FS can be set to 100° C. or less (usually about room temperature), but when forming a film by a mist CVD method, the temperature of the substrate FS needs to be set to about 100° C. to 200° C. For this reason, when forming a film using the mist CVD method, substrate materials that do not deform or change in quality even at temperatures of around 200°C (such as polyimide resin, ultra-thin glass, metal sheets, etc.) are used.

[0095] The flexibility of the substrate FS refers to the property of bending the substrate FS without breaking or breaking even when a force of about its own weight is applied to the substrate FS. The property of bending due to a force of about its own weight is also included in the flexibility. The degree of flexibility varies depending on the material, size, thickness, layer structure formed on the substrate FS, and environment such as temperature and humidity. In any case, when the substrate FS is properly wrapped around various transport rollers, turn bars, rotating drums, etc. provided in the transport path of the thin-film manufacturing apparatus 1 according to this embodiment or the manufacturing apparatus that controls the processes before and after it, if the substrate FS can be transported smoothly without buckling and forming creases or breaking (breaking or cracking), it can be said to be within the range of flexibility.

[0096] The substrate FS supplied from the supply roll RL1 shown in FIG. 19 may be a substrate in an intermediate process. That is, a specific layer structure for electronic devices may already be formed on the surface of the substrate FS wound around the supply roll RL1. The layer structure is a single layer such as a resin film (insulating film) or a metal thin film (copper, aluminum, etc.) formed with a certain thickness on the surface of a base sheet substrate, or a multilayer structure made of these films. In addition, the substrate FS to which the mist deposition method is applied in the thin film manufacturing apparatus 1 of FIG. 19 may have a surface state in which a large difference in lyophilicity / lyophobicity against a mist liquid is given between the irradiated and unirradiated portions of the substrate by applying a photosensitive silane coupling material to the surface of the substrate and drying the material, as disclosed in WO2013 / 176222, for example, and then irradiating the substrate with ultraviolet light (wavelength 365 nm or less) with a distribution according to the shape of a pattern for electronic devices by an exposure device. At this time, the mist adheres to the hydrophilic parts of the irradiated or unirradiated parts, and by using the mist deposition method using the thin-film manufacturing equipment 1 of Figure 1, the mist can be selectively adhered to the surface of the substrate FS according to the shape of the pattern.

[0097] Furthermore, the long sheet substrate FS supplied to the thin-film manufacturing apparatus 1 of Fig. 19 may be a long, thin metal sheet (for example, a SUS belt with a thickness of about 0.1 mm) on whose surface individual resin sheets or the like having dimensions corresponding to the size of the electronic device to be manufactured are attached at regular intervals in the longitudinal direction of the metal sheet. In this case, the object to be processed on which a film is formed by the thin-film manufacturing apparatus 1 of Fig. 19 is an individual resin sheet.

[0098] Next, the configuration of each part of the thin-film manufacturing apparatus 1 of FIG. 19 will be described with reference to FIG. 19 as well as FIGS.

[0099] (Mist supply units 22A, 22B) 20 is an example of a perspective view of the mist supply unit 22A (22B as well) seen from the -Zt side of the coordinate system Xt·Y·Zt, i.e., the substrate FS side. The mist supply unit 22A is made of a quartz plate, has a certain length in the Y-axis direction, and is composed of inclined inner walls Sfa and Sfb that gradually narrow in the Xt direction width toward the -Zt direction, an inner wall Sfc on a side parallel to the Xt·Zt plane, and a top plate 25A (25B) parallel to the Y·Xt plane. In the top plate 25A (25B), a duct 21A (21B) from the mist generating unit 20A (20B) is connected to an opening Dh, and mist gas Mgs is supplied into the mist supply unit 22A (22B). At the tip of the mist supply part 22A (22B) in the -Zt axis direction, a slot-shaped opening SN is formed, which extends elongatedly over a length La in the Y axis direction, and a pair of electrodes 24A (24B) is provided to sandwich the opening SN in the Xt direction. Therefore, the mist gas Mgs (positive pressure) supplied into the mist supply part 22A (22B) through the opening Dh passes between the pair of electrodes 24A (24B) from the slot-shaped opening SN and is ejected with a uniform flow rate distribution in the -Zt axis direction.

[0100] The pair of electrodes 24A is composed of a wire-shaped electrode EP extending in the Y-axis direction by a length La or more, and a wire-shaped electrode EG extending in the Y-axis direction by a length La or more. The electrodes EP and EG are held in a cylindrical quartz tube Cp1 functioning as a dielectric Cp and a quartz tube Cg1 functioning as a dielectric Cg so as to be parallel to each other at a predetermined interval in the Xt direction, and are fixed to the tip of the mist supply unit 22A (22B) so that the quartz tubes Cp1 and Cg1 are located on both sides of the slot-shaped opening SN. It is preferable that the quartz tubes Cp1 and Cg1 do not contain metal components inside. The dielectrics Cp and Cg may be ceramic tubes with high dielectric strength.

[0101] FIG. 21 is an example of a cross-sectional view of the tip of the mist supply unit 22A (22B) and the pair of electrodes 24A (24B) viewed from the Y-axis direction. In this embodiment, as an example, the outer diameter φa of the quartz tubes Cp1 and Cg1 is set to about 3 mm, and the inner diameter φb is set to about 1.6 mm (wall thickness 0.7 mm), and the electrodes EP and EG are made of wires with a diameter of 0.5 nm to 1 mm made of low-resistance metal such as tungsten or titanium. The electrodes EP and EG are held by insulators at both ends of the quartz tubes Cp1 and Cg1 in the Y direction so as to pass linearly through the center of the inner diameter of the quartz tubes Cp1 and Cg1. Note that only one of the quartz tubes Cp1 and Cg1 may be present. For example, the electrode EP connected to the positive electrode of the high-voltage pulse power supply unit 40 may be surrounded by the quartz tube Cp1, and the electrode EG connected to the negative electrode (ground) of the high-voltage pulse power supply unit 40 may be exposed. However, depending on the gas components of the mist gas Mgs sprayed from the opening SN at the tip of the mist supply part 22A (22B), contamination and corrosion of the exposed electrode EG may occur, so it is preferable to surround both electrodes EP, EG with quartz tubes Cp1, Cg1 so that the mist gas Mgs does not come into direct contact with the electrodes EP, EG.

[0102] Here, each of the wire-shaped electrodes EP and EG is disposed parallel to the surface of the substrate FS at a height position of the working distance WD from the surface of the substrate FS, and is disposed at an interval Lb in the transport direction (Xt direction) of the substrate FS. The interval Lb is set as narrow as possible, for example, about 5 mm, in order to stably and continuously generate atmospheric pressure plasma in a non-thermal equilibrium state with uniform distribution in the -Zt axis direction. Therefore, the effective width (gap) Lc in the Xt direction when the mist gas Mgs ejected from the opening SN of the mist supply unit 22A (22B) passes between the pair of electrodes is Lc = Lb - φa, and when a quartz tube with an outer diameter of 3 mm is used, the width Lc is about 2 mm.

[0103] Furthermore, although it is not essential, it is better to make the working distance WD larger than the distance Lb between the wire electrodes EP and EG in the Xt axis direction. This is because if the arrangement relationship is Lb>WD, plasma or arc discharge may occur between the positive electrode EP (quartz tube Cp1) and the substrate FS.

[0104] In other words, it is desirable that the working distance WD, which is the distance from the electrodes EP, EG to the substrate FS, is longer than the distance Lb between the electrodes EP, EG.

[0105] However, if the potential of the substrate FS can be set between the potential of the electrode EG serving as the ground electrode and the potential of the electrode EP serving as the positive electrode, it is also possible to set Lb>WD.

[0106] The plane formed by the electrodes 24A and 24B does not have to be parallel to the substrate FS. In that case, the distance from the part of the electrode closest to the substrate FS to the substrate FS is defined as the distance WD, and the installation position of the mist supply unit 22A (22B) or the substrate FS is adjusted.

[0107] In this embodiment, the plasma in a non-thermal equilibrium state is generated strongly in the region where the gap between the pair of electrodes 24A (24B) is narrowest, that is, in the limited region PA in the Zt axis direction between the width Lc in FIG. 21. Therefore, by reducing the working distance WD, the time from when the mist gas Mgs is irradiated with the plasma in a non-thermal equilibrium state until it reaches the surface of the substrate FS can be shortened, and an improvement in the film formation rate (deposition film thickness per unit time) can be expected. In FIG. 21, the gap Lb between the wire-shaped electrodes EP and EG in the Xt direction may be 10 μm to 20 mm from the viewpoint of plasma generation efficiency, and the lower limit value is preferably 0.1 mm, and more preferably 1 mm. The upper limit value is preferably 15 mm, and more preferably 10 mm.

[0108] When the spacing Lb (or width Lc) and working distance WD between the pair of electrodes 24A (24B) are not changed, the film formation rate varies depending on the peak value and frequency of the pulse voltage applied between the electrodes EP and EG, the flow rate (speed) of the mist gas Mgs ejected from the opening SN, the concentration of the specific substance for film formation (particles, molecules, ions, etc.) contained in the mist gas Mgs, or the controlled temperature by the substrate temperature control unit 27A (27B) arranged on the back side of the substrate FS, and therefore these conditions are appropriately adjusted by the main control unit 100 depending on the type of specific substance to be formed on the substrate FS, the thickness of the film formed, flatness, etc.

[0109] (High voltage pulse power supply unit 40) FIG. 22 is a block diagram showing an example of a schematic configuration of the high voltage pulse power supply unit 40, which is composed of a variable DC power supply 40A and a high voltage pulse generating unit 40B. The variable DC power supply 40A receives a commercial AC power supply of 100V or 200V and outputs a smoothed DC voltage Vo1. The voltage Vo1 is variable between 0V and 150V, for example, and is also called a primary voltage because it is a power supply to the next stage, high voltage pulse generating unit 40B. The high voltage pulse generating unit 40B includes a pulse generating circuit unit 40Ba that repeatedly generates a pulse voltage (a rectangular short pulse wave whose peak value is approximately the primary voltage Vo1) corresponding to the frequency of the high voltage pulse voltage applied between the wire-shaped electrodes EP and EG, and a boost circuit unit 40Bb that receives the pulse voltage and generates a high voltage pulse voltage with an extremely short rise time and pulse duration as an inter-electrode voltage Vo2.

[0110] The pulse generating circuit section 40Ba is composed of a semiconductor switching element or the like that turns on / off the primary voltage Vo1 at high speed at a frequency f. The frequency f is set to a few KHz or less, but the rise time / fall time of the pulse waveform due to switching is set to a few tens of nS or less, and the pulse time width is set to a few hundred nS or less. The boost circuit section 40Bb boosts such a pulse voltage by about 20 times, and is composed of a pulse transformer or the like.

[0111] The pulse generating circuit section 40Ba and the boost circuit section 40Bb are merely examples, and any configuration may be used as long as the final interelectrode voltage Vo2 can be continuously generated with a peak value of about 20 kV, a pulse rise time of about 100 nS or less, and a pulse time width of several hundred nS or less at a frequency f of several kHz or less. Note that the higher the interelectrode voltage Vo2 is, the wider the interval Lb (and width Lc) between the pair of electrodes 24A (24B) shown in Fig. 20 can be made, and the spray area of ​​the mist gas Mgs on the substrate FS can be expanded in the Xt direction, thereby increasing the film formation rate.

[0112] In addition, in order to adjust the generation state of plasma in a non-thermal equilibrium state between the pair of electrodes 24A (24B), the variable DC power supply 40A has a function of changing the primary voltage Vo1 (i.e., the inter-electrode voltage Vo2) in response to a command from the main control unit 100, and the high-voltage pulse generating unit 40B has a function of changing the frequency f of the pulse voltage applied between the pair of electrodes 24A (24B) in response to a command from the main control unit 100.

[0113] FIG. 23 shows an example of the waveform characteristic of the interelectrode voltage Vo2 obtained by the high-voltage pulse power supply unit 40 configured as shown in FIG. 22, with the vertical axis representing the voltage Vo2 (kV) and the horizontal axis representing time (μS). The characteristic in FIG. 23 shows the waveform of one pulse of the interelectrode voltage Vo2 obtained when the primary voltage Vo1 is 120V and the frequency f is 1kHz, and a pulse voltage Vo2 of about 18kV is obtained as a peak value. Furthermore, the rise time Tu from 5% to 95% of the first peak value (18kV) is about 120nS. In addition, in the circuit configuration in FIG. 22, a ringing waveform (attenuation waveform) is generated in the period up to 2μS after the waveform of the first peak value (pulse time width is about 400nS), but the voltage waveform in this portion does not lead to the generation of plasma or arc discharge in a non-thermal equilibrium state.

[0114] In the example electrode configuration exemplified above, electrodes EP and EG covered with quartz tubes Cp1 and Cg1 having an outer diameter of 3 mm and an inner diameter of 1.6 mm are placed at an interval Lb = 5 mm, the waveform portion of the first peak value shown in Figure 23 is repeated at a frequency f, thereby stably and continuously generating atmospheric pressure plasma in a non-thermal equilibrium state in the region PA (Figure 21) between the pair of electrodes 24A (24B).

[0115] (Substrate temperature control units 27A, 27B) Fig. 24 is a cross-sectional view showing an example of the configuration of the substrate temperature control section 27A (27B) in Fig. 19. Since the sheet substrate FS is continuously transported in the longitudinal direction (Xt axis direction) at a constant speed (for example, several mm to several cm per minute), there is a risk of scratching the rear surface of the substrate FS when the upper surface of the substrate temperature control section 27A (27B) is in contact with the rear surface of the sheet substrate FS. Therefore, in this embodiment, an air bearing gas layer with a thickness of about several µm to several tens of µm is formed between the upper surface of the substrate temperature control section 27A (27B) and the rear surface of the substrate FS, so that the substrate FS is transported in a non-contact state (or in a low-friction state).

[0116] The substrate temperature control unit 27A (27B) is composed of a base stand 270 arranged opposite the back surface of the substrate FS, spacers 272 of a fixed height arranged at multiple locations on the base stand 270 (in the Zt axis direction), a flat metal plate 274 arranged on the multiple spacers 272, and multiple substrate temperature adjustment units 275 arranged between the multiple spacers 272, between the base stand 270 and the plate 274.

[0117] Each of the spacers 272 is formed with a gas outlet 274A that penetrates to the surface of the plate 274, and an intake hole 274B that sucks in gas. The outlet 274A that penetrates each spacer 272 is connected to a gas inlet port 271A via a gas flow path formed in the base 270, and the intake hole 274B that penetrates each spacer 272 is connected to a gas exhaust port 271B via a gas flow path formed in the base 270. The inlet port 271A is connected to a supply source of pressurized gas, and the exhaust port 271B is connected to a reduced pressure source that creates a vacuum pressure.

[0118] On the surface of plate 274, because outlet hole 274A and intake hole 274B are provided close to each other in the Y·Xt plane, the gas ejected from outlet hole 274A is immediately sucked into intake hole 274B. This forms an air bearing gas layer between the flat surface of plate 274 and the back surface of substrate FS. When substrate FS is transported with a certain tension in the longitudinal direction (Xt axis direction), substrate FS maintains a flat state following the surface of plate 274.

[0119] In addition, since the gap between the front surface of the plate 274, whose temperature is adjusted by the multiple substrate temperature adjustment parts 275, and the rear surface of the substrate FS is only about several μm to several tens of μm, the substrate FS is immediately adjusted to the set temperature by the radiant heat from the front surface of the plate 274. The set temperature is controlled by the temperature adjustment control part 28 shown in FIG.

[0120] Furthermore, when it is necessary to adjust the temperature not only from the back surface of the substrate FS but also from the top surface (surface to be processed) side, a temperature adjustment plate (a set of plate 274 and substrate temperature adjustment unit 275 in Figure 24) 27C, which faces the top surface of the substrate FS with a predetermined gap, is provided upstream of the injection area of ​​the mist gas Mgs in the transport direction of the substrate FS.

[0121] As described above, the substrate temperature control unit 27A (27B) has both a temperature control function for adjusting the temperature of a portion of the substrate FS receiving the spray of the mist gas Mgs, and a non-contact (low friction) support function for floating the substrate FS by a hair bearing method and supporting it flat. It is desirable to keep the working distance WD in the Zt direction between the upper surface of the substrate FS and the pair of electrodes 24A (24B) shown in FIG. 23 constant even during transportation of the substrate FS in order to maintain the uniformity of the film thickness during film formation. As shown in FIG. 24, the substrate temperature control unit 27A (27B) of this embodiment supports the substrate FS by a vacuum pressurized air bearing, so that the gap between the back surface of the substrate FS and the upper surface of the plate 274 is kept almost constant, and the positional fluctuation of the substrate FS in the Zt direction is suppressed.

[0122] As described above, in the thin-film manufacturing apparatus 1 according to the configuration of this embodiment (FIGS. 19 to 24), while the substrate FS is transported in the longitudinal direction at a constant speed, the high-voltage pulse power supply unit 40 is operated to generate atmospheric pressure plasma in a non-thermal equilibrium state between the pair of electrodes 24A, 24B, and the mist gas Mgs is sprayed at a predetermined flow rate from the openings SN of the mist supply units 22A, 22B. The mist gas Mgs that has passed through the area PA (FIG. 21) where the atmospheric pressure plasma is generated is sprayed onto the substrate FS, and the specific substance contained in the mist of the mist gas Mgs is continuously deposited on the substrate FS.

[0123] In this embodiment, by arranging two mist supply units 22A and 22B in the transport direction of the substrate FS, the deposition rate of a thin film of a specific substance deposited on the substrate FS is increased by about a factor of two. Therefore, by increasing the number of mist supply units 22A and 22B in the transport direction of the substrate FS, the deposition rate is further increased.

[0124] In this embodiment, mist generators 20A, 20B are provided for each of the mist supply parts 22A, 22B, and substrate temperature control parts 27A, 27B are provided for each of the mist supply parts 22A, 22B, so that the characteristics (concentration of a specific substance in the precursor LQ, the ejection flow rate and temperature of the mist gas, etc.) of the mist gas Mgs ejected from the opening SN of the mist supply part 22A and the mist gas Mgs ejected from the opening SN of the mist supply part 22B can be made different, or the temperature of the substrate FS can be made different. By making the characteristics of the mist gas Mgs ejected from the opening SN of each of the mist supply parts 22A, 22B and the temperature of the substrate FS different, the film formation state (film thickness, flatness, etc.) can be adjusted.

[0125] Since the thin film manufacturing apparatus 1 in Fig. 19 transports the substrate FS by a roll-to-roll method alone, the film formation rate can also be adjusted by changing the transport speed of the substrate FS. However, when a pre-processing device that performs surface treatment, etc. on the substrate FS before the film is formed in the thin film manufacturing apparatus 1 as shown in Fig. 19, or a post-processing device that immediately applies a coating process, such as a photosensitive resist or a photosensitive silane coupling material, to the substrate FS after the film is formed, is connected, it may be difficult to change the transport speed of the substrate FS. Even in such a case, the thin film manufacturing apparatus 1 according to the present embodiment can adjust the film formation state to suit the set transport speed of the substrate FS.

[0126] Of course, the mist gas Mgs generated in one mist generation unit 20A may be distributed and supplied to each of two mist supply units 22A and 22B, or to more than two mist supply units.

[0127] In this embodiment, the configuration in which the mist gas Mgs is supplied to the substrate FS from the Zt axis direction has been described, but the present invention is not limited to this, and the mist gas Mgs may be supplied to the substrate FS from the -Zt direction. In the case of a configuration in which the mist gas Mgs is supplied to the substrate from the Zt direction, there is a possibility that the droplets accumulated in the mist supply units 22A and 22B may fall onto the substrate FS, but this can be suppressed by a configuration in which the mist gas Mgs is supplied to the substrate FS from the -Zt axis direction. The direction from which the mist gas Mgs is supplied may be appropriately determined depending on the supply amount of the mist gas Mgs and other manufacturing conditions.

[0128] [Eighth embodiment] The eighth embodiment will be described with reference to Fig. 25. Fig. 25 is a schematic diagram showing an example of a mist generating device 90 in the eighth embodiment. Unless otherwise specified, each configuration in the eighth embodiment is the same as that in the first embodiment. The mist generating device 90 in the embodiment and the modified example shown in Figs. 25 to 28 includes an external container 91 and a mist generating section 80 similar to those in the above-mentioned embodiment. In the examples shown below, the mist generating section 80 and the external container 91 are not shown unless otherwise specified.

[0129] The mist generator 90 in this embodiment has a plasma generating unit 82. In addition to the electrode 78A described above, the plasma generating unit 82 has a hollow body 83, a plug 84, and a gas inlet 85. The hollow body 83 is a member that surrounds at least a portion of the electrode and has a cavity therein.

[0130] One end of the hollow body 83 is located below the liquid level of the dispersion liquid 63 and is open. The other end is closed, and the inside of the hollow body 83 is filled with gas. As an example, the other end of the hollow body 83 is sealed with a plug 84 through which the electrode 78A is inserted. Also, the hollow body may not be structured to be sealed with a plug, but may be structured such that the other end of the hollow body itself is closed. In the example shown in FIG. 25, the hollow body 83 penetrates the lid portion 61A. That is, the plug 84 is located outside the container 62A.

[0131] The hollow body 83 is formed of an insulating material so that the plasma generated from the electrode 78A is stably output to the dispersion liquid 63. The hollow body 83 is formed of, for example, glass, quartz, resin, or the like. Note that, since there is a possibility that heat will be generated when the plasma is generated from the electrode 78A, the hollow body 83 is preferably formed of a heat-resistant material. Also, in order to confirm that the plasma is stably generated with respect to the liquid surface of the dispersion liquid 63, the hollow body 83 may be formed of a material having transparency. From this point of view, it is more preferable that the hollow body 83 is formed of glass or quartz.

[0132] The gas introduction part 85 introduces a gas into the hollow body 83. As an example, the gas introduction part 85 penetrates the plug 84. The gas introduced by the gas introduction part 85 is used to stably irradiate the plasma generated by the electrode 78A onto the liquid surface of the dispersion liquid 63. Specific examples of the gas include helium, argon, xenon, oxygen, nitrogen, and air. Among these, it is preferable to include at least one of helium, argon, and xenon, which are highly stable.

[0133] The installation position of gas introduction part 85 is not limited to the position shown in Fig. 25. For example, a gas introduction port functioning as gas introduction part 85 may be provided on the wall surface of hollow body 83. Gas introduction part 85 may be provided outside container 62A or may be provided inside container 62A.

[0134] Even when the inside of hollow body 83 is filled with gas and the upper end is sealed with plug 84, a small amount of gas may leak from inside hollow body 83, for example, if the sealing is not complete. The gas is introduced from gas inlet 85 to make up for the leaked gas, and is introduced to the extent that gas does not leak out from the opening at the lower end of hollow body 83. Note that gas inlet 85 is not an essential component in this embodiment.

[0135] 25 has one hollow body 83 surrounding one electrode 78A, the number of hollow bodies 83 and electrodes 78A of the mist generator 90 is not limited to this. The mist generator 90 may have a plurality of plasma generating units 82 each having one hollow body 83 surrounding one electrode 78A. That is, the container 62A may have a plurality of hollow bodies 83 each having one electrode 78A. Furthermore, the one or more hollow bodies 83 included in the mist generator 90 may have a plurality of electrodes 78A.

[0136] By having the mist generator 90 have a plurality of electrodes 78A surrounded by the hollow body 83, the amount of plasma irradiated onto the liquid surface increases, and the dispersibility of the particles 66 in the dispersion liquid 63 can be improved.

[0137] Fig. 26 is a diagram for explaining an overview of the plasma generating unit 82. Fig. 26A is an example of the appearance of the tip portion of the plasma generating unit 82, and Fig. 26B is an example (part 1) of a cross-sectional view (top view) of the plasma generating unit 82. Fig. 26C is an example (part 2) of a cross-sectional view (top view) of the plasma generating unit 82.

[0138] As in the above-described embodiments, the shape of electrode 78A in this embodiment is not limited to the example shown in Fig. 26. For example, electrode 78A may be electrode 78B or electrode 78C shown in Fig. 2. From the viewpoint of plasma generation efficiency, it is preferable that electrode 78A in this embodiment has a small area at the tip of electrode 78A closest to the liquid surface, as in the first embodiment shown in Fig. 2.

[0139] As shown in FIG. 26A, the liquid level LS, which is the boundary between the gas inside the hollow body 83 and the dispersion liquid 63, is located at the opening at the tip of the hollow body 83. The electrode 78A is provided at a position where the tip does not contact the liquid level LS of the dispersion liquid 63. In the mist generator 90, in order to improve the dispersibility of the particles 66, it is desirable that the plasma be irradiated from the electrode 78A to the dispersion liquid 63 in a stable manner. If the distance between the liquid level LS of the dispersion liquid 63 and the tip of the electrode 78A is long, the stability of the plasma irradiation is impaired. The upper limit of the distance Dt between the tip of the electrode 78A and the lower end of the hollow body 83 is preferably 30 mm, more preferably 25 mm.

[0140] Furthermore, if the distance between the liquid level LS of the dispersion liquid 63 and the tip of the electrode 78A is short, there is a possibility that the liquid level LS and the tip of the electrode 78A may come into contact with each other when the liquid level LS is shaken, etc. The lower limit of the distance Dt between the tip of the electrode 78A and the lower end of the hollow body 83 is preferably 10 mm, and more preferably 15 mm.

[0141] When the generation of mist from the mist generating section causes the liquid level of dispersion liquid 63 in container 62A to tremble, the distance between the tip of electrode 78A and the liquid level fluctuates, compromising the stability of the plasma irradiation and reducing the dispersibility of particles 66. By surrounding electrode 78A with hollow body 83 and providing the tip of hollow body 83 below the liquid level of dispersion liquid 63, trembling of the liquid level LS is suppressed and dispersion liquid 63 can be stably irradiated with plasma.

[0142] 26A, gas can be filled into hollow body 83 so that liquid level LS protrudes downward from the tip of hollow body 83. The surface tension of the liquid level LS suppresses shaking of the liquid level LS when the mist-generating unit generates mist, so that plasma can be irradiated to dispersion liquid 63 in a stable manner and the dispersibility of particles 66 in dispersion liquid 63 can be improved.

[0143] 26B and 26C are examples of cross-sectional views of the plasma generating part 82 as viewed from the Z-axis direction. The cross section of the hollow body 83 and the cross section of the electrode 78A shown in FIG. 26B are substantially circular. The cross section of the hollow body 83 shown in FIG. 26C is substantially circular, and the cross section of the electrode 78A is substantially square. As shown in FIG. 26B and FIG. 26C, the shape of the cross section of the electrode 78A is not limited. The shape of the cross section of the hollow body 83 is not limited to the example shown in this figure.

[0144] The plasma generating section 82 can be configured so that the axis of the electrode 78A coincides with the central axis of the hollow body 83. This allows the plasma generated from the electrode 78A to be stably guided to the liquid surface LS.

[0145] The storage unit 60A shown in Fig. 25 has a tapered shape with the wall surface tapering downward. However, the shape of the storage unit is not limited to the example shown in Fig. 25 and may be, for example, a cylinder. The storage unit may be made of a material and have a thickness that can propagate the vibration of the mist-generating unit to the dispersion liquid 63. The shape, material, and thickness of the storage unit are the same as those of the storage units in the other embodiments described above.

[0146] [Eighth embodiment: Modification 1] Fig. 27 is a schematic diagram showing an example of a mist generator 90 in a first modified example of the eighth embodiment. In this figure, the plug 84 and the gas inlet 85 are omitted. The hollow body 83 and the electrode 78A in this modified example are installed at an angle to the liquid surface. The hollow body 83 and the electrode 78A may be installed perpendicular to the liquid surface of the dispersion liquid 63, or may be installed at an angle.

[0147] [Eighth embodiment: Modification 2] 28 is a schematic diagram showing an example of a mist generator 90 in Modification 2 of the eighth embodiment. In this modification, the upper end of the hollow body 83 is located below the lid portion 61A. In other words, the entire hollow body 83 is located inside the storage portion 60A.

[0148] If the tip of electrode 78A is accommodated inside hollow body 83 and the lower end of hollow body 83 is located below the liquid surface of dispersion liquid 63, plasma generated from the tip can be stably irradiated onto dispersion liquid 63. Also in this modification, plasma generating unit 82 may have a gas inlet unit 85.

[0149] [Eighth embodiment: Modification 3] 29 is a schematic diagram showing an example of a mist generator 90 in Modification 3 of the eighth embodiment. The mist generator 90 in this modification has a ground electrode 86. The ground electrode 86 is placed at the bottom of the container 62A, and functions as a ground electrode for the voltage applied to the electrode 78A.

[0150] A predetermined area above the ground electrode 86 in the container 62A is defined as the ground upper area PC. That is, the ground upper area PC is the area directly above the ground electrode 86. For example, assuming that the upper end of the ground electrode 86 extends to the bottom surface of the container 62A, the ground upper area PC is an area in the housing part 60A that has a bottom surface within a predetermined range from the upper end of the ground electrode 86 and rises directly upward from the bottom surface to the lid part 61A. The electrode 78A is placed so that at least its tip is located in the ground upper area PC.

[0151] The plasma emitted from the tip of the electrode 78A is guided toward the ground electrode 86. By configuring the tip of the electrode 78A to be located directly above the ground electrode 86, the plasma can be appropriately guided to the liquid surface LS. In other words, the particles 66 can be dispersed more efficiently.

[0152] The area directly above the mist generating section 80 in the container 62A is referred to as the mist generating section upper area PB. The mist generating section 80 in this modified example is, for example, an ultrasonic vibrator. When the mist generating section 80 is driven, the liquid surface in the mist generating section upper area PB tends to sway. The hollow body 83 in this modified example is placed in a position other than the mist generating section upper area PB to reduce the effect of the liquid surface swaying on the plasma. More specifically, the hollow body 83 is placed in a position other than the mist generating section upper area PB, which is a predetermined range of area above the mist generating section 80.

[0153] 27, the hollow body 83 may be installed at an angle to the liquid surface. The hollow body 83 may be installed so that its lower end is located outside the upper region PB of the mist generating section. With this configuration, the plasma can be stably applied to the dispersion liquid 63, and the dispersibility of the particles 66 in the dispersion liquid 63 can be further improved.

[0154] In addition, the mist generator 90 in the eighth embodiment can be configured so that the supply direction of the gas supplied from the gas supply port of the gas supply unit 70A is different from the direction of gravity, as in the other embodiments described above. For example, the angle between the supply direction of the gas supplied from the gas supply port and the direction of gravity can be set to 90 degrees or more and 150 degrees or less. In addition, in order to make it easier to discharge the generated mist from the storage unit 60, it is preferable that the exhaust port 76 is located above the gas supply port 72 as shown in FIG. 25. [Explanation of symbols]

[0155] 1: thin film manufacturing equipment, 10: first chamber, 10A and 10B: air seal unit, 12: second chamber, 12A and 12B: air seal unit, 12C: duct, 20A and 20B: mist generating unit, 21A and 21B: duct, 22A and 22B: mist supply unit, 23A and 23B: temperature control unit, 24A and 24B: electrodes, 25A and 25B: top plate, 27A and 27B: substrate temperature control unit, 27C: temperature adjustment plate, 28: temperature control unit, 30: exhaust control unit, 30A: duct, 40: high voltage pulse power supply unit, 40A: variable DC power supply, 40B: high voltage pulse generating unit, 40Ba: pulse generation circuit section, 40Bb: boost circuit section, 50: drying section, 60, 60A, 60B, 60C: storage section, 61, 61A, 61B, 61C: lid section, 62, 62A, 62B, 62C: container, 70A, 70B, 70C, 70D, 70E, 70F, 70G, 70H, 70I, 70J: gas supply section, 72, 72A, 72B, 72C, 72D, 72E, 72F, 72G, 72H, 72I, 72J: gas supply port, 74, 74A, 74B, 74C, 74D, 74E, 74F: exhaust section, 76, 76A, 76B, 76C, 76D, 76E1, 76E2, 76F1, 76F2: Exhaust port, 78, 78A, 78B, 78C: electrodes, 79, 79A, 79B, 79C: tips, 80: mist generating section, 81: plate-shaped member, 82: plasma generating section, 83: hollow body, 84: plug, 85: gas inlet, 86: ground electrode, 90: mist generating device, 91: outer container, 94: partition, 96: storage space, 98: empty space, 100: main control unit, 270: base, 271A: inlet port, 271B: exhaust port, 272: spacer, 274: plate, 274A: ejection hole, 274B: intake hole, 275: substrate temperature control section, Cg, Cp: dielectric, Cg1 ·Cp1: quartz tube, CR1·CR2·CR3·CR4: rollers, Dh: opening, Dt: distance, EG·EP·EP1·EP2: electrodes, EQ1·EQ2: stand, ES1·ES2: edge sensor, FS: substrate, La·Lb·Lc: interval, LS: liquid level, Mgs: mist gas, PA: area, PB: upper area of ​​mist generator, PC: upper area of ​​ground, RL1: supply roll, RL2: recovery roll, Sfa·Sfb·Sfc: inner wall, SN: opening, TB1·TB2: air turn bar, Tu: time, Vo1·Vo2: voltage, WD: interval, φa: outer diameter, φb: inner diameter

Claims

1. A mist generating device for turning a liquid containing particles into mist, comprising: A container for containing the liquid; A mist generating unit that generates mist from the liquid; a gas supply unit that supplies a first gas into the container from a gas supply port; a plasma generating unit including an electrode for generating plasma between the electrode and a surface of the liquid, and a hollow body surrounding the electrode; A mist generating device, wherein one end of the hollow body is positioned below the liquid level of the liquid.

2. The mist generating device according to claim 1 , wherein the electrode is provided at a position where a tip of the electrode on the liquid surface side does not come into contact with the liquid surface.

3. 3. The mist generating device according to claim 1, wherein the plasma generating section has a gas inlet section that introduces a second gas into the hollow body.

4. A mist generating device as described in claim 3, wherein a tip of the hollow body located above the liquid level is closed, and the second gas is filled into the hollow body.

5. 5. The mist generating device according to claim 1, wherein the electrode is disposed within the hollow body such that an axis of the electrode coincides with a central axis of the hollow body.

6. The mist generating device according to claim 1 , wherein the mist generating unit is an ultrasonic vibrator.

7. 7. The mist generating device according to claim 1, wherein the hollow body is provided at a position excluding an upper region of the mist generating section, which is a predetermined range of an upper region of the mist generating section within the container.

8. 5. The mist generating device according to claim 3, wherein the second gas contains at least one of helium, xenon, and argon.

9. a ground electrode for the voltage applied to the electrodes is provided at a lower portion of the container; The mist generator according to claim 1 , wherein the electrode is provided so as to be located in an upper ground area, which is a predetermined area above the ground electrode within the container.

10. A mist generating device as described in any one of claims 1 to 9, wherein the first gas is a carrier gas that carries the misted liquid outside the container.

11. The mist generator according to any one of claims 1 to 10, wherein the gas supply unit is configured such that a supply direction of the first gas supplied from the gas supply port of the gas supply unit is different from a direction of gravity.

12. an angle between a supply direction of the first gas supplied from the gas supply port of the gas supply unit and a direction of gravity in which gravity acts is 90 degrees to 150 degrees; The mist generating device according to claim 11.

13. A discharge part is provided for discharging the mist of the liquid from the container. A mist generating device according to any one of claims 1 to 12.

14. The container includes a storage portion having an opening and a lid portion that covers the opening, The electrode, the gas supply unit, and the exhaust unit are disposed through the lid unit.

14. The mist generating device according to claim 13.

15. an angle between a discharge direction of the first gas discharged from the discharge port of the discharge unit and a gravitational direction in which gravity acts is 120 degrees to 180 degrees; 15. A mist generating device according to claim 13 or 14.

16. an angle between a supply direction of the first gas supplied from the gas supply port of the gas supply unit and a discharge direction of the first gas discharged from the discharge port is 30 degrees to 150 degrees; 16. The mist generating device according to claim 15.

17. The discharge section has two or more discharge ports.

17. A mist generating device according to claim 15 or 16.

18. The gas supply port is disposed below the exhaust port.

18. A mist generating device according to any one of claims 15 to 17.

19. The gas supply unit has two or more gas supply units.

19. A mist generating device according to any one of claims 1 to 18.

20. The gas supply port has two or more.

20. A mist generating device according to any one of claims 1 to 19.

21. The electrodes are two or more.

21. A mist generating device according to any one of claims 1 to 20.

22. The container is made of plastic or metal.

22. A mist generating device according to any one of claims 1 to 21.

23. The tip of the electrode is spherical in shape.

23. A mist generating device according to any one of claims 1 to 22.

24. The tip of the electrode has a needle-like shape.

24. A mist generating device according to any one of claims 1 to 23.

25. The first gas is any one of helium, argon, and xenon.

25. A mist generating device according to any one of claims 1 to 24.

26. A power supply unit that applies a voltage to the electrodes, The power supply unit applies a voltage at a frequency of 0.1 Hz to 50 kHz.

26. A mist generating device according to any one of claims 1 to 25.

27. The power supply unit applies a voltage of 21 kV or more.

27. The mist generating device according to claim 26.

28. The power supply unit applies a voltage to the electrodes, thereby generating a current of 1.1×10 ６ Generates an electric field of 100 V / m or more.

28. A mist generating device according to claim 26 or 27.

29. The liquid is a dispersion liquid containing particles and a dispersion medium.

29. A mist generating device according to any one of claims 1 to 28.

30. The dispersion medium includes water.

30. The mist generating device of claim 29.

31. The particles are inorganic oxides.

31. A mist generating device according to claim 29 or 30.

32. The particles include one or more of silicon dioxide, zirconium oxide, indium oxide, zinc oxide, tin oxide, titanium oxide, indium tin oxide, potassium tantalate, tantalum oxide, aluminum oxide, magnesium oxide, hafnium oxide, and tungsten oxide; 32. A mist generating device according to any one of claims 29 to 31.

33. The average particle size of the particles is 5 nm to 1000 nm.

33. A mist generating device according to any one of claims 29 to 32.

34. The concentration of the particles contained in the dispersion liquid is 0.001% by mass to 80% by mass.

34. A mist generating device according to any one of claims 29 to 33.

35. A thin film manufacturing apparatus for forming a film on a substrate, A mist generating device according to any one of claims 1 to 34; a mist supply unit that supplies the mist of the liquid onto a predetermined substrate; A thin film manufacturing device having the above structure.

36. A thin film manufacturing method for forming a film on a substrate, comprising the steps of: A step of turning the liquid into mist using the mist generating device according to any one of claims 1 to 34; supplying the mist of the liquid onto a predetermined substrate; A thin film manufacturing method comprising:

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