JP7596933B2 - Mist generating device, thin film manufacturing device, and thin film manufacturing method - Google Patents

Description

The present invention relates to a mist generating device, a thin film manufacturing device, and a thin film manufacturing method.

Conventionally, the deposition method shown in Patent Document 1 has been used as a technique for forming a thin film on a substrate. In addition to deposition, other techniques that require a vacuum or reduced pressure environment, such as sputtering, are generally used in the film formation process. This results in problems such as the large size and high cost of the equipment.

Patent Publication 2010-265508

The first aspect of the present invention is a mist generating device comprising a container for storing 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.

The 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 supply unit for supplying the misted liquid onto a specified substrate.

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 the liquid into a mist using the apparatus of the first aspect; and supplying the misted liquid to a specified substrate.

1 is a schematic diagram illustrating an example of a mist generating device according to a first embodiment. 2A is a schematic diagram showing an example of a tip portion 79 of an electrode 78 in the first embodiment. Fig. 2A shows an example of an electrode 78A in which a tip portion 79A has a needle-like shape, Fig. 2B shows an example of an electrode 78A in which a tip portion 79B has a plurality of needle-like portions, and Fig. 2C shows an example of an electrode 78C in which a tip portion 79C has a spherical shape. 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; Fig. 3C is a diagram illustrating the angle θ in Fig. 3A; 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. 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 an example of an angle β between a supply direction and a discharge direction. FIG. 2 is a schematic diagram illustrating an example of a mist generating device according to a first modified example of the first embodiment. FIG. 11 is a schematic diagram showing an example of a mist generating device according to a second modified example of the first embodiment. FIG. 11 is a schematic diagram showing an example of a mist generating device according to a third modified example of the first embodiment. FIG. 11 is a schematic diagram showing an example of a mist generating device according to a fourth modified example of the first embodiment. FIG. 13 is a schematic diagram showing an example of a mist generating device according to a fifth modified example of the first embodiment. FIG. 11 is a schematic diagram illustrating an example of a mist generating device according to a second embodiment. FIG. 13 is a schematic diagram illustrating an example of a mist generating device according to a third embodiment. FIG. 13 is a schematic diagram showing a modified example of the mist generating device according to the third embodiment. FIG. 13 is a schematic diagram illustrating an example of a mist generating device according to a fourth embodiment. FIG. 13 is a schematic diagram illustrating an example of a mist generating device according to a fifth embodiment. FIG. 13 is a schematic diagram showing a modified example of the mist generating device according to the fifth embodiment. FIG. 13 is a schematic diagram illustrating an example of a mist generating device according to a sixth embodiment. FIG. 13 is a schematic diagram showing a modified example of the mist generating device according to the sixth embodiment. FIG. 13 is a diagram showing a configuration example of a thin-film manufacturing apparatus according to a seventh embodiment. 13 is an example of a perspective view of a mist supply unit as viewed from the substrate side. FIG. 13 is an example of a cross-sectional view of the tip of the mist supply portion and a pair of electrodes as viewed from the Y-axis direction. FIG. 2 is a block diagram showing an example of a schematic configuration of a high-voltage pulse power supply unit. 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. FIG. 2 is a cross-sectional view showing an example of a configuration of a substrate temperature control unit. FIG. 23 is a schematic diagram showing an example of a mist generating device according to an eighth embodiment. 26A is a diagram for explaining an outline of a plasma generating unit, Fig. 26A is an example of the appearance of a 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. FIG. 23 is a schematic diagram showing an example of a mist generating device in a first modified example of the eighth embodiment. FIG. 23 is a schematic diagram showing an example of a mist generating device in a second modified example of the eighth embodiment. FIG. 23 is a schematic diagram showing an example of a mist generating device in a third modified example of the eighth embodiment.

The following describes in detail preferred embodiments of 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, with reference to the accompanying drawings. 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.

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

<Mist generating device>
The mist generator 90 shown in Fig. 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.

The flow of mist generation using the mist generating device 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 mistizes the dispersion liquid 63 in the storage unit 60A. 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 misted. The dispersion liquid 63 may be misted while the plasma is being generated, or may be misted after the plasma is generated. The dispersion liquid 63 may be misted after the plasma irradiation to prevent the particles 66 from agglomerating, but it is preferable to mist the dispersion liquid 63 during the plasma irradiation to improve the dispersibility of the particles 66. The misted dispersion liquid 63 (hereinafter, simply referred to as "mist") is discharged to the outside from the exhaust section 74 together with the gas supplied from the gas supply section 70.

The plasma in this embodiment is above-water plasma. Above-water plasma refers to plasma generated between one or more electrodes placed opposite the liquid surface and the liquid surface. In FIG. 1, 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 two or more electrodes may be provided in order to generate plasma uniformly within the storage section 60A. The distance between the liquid surface of the stationary liquid and electrode 78 is preferably 30 mm or less, and 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.

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

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. In addition, the voltage applied to the electrodes is preferably 21 kV (electric field is 1.1 x ¹⁰⁶ V/m) or more.

The material of electrode 78A is not particularly limited, but copper, iron, titanium, etc. can be used.

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 an electrode 78A in which the tip 79A is needle-shaped, FIG. 2B is an example of an electrode 78A in which the tip 79B has multiple needle-shaped portions, and FIG. 2C is an example of an electrode 78C in which the tip 79C is spherical. Note that electrodes 78B and 78C are modified versions of electrode 78A. Electrode 78A has tip 79A. When tip 79A is viewed from the -Z axis direction, it is preferable that the area of the part of tip 79A closest to the liquid surface is small from the viewpoint of plasma generation efficiency. Therefore, tip 79A has a needle shape (FIG. 2A). In addition, the shape of the tip of the electrode is not limited to this. Electrode 78B has tip 79B in a shape having multiple needles (FIG. 2B). In addition, 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 diagram.

In addition, although the electrodes 78 shown in Figures 1 and 2 are linear, they may each be curved.

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 will aggregate and settle in the dispersion liquid 63, so that the dispersion property may not be maintained. 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.

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 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. With this configuration, the vibrations generated in the mist generating unit 80 can be propagated to the container 62A. It is also possible to cool the heat generated in the mist generating unit 80 due to the vibrations. The liquid may be any liquid that can propagate vibrations, and water is preferable.

The mist obtained by the device according to this embodiment can be suitably used in the film forming device and film forming method described below.

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 generating device 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 be structured to seal the container 62A. If the lid portion 61A is structured to seal the container 62A, it is easier to fill the container 62A with gas, and the efficiency of plasma generation can be improved.

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

The particles 66 are preferably inorganic oxides. Although there are no particular limitations on the inorganic oxides, 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. are preferred. These may be used alone or in any combination of two or more.

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

The type of dispersion medium 64 is not particularly limited, and may be any type that allows the particles to be dispersed. Examples of the dispersion medium that can be used include water, alcohols such as isopropyl alcohol (IPA), ethanol, and methanol, acetone, dimethylformamide (DMF), dimethyl sulfoxide (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 viewpoint of particle dispersibility and dielectric constant.

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

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 gas include helium, argon, xenon, oxygen, nitrogen, and air. Among these, helium, argon, and xenon are preferred due to their high stability.

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, it is desirable that the total generation time is the irradiation time described above.

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 in the storage unit 60A. The shape of the gas supply port 72A is not limited to a circular shape.

Figure 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. Figure 3A is a schematic diagram showing an example of a gas supply unit 70A of the first embodiment and explaining the supply direction. Figure 3B is a schematic diagram explaining the supply direction of gas supply unit 70B. Figure 3C is a diagram for explaining the angle θ in Figure 3A.

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 using Figures 3A and 3B. 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 Figure 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 Figure 3B, the extension direction of gas supply unit 70B is the direction of gravity, and the supply direction is the direction of gravity (-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.

Next, the angle θ between the supply direction and the direction of gravity (g) will be described using FIG. 3C (FIG. 3C uses the gas supply unit of FIG. 3A). 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.

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 weakens. 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 generate plasma stably 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.

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

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

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

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

Next, the angle α between the discharge direction and the direction of gravity (g) will be explained using Figure 4C (Figure 4C uses the discharge section of Figure 4A). As shown in Figure 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. Note that 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 called α. In Figure 4C, 180 degrees is defined using a counterclockwise angle as viewed from the direction of gravity, but it is also possible to define 180 degrees using a clockwise angle.

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

The gas supply port 72A may be located either above or below the exhaust port 76A. However, it is preferable that the gas supply port 72A be located below the exhaust port 76A so that the supplied gas is more easily agitated and a uniform mist is discharged to the outside of the container 62A.

Figure 5 is an explanatory diagram showing an example of the angle β between the supply direction and the exhaust direction. Figure 5A is a schematic diagram of the gas supply unit 70C and the exhaust unit 74C of the first embodiment. Figure 5B is a diagram for explaining the angle β. The supply direction (represented by the arrow (a) here) and the exhaust direction (represented by the arrow (b) here) shown in Figure 5A are illustrated in Figure 5B. In Figure 5B, the smaller angle between the two directions is called the angle β between the supply direction and the exhaust direction. It is desirable to set the angle β to an angle that causes mist to be included in the gas exhausted from the exhaust unit 74C. 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.

Note that while Figures 3A and 4A show the case where θ = 90 degrees and α = 180 degrees, this embodiment is not limited to this. Modifications are shown below.

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

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 modified example, 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 modified example, the first intersection of the arrow (a) is not limited to the side of the container 60A, but may be the exhaust unit 74A or the electrode 78A.

[First embodiment: Modification 2]
FIG. 7 is a schematic diagram showing an example of a mist generating device 90 in the second modified example of the first embodiment. In the mist generating device 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.

[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, a gas supply unit 70F is inserted from the side of the storage unit 60A. In this modification, the first intersection of the arrow (a) (a line drawn from the center of gravity of the gas supply port 72F in the supply direction) is the electrode 78A. The first intersection of the arrow (a) 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.

[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 kept at 180 degrees, and the angle θ between the supply direction and the direction of gravity is greater than 90 degrees. It is desirable that the first intersecting portion of the arrow (a) (a line drawn in the supply direction from the center of gravity of the gas supply port 72G) 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.

[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.

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 of the second embodiment is the same as that of the above-mentioned first embodiment unless otherwise specified.

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

The mist generator 90 shown in FIG. 11 has two gas supply units 70A. Increasing the number of gas supply units 70A allows a large amount of gas to be supplied to the container 62A at one time. When attempting to supply a large amount of gas to the container 62A using one gas supply unit 70A, even if the gas is not supplied directly to the liquid surface of the dispersion liquid 63, gas with a high flow rate is supplied locally, which may cause significant disturbance in the airflow in the container 62A and significant rippling of the liquid surface. Increasing the number of gas supply units 70A increases the amount of gas supplied while suppressing an increase in the flow rate of the gas supplied from one gas supply unit 70A, thereby suppressing significant rippling of the liquid surface of the dispersion liquid 63.

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.

[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.

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

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 supplied directly to the liquid surface, gas with a high flow rate is supplied locally in the container 62A, which may cause the air flow in the container 62A to be significantly disturbed and the liquid surface of the dispersion liquid 63 to be significantly 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 can be prevented from being significantly wavy.

The number of gas supply ports 72H1 (H2) is not limited to two, and may be three 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.

[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. 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 angle θ and angle 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.

[Fourth embodiment]
The fourth embodiment will be described with reference to Fig. 14. Unless otherwise specified, the configurations of the fourth embodiment are the same as those of the first embodiment. A mist generator 90 in this embodiment has two or more exhaust units 74A.

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

The mist generating device 90 shown in FIG. 14 has two exhaust sections 74A. By increasing the number of exhaust sections 74A, a large amount of gas can be exhausted from inside the container 62A at one time. In addition, the mist generated inside the container 62A can be exhausted evenly.

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 this is not limiting, and two or more discharge sections 74 may be provided in the first to third embodiments described above.

[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.

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

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

The number of outlets 76E1 (E2) is not limited to two, and may be three or more. The configuration of the outlet 74E is not limited to the configuration shown in FIG. 15.

[Fifth embodiment: modified example]
Fig. 16 is a schematic diagram showing a modification of the mist generating device 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 discharge port 76E may satisfy the above-mentioned angle α and angle β with respect to each discharge direction as described in the first embodiment. Also, as described in the fourth embodiment, the mist generating device 90 may use a combination of a plurality of discharge sections 74.

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.

Figure 17 is a schematic diagram showing an example of a mist generating device 90 in the sixth embodiment. Figure 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 generating device according to the sixth embodiment. Note that the mist generating unit 80 is not shown in Figure 17.

The container 62B shown in FIG. 17 has a partition 94 in the storage section 60B. There are two spaces in the storage section 60B. The space that contains the dispersion liquid is the storage space 96. The space that does not contain the dispersion liquid 63 is the empty space 98. The number of storage spaces 96 and empty spaces 98 is not limited to one, and there may be multiple spaces. The gas supply port 72J is installed in the empty space 98.

In order to exhaust the gas supplied from the gas supply port 72J into the container 62B from the exhaust section 74A, the partition 94 does not have a height that reaches the lid section 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 section 60B. In other words, the storage space 96 is the space that is separated by the partition 94, contains the dispersion liquid 63, and extends upward until it reaches the lid section 61B, and the empty space 98 is the space that is separated by the partition 94, does not contain the dispersion liquid, and extends upward until it reaches the lid section 61B.

By providing a gas supply port 72J in the empty space 98, gas can be filled into the container 62B without directly spraying the gas onto the dispersion liquid 63. In addition, the exhaust section 74A is located within the storage 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.

[Sixth embodiment: modified example]
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.

The gas supply port 72J is located at a position that does not face the liquid surface. This allows the container 62C to be filled with gas without supplying gas directly to the liquid surface. The exhaust port 76A is located at a position that faces 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.

[Seventh embodiment]
<Thin film manufacturing equipment/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, which will be described below with reference to FIG.

Figure 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. In addition, the ducts 21A and 21B correspond to the exhaust unit 74 described above.

In this embodiment, the thin-film manufacturing apparatus 1 uses a roll-to-roll method to continuously form a thin film of particles 66 on the surface of a flexible long sheet substrate FS.

(General configuration of the device)
In Fig. 19, an orthogonal coordinate system XYZ is defined such that the floor of the factory where the main body of the apparatus is installed is the XY plane, and the direction perpendicular to the floor is the Z axis direction. In addition, in the thin-film manufacturing apparatus 1 of Fig. 19, the sheet substrate FS is transported in the longitudinal direction in a state in which the surface of the sheet substrate FS is always perpendicular to the XZ plane.

A long sheet substrate FS (hereinafter simply referred to as substrate FS) is wound over a predetermined length as the object to be processed on the supply roll RL1 mounted on the frame EQ1. The frame EQ1 is provided with a roller CR1 around which the sheet substrate FS drawn from the supply roll RL1 is wound, and the supply roll RL1 and the roller CR1 are arranged to extend in the Y-axis direction (perpendicular to the paper surface of FIG. 19) so that their central axes of rotation 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 diagonally 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 transport direction while slightly floating it by an air bearing (gas layer), as described in WO2013/105317, for example. The air turn bar TB1 can be moved in the Z-axis direction by driving a pressure adjustment unit (not shown), and applies tension to the substrate FS without contact.

After passing through roller CR2, substrate FS passes through slit-shaped air seal 10A of first chamber 10, and then passes through slit-shaped air seal 12A of second chamber 12, which houses the deposition body, and is conveyed diagonally upwards in a straight line into second chamber 12 (deposition body). When substrate FS is conveyed through second chamber 12 at a constant speed, a film of particles 66 is formed to a predetermined thickness on the surface of substrate FS by mist deposition assisted by atmospheric pressure plasma or mist CVD (Chemical Vapor Deposition).

After the substrate FS has been subjected to the film formation process in the second chamber 12, it exits the second chamber through the slit-shaped air seal section 12B, is folded back in the -Z-axis direction by roller CR3, then folded by roller CR4 provided on the stand section EQ2, and wound up on the recovery roll RL2. The recovery roll RL2 and roller CR4 are provided on the stand section EQ2, extending in the Y-axis direction (perpendicular to the paper surface of FIG. 19) so that their central axes of rotation 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.

The air seal parts 10A, 10B, 12A, and 12B shown in FIG. 19 have 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, as disclosed in WO2012/115143, for example. 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 edge 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.

In this 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 the transport speed of the substrate FS is set to a target value and a predetermined tension (longitudinal direction) is applied to the substrate FS at least between the rollers CR2 and CR3. 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.

In addition, the frame unit EQ1 (and the supply roll RL1 and roller CR1) has a function to move slightly in the Y-axis direction within a range of about ± several mm by a servo motor or the like in response to the detection results from the edge sensor ES1, which measures the fluctuation in the Y-axis direction (the width direction perpendicular to the long direction of the sheet substrate FS) of both edges (ends) of the sheet substrate FS just before it reaches the air turn bar TB1, i.e., an EPC (edge position control) function. As a result, even if there is uneven winding in the Y-axis direction of the sheet substrate wound around the supply roll RL1, the center position in the Y-axis direction of the sheet substrate FS passing through the roller CR2 is always kept 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.

Similarly, the stand EQ2 (and roll RL2, roller CR4) has an EPC function that moves slightly in the Y-axis direction by a servo motor or the like within a range of ± several meters in response to the detection results from the edge sensor ES2, which 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).

In the device 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 onto the sheet substrate FS by the mist deposition method or the mist CVD method to remain adequately on the surface of the sheet substrate FS, 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, with the plane parallel to the processed surface of the substrate FS being the Y-Xt plane and the direction perpendicular to the Y-Xt plane being Zt.

In this embodiment, two mist supply units 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 units 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 spraying mist gas (mixture of gas and mist) Mgs toward the substrate FS. Furthermore, a pair of parallel wire-shaped electrodes 24A, 24B are provided near the openings of the mist supply units 22A, 22B for generating atmospheric pressure plasma in a non-thermal equilibrium state. A pulse voltage from the high-voltage pulse power supply unit 40 is applied to each of the pair of electrodes 24A, 24B at a predetermined frequency.

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

In addition, temperature adjustment units 23A and 23B are provided on the outer periphery of the mist supply units 22A and 22B to maintain the internal space of the mist supply units 22A and 22B at a set temperature. The temperature adjustment units 23A and 23B are controlled by the temperature control unit 28 to maintain the set temperature.

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 each of the mist supply units 22A and 22B via the ducts 21A and 21B at a predetermined flow rate. The mist gas Mgs of the dispersion liquid 63 ejected in the -Zt axis direction from the slit-shaped openings of the mist supply units 22A and 22B is sprayed onto the upper surface of the substrate FS at a predetermined flow rate, and would immediately 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 in by the exhaust control unit 30 via the duct 12C. That is, by creating a gas flow from the slit-shaped openings of the mist supply units 22A and 22B in the second chamber 12 toward the duct 12C, the mist gas Mgs of the dispersion liquid 63 is controlled to flow immediately downward (in the -Z axis direction) from the upper surface of the substrate FS.

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.

When depositing a film on the substrate FS by mist CVD using the mist gas Mgs of the dispersion liquid 63 from each of the mist supply units 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 units 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 units 22A and 22B across the substrate FS, and the temperature of the area on the substrate FS where the mist gas Mgs of the dispersion liquid 63 is sprayed is controlled by the temperature adjustment control unit 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 units 27A and 27B, but if 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 units 27A and 27B can be operated as appropriate.

The mist generating units 20A and 20B, temperature 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 and drive the supply roll RL1 and the recovery roll RL2) described above are all controlled by a main control unit 100 that includes a computer.

(Sheet substrate)
Next, the sheet substrate FS as the object to be processed will be described. As described above, the substrate FS is, for example, a resin film, a foil made of a metal or an alloy such as stainless steel, or the like. The material of the resin film may be, for example, 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 in which the substrate FS does not develop folds or irreversible wrinkles due to buckling when transported. When making flexible display panels, touch panels, color filters, electromagnetic wave protection filters, and the like as electronic devices, inexpensive resin sheets such as PET (polyethylene terephthalate) and PEN (polyethylene naphthalate) having a thickness of about 25 μm to 200 μm are used.

It is desirable to select a substrate FS having a thermal expansion coefficient that is not significantly large 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 the base resin film. The substrate FS may be a single layer of ultra-thin glass having a thickness of about 100 μm manufactured by the float method or a single layer of a metal sheet in which a metal such as stainless steel is rolled into a thin film, or may be a laminate in which the ultra-thin glass or metal sheet is laminated with the above-mentioned resin film or a metal layer (foil) such as aluminum or copper. Furthermore, when forming a film by the 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 the 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 (e.g. polyimide resin, ultra-thin glass, metal sheets, etc.) are used.

The flexibility of the substrate FS refers to the ability of the substrate FS to bend without breaking or breaking even when a force equivalent to its own weight is applied to the substrate FS. The property of bending due to a force equivalent to its own weight is also included in flexibility. The degree of flexibility varies depending on the material, size, and thickness of the substrate FS, the layer structure formed on the substrate FS, and the 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 manages the processes before and after it, if the substrate FS can be transported smoothly without buckling and creating creases or breaking (breaking or cracking), it can be said to be within the range of flexibility.

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 of a resin film (insulating film) or a metal thin film (copper, aluminum, etc.) formed to a certain thickness on the surface of the 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, as disclosed in WO2013/176222, for example, a photosensitive silane coupling material is applied to the surface of the substrate and dried, and then ultraviolet rays (wavelength 365 nm or less) are irradiated by an exposure device in a distribution according to the shape of the pattern for the electronic device, resulting in a large difference in the liquid affinity/repellency to the mist liquid between the irradiated and unirradiated portions of the ultraviolet light. At this time, the mist adheres to the hydrophilic parts of the irradiated or unirradiated parts, and the mist can be selectively adhered to the surface of the substrate FS according to the shape of the pattern by the mist deposition method using the thin-film manufacturing apparatus 1 shown in Figure 1.

Furthermore, the long sheet substrate FS supplied to the thin-film manufacturing apparatus 1 of FIG. 19 may be a long, thin metal sheet (e.g., 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.

Next, the configuration of each part of the thin-film manufacturing apparatus 1 in FIG. 19 will be described with reference to FIG. 19 as well as FIG. 20 to FIG. 24.

(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, that is, 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 width in the Xt direction 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. The top plate 25A (25B) has a duct 21A (21B) from the mist generating unit 20A (20B) connected to an opening Dh, and the mist gas Mgs is supplied into the mist supply unit 22A (22B). At the tip of the mist supply unit 22A (22B) in the -Zt axis direction, a slot-shaped opening SN is formed that extends elongatedly over a length La in the Y axis direction, and a pair of electrodes 24A (24B) are provided to sandwich the opening SN in the Xt direction. Therefore, the mist gas Mgs (positive pressure) supplied into the mist supply unit 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.

The pair of electrodes 24A is composed of a wire-shaped electrode EP extending in the Y-axis direction to a length La or more, and a wire-shaped electrode EG extending in the Y-axis direction to 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 that they are 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 also be ceramic tubes with high insulation voltage resistance.

Figure 21 is an example of a cross-sectional view of the tip of the mist supply unit 22A (22B) and a 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, 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 in a straight line 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 that is sprayed from the opening SN at the tip of the mist supply unit 22A (22B), contamination and corrosion of the exposed electrode EG may occur, so it is better to surround both electrodes EP and EG with quartz tubes Cp1 and Cg1 so that the mist gas Mgs does not come into direct contact with the electrodes EP and EG.

Here, each of the wire-shaped electrodes EP, EG is arranged 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 arranged at a distance Lb from the surface of the substrate FS in the transport direction (Xt direction) of the substrate FS. The distance 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.

Furthermore, although not essential, it is advisable to make the working distance WD larger than the distance Lb between the wire-shaped electrodes EP and EG in the Xt axis direction. This is because if the arrangement is such that Lb>WD, plasma may be generated or arc discharge may occur between the positive electrode EP (quartz tube Cp1) and the substrate FS.

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

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

The plane formed by 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 set as the distance WD, and the installation position of the mist supply unit 22A (22B) or the substrate FS is adjusted.

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 in the Xt direction between the wire-shaped electrodes EP and EG may be 10 μm to 20 mm from the viewpoint of plasma generation efficiency, with the lower limit being preferably 0.1 mm, and more preferably 1 mm. The upper limit being preferably 15 mm, and more preferably 10 mm.

When the spacing Lb (or width Lc) and working distance WD between the pair of electrodes 24A (24B) are not changed, the deposition 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 (particles, molecules, ions, etc.) contained in the mist gas Mgs for deposition, or the controlled temperature by the substrate temperature control unit 27A (27B) located on the back side of the substrate FS, etc. These conditions are appropriately adjusted by the main control unit 100 depending on the type of specific substance deposited on the substrate FS, the thickness of the deposition, flatness, etc.

(High voltage pulse power supply unit 40)
22 is a block diagram showing an example of the 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, for example, 0V and 150V, 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 boosting 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.

The pulse generating circuit section 40Ba is composed of semiconductor switching elements etc. that rapidly turn on/off the primary voltage Vo1 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 etc.

These pulse generating circuit unit 40Ba and boost circuit unit 40Bb are just examples, and any configuration may be used as long as it can continuously generate a pulse voltage 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 as the final interelectrode voltage Vo2 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.

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 to change 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 to change 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.

Figure 23 shows an example of the waveform characteristics of the interelectrode voltage Vo2 obtained by the high-voltage pulse power supply unit 40 configured as in Figure 22, with the vertical axis representing the voltage Vo2 (kV) and the horizontal axis representing time (μS). The characteristics in Figure 23 show 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 with a peak value of about 18kV is obtained. Furthermore, the rise time Tu from 5% to 95% of the first peak value (18kV) is about 120nS. In addition, in the circuit configuration of Figure 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.

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

(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 (similar to 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), if the upper surface of the substrate temperature control section 27A (27B) is in contact with the rear surface of the sheet substrate FS, there is a risk of scratching the rear surface of the substrate FS. Therefore, in this embodiment, an air bearing gas layer with a thickness of 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).

The substrate temperature control unit 27A (27B) is composed of a base 270 arranged opposite the back surface of the substrate FS, spacers 272 of a fixed height arranged at multiple locations on the base 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 270 and the plate 274.

Each of the spacers 272 is formed with a gas outlet 274A that penetrates to the surface of the plate 274, and an intake 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 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 source of pressurized gas, and the exhaust port 271B is connected to a reduced pressure source that creates a vacuum pressure.

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

In addition, the gap between the front surface of the plate 274, whose temperature is adjusted by the multiple substrate temperature adjustment units 275, and the rear surface of the substrate FS is only a few μm to a few tens of μm, so 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 unit 28 shown in FIG. 19.

In addition, if 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 27C (a set of plate 274 and substrate temperature adjustment unit 275 in FIG. 24) that faces the top surface of the substrate FS with a predetermined gap is provided upstream of the spray area of the mist gas Mgs in the transport direction of the substrate FS.

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 supporting the substrate FS flat by floating it using a hair bearing method. 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 with 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.

As described above, in the thin-film manufacturing apparatus 1 configured in 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 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.

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 approximately two times. 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.

In this embodiment, mist generating units 20A, 20B are provided for each of the mist supply units 22A, 22B, and substrate temperature control units 27A, 27B are provided for each of the mist supply units 22A, 22B. This makes it possible to differentiate the characteristics (concentration of a specific substance in the precursor LQ, the mist gas ejection flow rate and temperature, etc.) of the mist gas Mgs ejected from the opening SN of the mist supply unit 22A from the mist gas Mgs ejected from the opening SN of the mist supply unit 22B, or to differentiate the temperature of the substrate FS. By differentiating the characteristics of the mist gas Mgs ejected from the opening SN of each of the mist supply units 22A, 22B, or the temperature of the substrate FS, the film formation state (film thickness, flatness, etc.) can be adjusted.

The thin film manufacturing apparatus 1 in FIG. 19 transports the substrate FS by a roll-to-roll method alone, so the film formation rate can also be adjusted by changing the transport speed of the substrate FS. However, if a pre-processing device that performs surface treatment, etc. on the substrate FS before the film is formed by the thin film manufacturing apparatus 1 as shown in FIG. 19, or a post-processing device that immediately applies coating treatment, such as photosensitive resist or 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 cases, the thin film manufacturing apparatus 1 according to this embodiment can adjust the film formation state to suit the set transport speed of the substrate FS.

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

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. When the mist gas Mgs is supplied to the substrate from the Zt direction, there is a possibility that droplets accumulated in the mist supply units 22A and 22B may fall onto the substrate FS, but this can be suppressed by supplying the mist gas Mgs 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.

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 FIG. 25 to FIG. 28 includes an external container 91 and a mist generating unit 80 similar to those in the above-mentioned embodiment. In the examples shown below, the mist generating unit 80 and the external container 91 are omitted from illustration unless otherwise specified.

The mist generating device 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 introduction unit 85. The hollow body 83 is a member that surrounds at least a portion of the electrode and has a cavity inside.

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 Figure 25, the hollow body 83 penetrates the lid portion 61A. That is, the plug 84 is located outside the container 62A.

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

The gas inlet 85 introduces gas into the hollow body 83. As an example, the gas inlet 85 penetrates the plug 84. The gas introduced by the gas inlet 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.

The installation position of the gas introduction section 85 is not limited to the position shown in FIG. 25. For example, a gas introduction port that functions as the gas introduction section 85 may be provided on the wall surface of the hollow body 83. The gas introduction section 85 may be provided outside the container 62A or inside the container 62A.

Even if the inside of the hollow body 83 is filled with gas and the upper end is sealed with the plug 84, a small amount of gas may leak from inside the hollow body 83, for example, if the seal is not complete. The gas is introduced from the 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 the hollow body 83. Note that the gas inlet 85 is not a required component in this embodiment.

Note that the mist generating device 90 shown in FIG. 25 has one hollow body 83 surrounding one electrode 78A, but the number of hollow bodies 83 and electrodes 78A of the mist generating device 90 is not limited to this. The mist generating device 90 may have multiple plasma generating units 82 each having one hollow body 83 surrounding one electrode 78A. That is, the container 62A may have multiple hollow bodies 83 each having one electrode 78A. Furthermore, one or more hollow bodies 83 included in the mist generating device 90 may have multiple electrodes 78A.

By having the mist generating device 90 have multiple electrodes 78A surrounded by a hollow body 83, the amount of plasma irradiated onto the liquid surface increases, improving the dispersibility of the particles 66 in the dispersion liquid 63.

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

The shape of electrode 78A in this embodiment is not limited to the example shown in FIG. 26, as in the above-described embodiment. 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 the area of the tip of electrode 78A in this embodiment, which is closest to the liquid surface, is small, as in the first embodiment shown in FIG. 2.

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 its tip does not contact the liquid level LS of the dispersion liquid 63. In the mist generating device 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 large, 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, and more preferably 25 mm.

In addition, if the distance between the liquid surface LS of the dispersion liquid 63 and the tip of the electrode 78A is short, there is a possibility that the liquid surface LS and the tip of the electrode 78A may come into contact with each other when the liquid surface LS sways. 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.

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

Also, as shown in FIG. 26A, gas can be filled into the hollow body 83 so that the liquid surface LS protrudes downward from the tip of the hollow body 83. The surface tension of the liquid surface LS suppresses shaking of the liquid surface LS when the mist generating section generates mist, so that the plasma can be irradiated stably onto the dispersion liquid 63, and the dispersibility of the particles 66 in the dispersion liquid 63 can be improved.

Figures 26B and 26C are examples of cross-sectional views of the plasma generating unit 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 Figure 26B are approximately circular. The cross-section of the hollow body 83 shown in Figure 26C is approximately circular, and the cross-section of the electrode 78A is approximately square. As shown in Figures 26B and 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 also not limited to the example shown in this figure.

The plasma generating unit 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.

The storage section 60A shown in FIG. 25 has a tapered shape with the wall surface tapering downward. However, the shape of the storage section is not limited to the example shown in FIG. 25 and may be, for example, a cylinder. The storage section may be made of a material and have a thickness that can transmit the vibrations of the mist generating section to the dispersion liquid 63. The shape, material, and thickness of the storage section are the same as those of the storage sections in the other embodiments described above.

[Eighth embodiment: modified example 1]
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.

[Eighth embodiment: modified example 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 within the storage portion 60A.

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

[Eighth embodiment: modified example 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.

A predetermined area above the ground electrode 86 in the container 62A is the ground upper area PC. In other words, 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 storage section 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 section 61A. The electrode 78A is installed so that at least its tip is located in the ground upper area PC.

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

The area directly above the mist-producing section 80 in the container 62A is the mist-producing section upper area PB. In this modified example, the mist-producing section 80 is, for example, an ultrasonic vibrator. When the mist-producing section 80 is driven, the liquid surface in the mist-producing section upper area PB tends to tremble. The hollow body 83 in this modified example is installed in a position other than the mist-producing section upper area PB to reduce the effect on the plasma of the trembling of the liquid surface. More specifically, the hollow body 83 is installed in a position other than the mist-producing section upper area PB, which is a predetermined range of area above the mist-producing section 80.

The hollow body 83 in this modified example may be installed at an angle to the liquid surface, similar to the hollow body 83 shown in FIG. 27. The hollow body 83 may be installed so that its lower end is located at a position other than the upper region PB of the mist generating section. With this configuration, the plasma can be stably irradiated onto the dispersion liquid 63, and the dispersibility of the particles 66 in the dispersion liquid 63 can be further improved.

Additionally, the mist generating device 90 in the eighth embodiment can be configured, as in the other embodiments described above, so that the supply direction of the gas supplied from the gas supply port of the gas supply unit 70A differs from the direction of gravity. For example, the angle between the supply direction of the gas supplied from the gas supply port and the direction of gravity in which gravity acts can be 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.

1: Thin film manufacturing equipment, 10: First chamber, 10A and 10B: Air seal section, 12: Second chamber, 12A and 12B: Air seal section, 12C: Duct, 20A and 20B: Mist generating section, 21A and 21B: Duct, 22A and 22B: Mist supply section, 23A and 23B: Temperature control section, 24A and 24B: Electrodes, 25A and 25B: Top plate, 27A and 27B: Substrate temperature control section, 27C: Temperature adjustment plate, 28: Temperature control section, 30: Exhaust control section, 30A: Duct, 40: High voltage pulse power supply section, 40A: Variable DC power supply, 40B: High voltage pulse generating section, 40Ba: Pulse generation circuit section, 40Bb: boost circuit section, 50: drying section, 60, 60A, 60B, 60C: storage sections, 61, 61A, 61B, 61C: lid sections, 62, 62A, 62B, 62C: containers, 70A, 70B, 70C, 70D, 70E, 70F, 70G, 70H, 70I, 70J: gas supply sections, 72, 72A, 72B, 72C, 72D, 72E, 72F, 72G, 72H, 72I, 72J: gas supply ports, 74, 74A, 74B, 74C, 74D, 74E, 74F: exhaust sections, 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: Roller, Dh: Opening, Dt: Distance, EG, EP, EP1, EP2: Electrode, EQ1, EQ2: Stand, ES1, ES2: Edge sensor, FS: Substrate, La, Lb, Lc: Distance, 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: Distance, φa: Outer diameter, φb: Inner diameter

Claims (36)

A mist generating device that turns a liquid containing particles into mist,
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. The mist generating device according to claim 1, wherein the electrode is provided at a position where the tip of the electrode on the liquid surface side does not come into contact with the liquid surface. The mist generating device according to claim 1 or 2, wherein the plasma generating unit has a gas inlet that introduces a second gas into the hollow body. 4. The mist generating device according to claim 3, wherein a tip of the hollow body located above the liquid surface is closed, and the hollow body is filled with the second gas. 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. The mist generating device according to claim 1 , wherein the mist generating unit is an ultrasonic vibrator. 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. 5. The mist generating device according to claim 3, wherein the second gas contains at least one of helium, xenon, and argon. 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. The mist generating device according to claim 1 , wherein the first gas is a carrier gas that carries the mist of the liquid outside the container. The mist generating device 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. 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;
A mist generating device as claimed in claim 1 1 . 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 . 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.
The mist generating device according to claim 13 . 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;
A mist generating device according to claim 13 or 14 . 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;
The mist generating device according to claim 15 . The discharge section has two or more discharge ports.
A mist generating device according to claim 15 or 16 . The mist generating device according to any one of claims 15 to 17 , wherein the gas supply port is disposed below the exhaust port. The gas supply unit has two or more gas supply units.
A mist generating device according to any one of claims 1 to 18 . The gas supply port has two or more.
A mist generating device according to any one of claims 1 to 19 . The electrodes are two or more.
21. A mist generating device according to any one of claims 1 to 20 . The container is made of plastic or metal.
A mist generating device according to any one of claims 1 to 21 . The tip of the electrode is spherical in shape.
A mist generating device according to any one of claims 1 to 22 . The tip of the electrode has a needle-like shape.
The mist generating device according to any one of claims 1 to 23 . The first gas is any one of helium, argon, and xenon.
A mist generating device according to any one of claims 1 to 24 . 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.
A mist generating device according to any one of claims 1 to 25 . The power supply unit applies a voltage of 21 kV or more.
The mist generating device according to claim 26 . The power supply unit applies a voltage to the electrodes to generate an electric field of 1.1×10 ⁶ V/m or more.
A mist generating device according to claim 26 or 27 . The liquid is a dispersion liquid containing particles and a dispersion medium.
A mist generating device according to any one of claims 1 to 28 . The dispersion medium includes water.
The mist generating device according to claim 29 . The particles are inorganic oxides.
The mist generating device according to claim 2, 9 or 30 . 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;
A mist generating device according to any one of claims 29 to 31 . The mist generating device according to any one of claims 29 to 32 , wherein the particles have an average particle size of 5 nm to 1000 nm. The mist generating device according to any one of claims 29 to 33 , wherein the concentration of the particles contained in the dispersion liquid is 0.001% by mass to 80% by mass. 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. 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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