Atomization device and film forming device.

Abstract

To provide an atomizer which is excellent in an atomization amount and atomization controllability.SOLUTION: In an atomizer, an ultrasonic wave transmission liquid is provided above an ultrasonic vibrator. The atomizer includes: a raw material partition wall in which a raw material liquid for atomization is stored; an ultrasonic wave transmission liquid tank in which the ultrasonic wave transmission liquid is stored; and the ultrasonic vibrator which is located on a bottom surface part of the ultrasonic wave transmission liquid tank and radiates ultrasonic waves to the bottom surface part of the raw material partition wall. The bottom surface part of the raw material partition wall is closed by an ultrasonic wave permeable base material. The ultrasonic vibrator is enclosed by a guide partition wall until the guide partition wall reaches the ultrasonic wave permeable base material. The atomizer is useful for producing mist, and, for example, is preferably used in a semiconductor device for membrane production.SELECTED DRAWING: Figure 1

Description

[Technical Field]

[0001] The present invention relates to an atomization device and a film-forming device that are useful for semiconductor film formation and the like. [Background technology]

[0002] Ultrasonic atomizers that use ultrasonic vibrators are known as devices for generating (atomizing) fine droplets from liquid. In these ultrasonic atomizers, the ultrasonic vibrator is placed at the bottom or other location of a container that stores the liquid to be atomized. When the ultrasonic vibrator vibrates, the liquid particles in the liquid vibrate in the direction of ultrasonic wave propagation, and the vibration energy concentrates on the liquid surface, forming a liquid column. The tip of the liquid column breaks off, scattering the liquid particles and generating mist.

[0003] In recent years, it has been described that atomization devices having a piezoelectric element made of piezoelectric ceramics and an insulating resin film covering the adherend surface of the piezoelectric element, including the liquid-facing surface that faces the liquid, and arranged in a manner such that the liquid-facing surface faces the liquid and the insulating resin film made of a paraxylylene-based polymer is in contact with the liquid, are highly chemical-resistant and stable against many chemical solutions, thereby reducing restrictions on the liquid that can be used (Patent Document 1). However, because the adherend surface of these atomization devices is fixed, it is difficult to clean the gap between the ultrasonic vibrator and the adherend surface after use, and further, with prolonged use, the liquid level drops, reducing the amount of atomization and worsening atomization efficiency. In addition, to maintain atomization efficiency, it is necessary to keep the liquid level constant, which increases the amount of solution used, making them unenvironmentally unfriendly. Furthermore, it has been studied that an atomization device consisting of an outer container with an ultrasonic vibrator fixed to the bottom, a transfer liquid contained in the outer container, an inner container attached to the inside of the outer container at a predetermined distance and having a horn-shaped protrusion formed on the part facing the ultrasonic vibrator, and an atomization liquid contained in the inner container, can be prepared in a number corresponding to the type of liquid to be atomized, and that does not need to be cleaned every time the liquid is changed (Patent Document 2). However, these atomization devices have the problem that even if a communication groove is formed so that the side of the inner container communicates with the upper end of the horn-shaped protrusion, air tends to remain due to insufficient degassing, reducing the amount of liquid atomized in the inner container. It has been described that an atomization device in which the bottom of a bottomless cylindrical body is sealed with an ultrasonically transparent substrate has excellent atomization efficiency and mist controllability (Patent Document 3). However, these atomization devices have problems such as scattering of ultrasonic waves transmitted to the liquid surface because they are not uniformly concentrated, resulting in insufficient atomization amount and atomization efficiency. In addition, there are problems such as the liquid level dropping over long periods of use, which reduces the atomization amount and atomization efficiency, and the need to repeatedly replenish the solution. Therefore, there has been a demand for an atomization device that is excellent in atomization amount and atomization controllability. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Patent No. 4512850 [Patent Document 2] Japanese Patent Application Laid-Open No. 2012-011360 [Patent Document 3] Patent No. 6680433 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present invention is to provide an atomization device that is excellent in atomization amount and atomization controllability. [Means for solving the problem]

[0006] As a result of intensive research into achieving the above-mentioned object, the present inventors have found that an atomization device comprising an ultrasonic wave transmission liquid provided above an ultrasonic vibrator, a raw material partition wall containing a raw material liquid to be atomized, an ultrasonic wave transmission liquid tank containing the ultrasonic wave transmission liquid, and an ultrasonic vibrator at the bottom of the ultrasonic wave transmission liquid tank for irradiating ultrasonic waves onto the bottom of the raw material partition wall, the bottom of the raw material partition wall being closed by the ultrasonic wave transparent substrate, and the ultrasonic vibrator being surrounded by a guide partition wall up to the ultrasonic wave transparent substrate, has good atomization controllability and a good atomization amount, etc., and is useful for semiconductor film production devices, etc., and have found that such an atomization device can solve the above-mentioned conventional problems at once. Furthermore, after obtaining the above findings, the present inventors conducted further studies and completed the present invention.

[0007] That is, the present invention relates to the following inventions. [1] An atomization device comprising an ultrasonic wave transmission liquid provided above an ultrasonic vibrator, a raw material partition wall containing the raw material liquid to be atomized, an ultrasonic wave transmission liquid tank containing the ultrasonic wave transmission liquid, and an ultrasonic vibrator at the bottom of the ultrasonic wave transmission liquid tank for irradiating ultrasonic waves onto the bottom of the raw material partition wall, the bottom of the raw material partition wall being closed by an ultrasonically transparent substrate, and characterized in that the ultrasonic vibrator is surrounded by a guide partition wall up to the ultrasonically transparent substrate. [2] The atomization device according to [1], wherein the guide partition has a substantially cylindrical shape. [3] The atomization device according to [1], wherein the guide partition has a truncated cone shape. [4] The atomization device according to [1], wherein the guide partition is perforated. [5] The atomization device according to [1], wherein the guide partition is configured to be detachable. [6] The atomization device according to [1], wherein the guide partition is made of metal or a high molecular weight polymer. [7] The atomization device according to [1], wherein the raw material for atomization contains a metal. [8] The atomization device according to [1], wherein the ultrasonic wave transmitting liquid is water. [9] The atomization device according to [1], wherein the ultrasonically transparent substrate is a polymer film.

[10] The atomization device according to [1], wherein the raw material partition wall is cylindrical or approximately cylindrical, or polygonal or approximately polygonal.

[11] The atomization device according to [1], wherein the raw material liquid for atomization is a raw material liquid for film formation, and the atomization device is an atomization device for film formation.

[12] A film-forming apparatus comprising at least a film-forming chamber and an atomizing device, wherein the atomizing device is the atomizing device described in

[11] above. [Effects of the Invention]

[0008] The atomization device of the present invention is useful for semiconductor devices and the like, and exhibits a good atomization amount and good atomization controllability. [Brief explanation of the drawings]

[0009] [Figure 1] 1 is a schematic diagram illustrating an example of a film-forming apparatus that can be suitably used in the present invention. [Figure 2] 1 is a diagram schematically illustrating an atomization device preferably used in the present invention. [Figure 3] FIG. 1 is a diagram showing the results of XRD diffraction in Example 1. [Figure 4] FIG. 1 is a diagram showing the results of XRD diffraction in Example 2. [Figure 5] FIG. 10 is a diagram showing an AFM image in Example 2. [Figure 6] FIG. 10 is a diagram showing an SEM image in Example 2. [Figure 7] FIG. 10 is a diagram showing an EDS image in Example 2. [Figure 8] FIG. 10 is a diagram showing the results of XRD diffraction in Example 3. [Figure 9] FIG. 10 is a diagram showing an SEM image in Example 3. [Figure 10] FIG. 2 is a diagram showing the atomization state (atomization state after 30 minutes) of the atomization device of the present invention. [Figure 11] FIG. 2 is a diagram showing the atomization state (atomization state after 60 minutes) of the atomization device of the present invention. [Figure 12] FIG. 10 is a diagram showing the atomization state (atomization state after 30 minutes) of a commercially available atomization device in Comparative Example 3. [Figure 13] FIG. 10 is a diagram showing the atomization state after 60 minutes of a commercially available atomization device in Comparative Example 3. [Figure 14] 1 is a schematic cross-sectional side view of an atomization device preferably used in the present invention. FIG. DETAILED DESCRIPTION OF THE INVENTION

[0010] The atomization device of the present invention is an atomization device in which an ultrasonic transmission liquid is provided above an ultrasonic vibrator, and which is equipped with a raw material partition wall that contains raw material liquid to be atomized, an ultrasonic transmission liquid tank that contains the ultrasonic transmission liquid, and an ultrasonic vibrator at the bottom of the ultrasonic transmission liquid tank that irradiates ultrasonic waves onto the bottom of the raw material partition wall, and the bottom of the raw material partition wall is closed by an ultrasonically transparent substrate, and the ultrasonic vibrator is surrounded by a guide partition wall up to the ultrasonically transparent substrate.

[0011] The ultrasonic vibrator is not particularly limited as long as it is an element capable of generating ultrasonic vibrations and can irradiate ultrasonic waves onto the bottom surface of the raw material partition wall, and may be a known ultrasonic vibrator. The frequency of the ultrasonic vibrator is not particularly limited as long as it does not impede the object of the present invention, but is preferably 2.4 MHz or higher, and more preferably 3.0 MHz or higher. For example, an ultrasonic vibrator may be used, in which electrodes are provided on both sides of a disc-shaped piezoelectric element, and an oscillator is connected to the electrodes to change the oscillation frequency, thereby generating ultrasonic waves having a resonant frequency in the thickness direction and a resonant frequency in the radial direction of the piezoelectric vibrator. Within this preferred range, the particle size of the mist generated by atomization can be further reduced, and the atomization efficiency can be improved.

[0012] The raw material partition wall in the present invention is not particularly limited as long as it can accommodate the raw material to be atomized. In the present invention, it is preferable that the raw material partition wall has no bottom, and that the raw material partition wall and the ultrasonic transmission liquid tank are fitted or screwed together via an ultrasonically transparent substrate, so that the raw material partition wall can accommodate the raw material liquid to be atomized. For example, when the ultrasonically transparent substrate is a polymer film, the polymer film is sandwiched and the bottom of the raw material partition wall is closed by the ultrasonically transparent substrate, so that the raw material partition wall can accommodate the raw material liquid to be atomized. The means for fitting or screwing the raw material partition wall and the ultrasonic transmission liquid tank is not particularly limited as long as it does not impede the objectives of the present invention, and any known means may be used. Examples of the fitting means include a means for providing a recess, protrusion, or concave / convex portion in the raw material partition wall and a corresponding fitting portion in the ultrasonic transmission liquid tank, or a means for providing a recess, protrusion, or concave / convex portion in the ultrasonic transmission liquid tank and a corresponding fitting portion in the raw material partition wall. Examples of the screwing means include a means for providing a male thread portion in the raw material partition wall and a female thread portion in the ultrasonic transmission liquid tank, or a means for providing a male thread portion in the ultrasonic transmission liquid tank and a female thread portion in the raw material partition wall. In the present invention, the raw material partition wall and the ultrasonic transmission liquid tank may be fitted and screwed together using known members. Note that, in order to more effectively use the ultrasonically transparent substrate, it is preferable that the raw material partition wall and the ultrasonic transmission liquid tank have approximately the same cross-sectional shape, and it is also preferable that they have approximately the same cross-sectional area.

[0013] In the present invention, the raw material partition wall is preferably a covered cylindrical body having a lid. The shape of the lid is not particularly limited as long as it can serve as a lid for the raw material partition wall. However, a lid that can seal the space inside the raw material partition wall is preferred because it improves atomization efficiency and mist controllability. The material of the lid is also not particularly limited, and may be the same material as the raw material partition wall or a different material. It may be a known material, an inorganic material, or an organic material. In the present invention, the material of the lid preferably contains glass, quartz, or a fluorine-based resin as a main component, and more preferably contains a fluorine-based resin as a main component. Examples of fluorine-based resins include polytetrafluoroethylene, modified polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymer, and ethylene-tetrafluoroethylene copolymer.

[0014] In the present invention, as described above, it is preferable that the raw material partition wall is a lidded cylindrical body. When the raw material partition wall has a lid, the interior of the raw material partition wall can be sealed, and the atomization raw material can be replenished by utilizing space pressure. More specifically, when the liquid level of the atomization raw material drops due to atomization, the space pressure of the raw material partition wall rises, and the liquid level reaches the tip of the piping. The space of the raw material partition wall and the space in the replenishment container containing the replenishment atomization raw material are connected via the piping, and gas in the space in the raw material partition wall can be extracted into the space in the replenishment container via the piping, and the atomization raw material in the replenishment container can be replenished into the raw material partition wall. Having such a replenishment means is one preferred embodiment of the present invention.

[0015] The atomization raw material is not particularly limited as long as it can be atomized, and may be a known atomization raw material liquid, including a liquid dispersion medium such as a sol. It may be a raw material liquid containing an organic compound, or a raw material liquid containing an inorganic compound. In the present invention, the atomization raw material liquid is preferably a raw material liquid for film formation, and more preferably contains a metal. Examples of the metal include gold (Au), silver (Ag), platinum (Pt), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), palladium (Pd), cobalt (Co), rhodium (Rh), ruthenium (Ru), chromium (Cr), molybdenum (Mo), germanium (Ge), titanium (Ti), tin (Sn), zirconia (Zr), vanadium (V), yttrium (Y), zinc (Zn), magnesium (Mg), scandium (Sc), hafnium ( Examples of suitable metals include one or more metals selected from the group consisting of Hf, antimony (Sb), bismuth (Bi), tantalum (Ta), iridium (Ir), tungsten (W), niobium (Nb), lanthanum (La), cerium (Ce), and aluminum (Al), but preferably one or more metals selected from the group consisting of gallium, germanium, titanium, tin, niobium, vanadium, antimony, bismuth, tantalum, aluminum, and indium. In the present invention, the atomization raw material liquid is preferably a film-forming raw material liquid, and more preferably a mist CVD raw material liquid, because it can exhibit excellent film-forming effects. The atomization raw material liquid may be one type or two or more types. For example, when two or more types of raw material liquids are used, at least one may be a raw material liquid containing an inorganic compound, and the other may be a raw material liquid containing an organic compound.

[0016] The ultrasonic transmission liquid vessel in the present invention is not particularly limited as long as it can accommodate the ultrasonic transmission liquid. The shape of the ultrasonic transmission liquid vessel is also not particularly limited, but in the present invention, it is preferably cylindrical, approximately cylindrical, or polygonal or approximately polygonal, more preferably cylindrical or approximately cylindrical, and most preferably cylindrical. The constituent material of the ultrasonic transmission liquid vessel is also not particularly limited, and may be inorganic or organic. However, in the present invention, the constituent material of the ultrasonic transmission liquid vessel preferably contains glass, quartz, or a fluorine-based resin as a primary component, and more preferably a fluorine-based resin as a primary component. The ultrasonic transmission liquid is not particularly limited as long as it is a liquid capable of transmitting ultrasonic waves, and includes liquid dispersion media such as sols. Examples of the ultrasonic transmission liquid include inorganic solvents and organic solvents. In the present invention, inorganic solvents are preferred, and water is more preferred. More specifically, examples of the water include pure water, ultrapure water, tap water, well water, mineral water, hot spring water, spring water, fresh water, and seawater, and examples of these waters include water that has been treated by, for example, purification, heating, sterilization, filtration, ion exchange, electrolysis, osmotic pressure adjustment, buffering, etc. (e.g., ozonated water, purified water, hot water, ion-exchanged water, saline, phosphate buffer, phosphate buffered saline, etc.) In the present invention, it is preferable to seal the interior of the ultrasonic transmission liquid tank, and by forming a sealed space, atomization efficiency and mist controllability can be improved.

[0017] The ultrasonically transparent substrate is not particularly limited as long as it does not impede the objectives of the present invention, and may be a known ultrasonically transparent substrate. Examples of the ultrasonically transparent substrate include polymer films. Examples of materials constituting the ultrasonically transparent substrate include thermoplastic resins and thermosetting resins, with thermoplastic resins being preferred in the present invention. Examples of the thermoplastic resin include polyolefins and fluororesins, with those containing fluororesins as the main component being preferred. Examples of the polyolefin include polyethylene and polypropylene. Examples of the fluororesin include polytetrafluoroethylene, modified polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, and ethylene-tetrafluoroethylene copolymers. In the present invention, the fluororesin is preferably at least one selected from polytetrafluoroethylene, modified polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, and ethylene-tetrafluoroethylene copolymers. Within such a preferred range, the ultrasonic waves can be transmitted to the atomization material more efficiently, thereby increasing the amount of atomization.

[0018] The material of the guide partition is not particularly limited as long as it does not impede the objectives of the present invention, and examples thereof include metals and polymers. Examples of the polymer include natural resins, thermoplastic resins, and thermosetting resins. The surface of the guide partition may be coated with a metal. Examples of the metal include Al, Cu, Ag, Ti, W, Mo, Fe, Ni, Cr, Zn, Sn, Rh, Pt, and Au. This preferred range allows for more efficient and effective transmission of ultrasonic vibrations. The shape of the guide partition is not particularly limited as long as it does not impede the objectives of the present invention, but according to this embodiment, it is preferably cylindrical or approximately cylindrical, or polygonal or approximately polygonal. Also, a truncated cone shape is preferred, with a truncated cone shape or approximately cylindrical shape being more preferred, and a truncated cone shape being most preferred. Furthermore, it is preferable that the guide partition is not particularly obstructed and is perforated as long as it does not impede the objectives of the present invention. According to such a preferred range, ultrasonic waves irradiated from the ultrasonic vibrator can be transmitted to the ultrasonically transparent substrate more efficiently and effectively. The guide partition is not particularly limited as long as it does not impede the object of the present invention, and may be configured to be detachable or may be installed on the ultrasonic radiation surface, but in the present invention, it is preferable that it is configured to be detachable. According to such a preferred range, the atomization device of the present invention can be more easily cleaned.

[0019] In the present invention, it is preferable that the atomization raw material solution is a film-forming raw material solution, the atomization device is a film-forming atomization device, and the atomization device is used in a film-forming device that includes at least a film-forming chamber and an atomization device. Within such a preferable range, a thin film with better crystallinity can be formed. [Example]

[0020] Example 1 Fig. 1 shows an example of a preferred embodiment of a film production apparatus when the atomization device of the present invention is used as a film production atomization table. The film production apparatus 19 comprises a film-forming sample 20, a sample stage 21, a carrier gas source 22a, a carrier gas source 22b, a flow rate control valve 23a, a flow rate control valve 23b, a film production chamber 27, a heater 28, and an atomization device 30. The atomization device 30 comprises a raw material partition 24, a raw material liquid to be atomized 24a, an ultrasonically transmitting substrate 24b, a stage 24c, an ultrasonic vibrator 26, a guide partition 31, an ultrasonic transmission liquid tank 35, and an ultrasonic transmission liquid 36. Fig. 2 shows an example of a preferred embodiment when the atomization device of the present invention is used as a film production atomization table. The atomization device 30 in FIG. 2 is composed of a flow control valve 23a, a flow control valve 23b, a raw material liquid for atomization 24a, an ultrasonically-transmitting substrate 24b, a base 24c, a guide partition 31, a dilution gas supply pipe 33, a carrier gas supply pipe 34, an ultrasonically-transmitting liquid tank 35, and an ultrasonically-transmitting liquid 36. The sample stage 21 is made of quartz, and the surface on which the film-forming sample 20 is placed is inclined from the horizontal. By making both the film-forming chamber 27 and the sample stage 21 out of quartz, impurities from the device are prevented from being mixed into the thin film formed on the film-forming sample 20. The raw material liquid 24a is contained in the mist generation source 24. The guide partition 31 is in contact with the ultrasonically-transmitting substrate 24b. The sample stage 21 is made of quartz, and the surface on which the film-forming sample 20 is placed is inclined from the horizontal. Both the film deposition chamber 27 and the sample stage 21 are made of quartz, which prevents impurities from the device from being mixed into the thin film formed on the film deposition sample 20. A raw material solution 24a is contained in the mist generation source 24. A guide partition 31 is in contact with an ultrasonically transparent substrate 24b. The atomization device 30 in Figure 14 consists of a raw material partition 24, an ultrasonically transparent substrate 24b, a stage 24c, an ultrasonic vibrator 26, a guide partition 31, and an ultrasonic transmission liquid tank 35. The guide partition 31 is in contact with the ultrasonic transmission liquid tank 35. By using the guide partition 31, the ultrasonic waves emitted from the ultrasonic vibrator 26 are more efficiently transmitted to the raw material partition 24.

[0021] Next, a c-plane sapphire substrate having a square shape with sides of 10 mm and an average thickness of 0.5 mm was placed on sample stage 21 as film deposition sample 20, and heater 28 was operated to raise the temperature inside film deposition chamber 27 to 750°C. Next, flow control valve 23 was opened to supply carrier gas from carrier gas source 22 into film deposition chamber 27. After the atmosphere inside film deposition chamber 27 was thoroughly replaced with carrier gas, the flow rate of the carrier gas was adjusted to 3 L / min. Oxygen gas was used as the carrier gas.

[0022] Next, the ultrasonic vibrator 26 was vibrated at 3.0 MHz, and the vibrations were propagated to the raw material solution 24a through the ultrasonic transmission liquid 36, thereby atomizing the raw material solution 24a and generating raw material fine particles. Iron (III) acetylacetonate was used as the raw material solution. These raw material fine particles were introduced into the film deposition chamber 27 by a carrier gas, where they reacted, forming an α-Fe2O3 crystalline film on the film deposition sample 20 through a CVD reaction on the film deposition surface of the film deposition sample 20. The film thickness was 1.39 μm.

[0023] The obtained crystalline film was measured using an X-ray diffractometer. Figure 3 shows the XRD diffraction results. As is clear from Figure 3, the obtained crystalline film was an α-Fe2O3 crystalline film, and a single crystalline film of α-Fe2O3 with good crystallinity was formed on the c-plane sapphire substrate.

[0024] Example 2 Fig. 1 shows an example of a preferred embodiment of a film production apparatus when the atomization device of the present invention is used as a film production atomization table. The film production apparatus 19 comprises a film-forming sample 20, a sample stage 21, a carrier gas source 22a, a carrier gas source 22b, a flow rate control valve 23a, a flow rate control valve 23b, a film production chamber 27, a heater 28, and an atomization device 30. The atomization device 30 comprises a raw material partition 24, a raw material liquid to be atomized 24a, an ultrasonically transmitting substrate 24b, a stage 24c, an ultrasonic vibrator 26, a guide partition 31, an ultrasonic transmission liquid tank 35, and an ultrasonic transmission liquid 36. Fig. 2 shows another preferred embodiment of a film production apparatus when the atomization device of the present invention is used as a film production atomization table. The atomization device 30 is composed of a raw material partition wall 24, a raw material liquid to be atomized 24a, an ultrasonically-transmitting substrate 24b, a base 24c, an ultrasonic vibrator 26, a guide partition wall 31, an ultrasonically-transmitting liquid tank 35, and an ultrasonically-transmitting liquid 36. The sample stage 21 is made of quartz, and the surface on which the film-forming sample 20 is placed is inclined from the horizontal. By fabricating both the film-forming chamber 27 and the sample stage 21 from quartz, impurities originating from the device are prevented from being mixed into the crystalline film formed on the film-forming sample 20. The raw material liquid 24a is contained in the mist source 24. The guide partition wall 31 is in contact with an ultrasonically-transmitting substrate 38. Figure 14 is a schematic cross-sectional side view of the atomization device used in the present invention. The atomization device 30 in Figure 14 is composed of the raw material partition wall 24, an ultrasonically-transmitting substrate 24b, a base 24c, an ultrasonic vibrator 26, a guide partition wall 31, and an ultrasonically-transmitting liquid tank 35. The guide partition 31 is in contact with the ultrasonic wave transmission liquid tank 35. By using the guide partition 31, the ultrasonic waves emitted from the ultrasonic vibrator 26 are transmitted to the raw material partition 24 more efficiently.

[0025] Next, a 10 mm square Si(111) substrate with a 900 nm average thickness 3C-SiC(111) thin film laminated thereon was placed on sample stage 21 as film-forming sample 20, and heater 28 was operated to raise the temperature in film-forming chamber 27 to 750°C. Next, flow control valve 23 was opened to supply carrier gas from carrier gas source 22 into film-forming chamber 27. After the atmosphere in film-forming chamber 27 was thoroughly replaced with carrier gas, the flow rate of the carrier gas was adjusted to 3 L / min. Oxygen gas was used as the carrier gas.

[0026] Next, ultrasonic vibrator 26 was vibrated at 3.0 MHz, and the vibration was propagated to raw material solution 24a through ultrasonic transmitter 25a, thereby atomizing raw material solution 24a and generating raw material fine particles. These raw material fine particles were introduced into film formation chamber 27 by carrier gas, and reacted in film formation chamber 27, forming a tetragonal GeO2 crystalline film on film formation sample 20 through a CVD reaction on the film formation surface of film formation sample 20. The film thickness was 1.2 μm.

[0027] Film formation was performed in the same manner as in Example 1, except that bis[2-carboxyethylgermanium(IV)] sesquioxide was used as the source solution and a Si(111) substrate with a 3C-SiC(111) thin film layer of 900 nm average thickness was used as the substrate. The resulting GeO2 crystalline film was measured using an X-ray diffractometer. Figure 4 shows the XRD diffraction results. As is clear from Figure 4, the resulting crystalline film was a GeO2 single crystal film with a (111)-oriented tetragonal rutile structure. The 2θ-ω half-width was 68 arcsec, indicating that a GeO2 crystalline film with good crystallinity was formed on the 3C-SiC(111) thin film grown on the Si(111) substrate.

[0028] Furthermore, when the surface of the obtained GeO2 crystal film was observed using an atomic force microscope (AFM), it was found that the surface roughness (RMS) based on JIS B0601 was 0.26 nm, as shown in Figure 5, indicating excellent surface smoothness.

[0029] The surface of the obtained GeO2 crystal film was observed using SEM. Figure 6 shows an SEM image. As is clear from Figure 5, GeO2 crystals with excellent surface smoothness and good crystallinity were formed. Furthermore, when the surface of the obtained crystal film was evaluated using EDS, as shown in Figure 7, a crystal film was formed over the entire surface to a thickness of 100 μm. 2 It was found that the pores were formed over an area of ​​more than 100m.

[0030] Example 3 Film formation was carried out in the same manner as in Example 1, except that a Si (100) substrate was used. The obtained crystalline film was measured using an X-ray diffractometer. Figure 8 shows the XRD diffraction results. As is clear from Figure 8, the obtained crystalline film was a GeO2 single crystal film with a (111)-oriented tetragonal rutile structure. GeO2 crystals with good crystallinity were formed on the Si (100) substrate. The film thickness was 1.5 μm.

[0031] The surface of the obtained crystalline film was observed using SEM. Figure 9 shows an SEM image. As is clear from Figure 9, a GeO2 crystalline film with excellent surface smoothness and good crystallinity was formed. The surface of the obtained crystalline film was also evaluated using EDS, and as shown in Figure 10, a crystalline film was formed over the entire surface to a thickness of 100 μm. 2 It was found that the pores were formed over an area of ​​more than 100m.

[0032] Example 4 A prototype atomization device of the present invention was manufactured and atomization was carried out. Figure 11 shows the atomization state inside the raw material partition of the atomization device after 30 minutes. Figure 12 shows the atomization state inside the raw material partition of the atomization device after 60 minutes. These results show that the atomization device of the present invention is capable of atomization for a long period of time, and that even when atomized for a long period of time, the atomization efficiency and mist controllability are better.

[0033] (Comparative Example 1) An α-Fe2O3 crystal film was formed in the same manner as in Example 2, except that a commercially available atomization device was used instead. The thickness of the α-Fe2O3 crystal film was 0.84 μm. These results show that the atomization device of the present invention, compared to the commercially available atomization device, has a greater atomization amount and improved atomization efficiency, making it possible to generate a good mist that is more suitable for film formation and to increase the growth rate of the crystal film.

[0034] (Comparative Example 2) When a GeO2 crystal film was formed in the same manner as in Example 1, except that the atomization device was replaced with a commercially available atomization device, only fine particles were formed on a portion of the substrate surface. From these results, it can be seen that the atomization device of the present invention can form a better crystal film than the commercially available atomization device.

[0035] (Comparative Example 3) As Comparative Example 3, atomization was performed using a commercially available atomization device, and Fig. 12 shows the atomization state inside the cylindrical body of the atomization device after 30 minutes, and Fig. 13 shows the atomization state inside the cylindrical body of the atomization device after 60 minutes. These results show that the atomization device of the present invention is capable of atomization for a longer period of time than the atomization device of Comparative Example 3, and even when atomized for a long period of time, it has better atomization efficiency, mist controllability, and atomization time, and can supply mist more stably. [Industrial Applicability]

[0036] The atomization device of the present invention is useful for producing mist and is suitably used, for example, in semiconductor devices for film production, etc. Furthermore, the film production device of the present invention can be used in all film production fields and is industrially useful. [Explanation of symbols]

[0037] 19 Film forming equipment 20 Film sample 21 Sample stage 22a Carrier gas source 22b Dilution gas source 23a Flow control valve 23b Flow control valve 24 Raw material bulkhead 24a Raw material liquid for atomization 24b Ultrasonic transparent base material 24c units 26 Ultrasonic vibrator 27 Film forming room 28 Heater 30 Atomization device 31 Guide bulkhead 33 Dilution gas supply pipe 34 Carrier gas supply pipe 35 Ultrasonic transmission fluid tank 36 Ultrasonic transmission fluid 37 Film forming room

Claims

1. A film production apparatus characterized by comprising at least an atomization device having a raw material partition that contains raw material liquid to be atomized, an ultrasonic transmission liquid tank that is provided at the bottom of the raw material partition and that contains ultrasonic transmission liquid, an ultrasonic vibrator that is provided at the bottom of the ultrasonic transmission liquid tank and that irradiates ultrasonic waves onto the bottom of the raw material partition, an ultrasonic transparent substrate that closes the bottom of the raw material partition, and a guide partition that is provided inside the ultrasonic transmission liquid tank and is formed separately from the ultrasonic transmission liquid tank and separates the inside of the area from around the ultrasonic vibrator to the ultrasonic transparent substrate from the outside area, and a film production chamber.

2. 2. The film forming apparatus according to claim 1, wherein the guide partition has a substantially cylindrical shape.

3. 2. The film forming apparatus according to claim 1, wherein the guide partition has a truncated cone shape.

4. 2. The film forming apparatus according to claim 1, wherein the guide partition is perforated.

5. 2. The film forming apparatus according to claim 1, wherein the guide partition is configured to be detachable.

6. 2. The film forming apparatus according to claim 1, wherein the guide partition is made of a metal or a polymer.

7. 2. The film forming apparatus according to claim 1, wherein the atomized raw material contains a metal.

8. 2. The film forming apparatus according to claim 1, wherein the ultrasonic wave transmitting liquid is water.

9. 2. The film-forming apparatus according to claim 1, wherein the ultrasonically transparent substrate is a polymer film.

10. 2. The film forming apparatus according to claim 1, wherein the raw material partition wall has a cylindrical or substantially cylindrical shape, or a polygonal or substantially polygonal cylindrical shape.

11. 2. The film-forming apparatus according to claim 1, wherein the atomization raw material liquid is a film-forming raw material liquid, and the atomization device is a film-forming atomization device.

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