Atomizer and membrane production 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 transducers are known as devices that generate (atomize) fine droplets from liquid. In these ultrasonic atomizers, the ultrasonic transducer is placed at the bottom of a container that stores the liquid to be atomized. When the ultrasonic transducer vibrates, the liquid particles in the liquid vibrate in the direction of ultrasonic propagation, and the vibration energy is concentrated on the liquid surface, forming a liquid column, which then breaks at the tip of the liquid column, scattering the liquid particles and generating mist.

[0003] In recent years, it has been described that a mist generating device 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 facing the liquid, and arranged in a form in which the liquid-facing surface faces the liquid and the insulating resin film made of a paraxylylene-based polymer is in contact with the liquid, has high chemical resistance and is stable against many chemical solutions, thereby reducing the restrictions on the liquid used (Patent Document 1). However, since the adherend surface of these mist generating devices is fixed, it is difficult to clean the space between the ultrasonic transducer and the adherend surface after use, and also, when used for a long time, the liquid level drops, reducing the amount of mist generated and reducing the mist generation efficiency, and since it is necessary to keep the liquid level constant in order to maintain the mist generation efficiency, the amount of solution used increases, which is not environmentally friendly. Also, it has been considered that the atomization device, which is composed of an outer container with an ultrasonic vibrator fixed to the bottom, a transmission liquid contained in the outer container, an inner container attached to the inside of the outer container with a predetermined interval therebetween 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 does not need to be washed every time the liquid is changed (Patent Document 2). However, these atomization devices have a problem that, even if a communication groove is formed so that the side of the inner container and the upper end of the horn-shaped protrusion are connected to each other, air is likely to remain due to insufficient deaeration, and the amount of liquid atomized in the inner container is reduced. It has been described that an atomizing device in which the bottom of a bottomless cylindrical body is blocked by an ultrasonically transparent base material has excellent atomization efficiency and mist controllability (Patent Document 3). However, these atomizing devices have problems such as the ultrasonic waves transmitted to the liquid surface being scattered because they are not uniformly concentrated, and the amount of atomization and the atomization efficiency are still insufficient. In addition, when used for a long time, the liquid level drops, so the amount of atomization decreases and the atomization efficiency deteriorates, and there are also problems such as the need to add the solution many times. 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] JP 2012-011360 A [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 transmission liquid provided above an ultrasonic transducer, a raw material partition wall in which a raw material liquid to be atomized is contained, an ultrasonic transmission liquid tank in which an ultrasonic transmission liquid is contained, and an ultrasonic transducer at the bottom of the ultrasonic transmission liquid tank for irradiating ultrasonic waves to the bottom of the raw material partition wall, the bottom of the raw material partition wall being closed by the ultrasonically transparent substrate, and the ultrasonic transducer being surrounded by a guide partition wall up to the ultrasonically transparent substrate, has good atomization controllability and good atomization amount, and is useful for semiconductor film forming 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 transmission liquid provided on top of an ultrasonic vibrator; a raw material partition wall in which raw material liquid to be atomized is contained; an ultrasonic transmission liquid tank in which ultrasonic transmission liquid is contained; and an ultrasonic vibrator at the bottom of the ultrasonic transmission liquid tank for irradiating ultrasonic waves to the bottom of the raw material partition wall, the bottom of the raw material partition wall being closed by an ultrasonically transparent substrate; and the ultrasonic vibrator being 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 removable. [6] The atomization device according to [1], wherein the guide partition is made of metal or 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 transmission 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 has a cylindrical or approximately cylindrical shape, or a polygonal or approximately polygonal cylindrical shape.

[11] The atomization device according to the above [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, the atomizing device being the atomizing device described in

[11] above. Effect of the Invention

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

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

[0010] The atomization device of the present invention is characterized in that it has an ultrasonic transmission liquid provided on the top of an ultrasonic vibrator, and is equipped with a raw material partition wall in which raw material liquid for atomization is contained, an ultrasonic transmission liquid tank in which ultrasonic transmission liquid is contained, and an ultrasonic vibrator at the bottom of the ultrasonic transmission liquid tank for irradiating ultrasonic waves to the bottom of the raw material partition wall, the bottom of the raw material partition wall being closed by an ultrasonically transparent base material, and the ultrasonic vibrator is surrounded by a guide partition wall up to the ultrasonically transparent base material.

[0011] The ultrasonic vibrator is not particularly limited as long as it is an element capable of generating ultrasonic vibration and can irradiate ultrasonic waves to 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 more, more preferably 3.0 MHz or more. For example, an ultrasonic vibrator in which electrodes are provided on both sides of a disk-shaped piezoelectric element, and when an oscillator is connected to the electrodes to change the oscillation frequency, ultrasonic waves having a resonant frequency in the thickness direction and a resonant frequency in the radial direction of the piezoelectric vibrator are generated. According to such a preferred range, the particle size of the mist generated by atomization can be made smaller, 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 for atomization. In the present invention, it is preferable that the raw material partition wall has no bottom, and the raw material partition wall and the ultrasonic transmission liquid tank are fitted or screwed together via an ultrasonic transmission base material, so that the raw material partition wall can accommodate the raw material liquid for atomization, and the bottom part of the raw material partition wall is closed by the ultrasonic transmission base material. For example, when the ultrasonic transmission base material is a polymer film, the polymer film is sandwiched and the bottom part of the raw material partition wall is closed by the ultrasonic transmission base material, and the closing is configured so that the raw material partition wall can accommodate the raw material liquid for atomization. The fitting or screwing means between the raw material partition wall and the ultrasonic transmission liquid tank is not particularly limited as long as it does not hinder the object of the present invention, and may be a known means. Examples of the fitting means include a means for providing a recess, a protrusion or a concave portion on the raw material partition wall and a corresponding fitting portion on the ultrasonic transmission liquid tank, or a means for providing a recess, a protrusion or a concave portion on the ultrasonic transmission liquid tank and a corresponding fitting portion on the raw material partition wall. Examples of the screwing means include a means for providing a male screw portion on the raw material partition wall and a female screw portion on the ultrasonic transmission liquid tank, or a means for providing a male screw portion on the ultrasonic transmission liquid tank and a female screw portion on 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 a known member. In addition, since the ultrasonically transparent base material can be used more effectively, 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 be used as a lid for the raw material partition wall, but a lid that can seal the space inside the raw material partition wall is preferable because it improves the atomization efficiency and the controllability of the mist. 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, and a fluorine-based resin as a main component, and more preferably contains a fluorine-based resin as a main component. Examples of the fluorine-based resin 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 is a lidded cylinder. When the raw material partition has a lid, the inside of the raw material partition can be sealed, and the atomization raw material can be replenished by utilizing the 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 rises and the liquid level reaches the tip of the pipe, and the space of the raw material partition and the space in the refill container in which the refill atomization raw material is stored are communicated through the pipe, and the gas in the space in the raw material partition can be extracted to the space in the refill container through the pipe, and the atomization raw material in the refill container can be replenished into the raw material partition. Having such a refilling means is also one of the preferred aspects 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 may be 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 the metal include one or more metals selected from Hf, antimony (Sb), bismuth (Bi), tantalum (Ta), iridium (Ir), tungsten (W), niobium (Nb), lanthanum (La), cerium (Ce) and aluminum (Al), and preferably one or more metals selected from gallium, germanium, titanium, tin, niobium, vanadium, antimony, bismuth, tantalum, aluminum and indium. In the present invention, since it can exhibit an excellent film formation effect, the atomization raw material liquid is preferably a film formation raw material liquid, and more preferably a mist CVD raw material liquid. In addition, 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 type may be a raw material liquid containing an inorganic compound, and the other type may be a raw material liquid containing an organic compound.

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

[0017] The ultrasonically transparent substrate is not particularly limited as long as it does not impede the object of the present invention, and may be a known ultrasonically transparent substrate. Examples of the ultrasonically transparent substrate include polymer films. Examples of the constituent materials of the ultrasonically transparent substrate include thermoplastic resins and thermosetting resins, and in the present invention, thermoplastic resins are preferred. Examples of the thermoplastic resin include polyolefins and fluorine-based resins, and among them, it is preferable to include fluorine-based resins as the main component. Examples of the polyolefins include polyethylene and polypropylene. Examples of the fluorine-based resins include polytetrafluoroethylene, modified polytetrafluoroethylene, tetrafluoroethylene-perfluoroalkyl vinyl ether copolymers, and ethylene-tetrafluoroethylene copolymers. In the present invention, it is preferable that the fluorine-based resin is 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 atomized raw material more efficiently, and the amount of atomization can be increased.

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

[0019] In the present invention, it is preferable that the atomization raw material liquid is a film-forming raw material liquid, the atomization device is a film-forming atomization device, and the atomization device is used in a film-forming device having at least a film-forming chamber and an atomization device. According to such a preferable range, a thin film having better crystallinity can be formed. EXAMPLES

[0020] Example 1 Fig. 1 is a diagram showing an example of a preferred embodiment of a film forming apparatus when the atomizing device of the present invention is used as a film forming atomizing table. The film forming apparatus 19 is composed of 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 forming chamber 27, a heater 28, and an atomizing device 30. The atomizing device 30 is composed of a raw material partition 24, a raw material liquid for atomization 24a, an ultrasonic transmission base material 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 is a diagram showing an example of a preferred embodiment when the atomizing device of the present invention is used as a film forming atomizing table. The atomization device 30 in FIG. 2 is composed of a flow rate control valve 23a, a flow rate control valve 23b, a raw material liquid for atomization 24a, an ultrasonic transmission base material 24b, a stand 24c, a guide partition 31, a dilution gas supply pipe 33, a carrier gas supply pipe 34, an ultrasonic transmission liquid tank 35, and an ultrasonic transmission 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 plane. By making both the film-forming chamber 27 and the sample stage 21 from quartz, it is possible to prevent impurities from the device 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 ultrasonic transmission base material 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 plane. Both the film-forming chamber 27 and the sample stage 21 are made of quartz, thereby preventing impurities from the device from being mixed into the thin film formed on the film-forming sample 20. The raw material solution 24a is contained in the mist generating source 24. The guide partition 31 is in contact with the ultrasonically transparent substrate 24b. The atomization device 30 in FIG. 14 is composed of the raw material partition 24, the ultrasonically transparent substrate 24b, the stage 24c, the ultrasonic transducer 26, the guide partition 31, and the ultrasonic transmission liquid tank 35. The guide partition 31 is in contact with the ultrasonic transmission liquid tank 35. The ultrasonic waves generated by the ultrasonic transducer 26 are transmitted to the raw material partition 24 more efficiently by using the guide partition 31.

[0021] Next, a c-plane sapphire substrate with a square shape of 10 mm on a side and an average thickness of 0.5 mm was placed on the sample stage 21 as the film-forming sample 20, and the heater 28 was operated to raise the temperature in the film-forming chamber 27 to 750° C. Next, the flow rate control valve 23 was opened to supply carrier gas from the carrier gas source 22 into the film-forming chamber 27, and after the atmosphere in the film-forming chamber 27 was sufficiently replaced with the 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 vibration was propagated to the raw material solution 24a through the ultrasonic transmission liquid 36, thereby atomizing the raw material solution 24a to generate raw material fine particles. Iron (III) acetylacetonate was used as the raw material solution. The raw material fine particles were introduced into the film deposition chamber 27 by the carrier gas, reacted in the film deposition chamber 27, and formed a crystal film of α-Fe2O3 on the film deposition sample 20 by 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 diffraction device. The XRD diffraction results are shown in Figure 3. As is clear from Figure 3, the obtained crystalline film was an α-Fe2O3 crystalline film, and a single crystal film of α-Fe2O3 with good crystallinity was formed on the c-plane sapphire substrate.

[0024] Example 2 Fig. 1 is a diagram showing an example of a preferred embodiment of a film-forming apparatus when the atomizing device of the present invention is used as a film-forming atomizing stage. The film-forming apparatus 19 is composed of 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-forming chamber 27, a heater 28, and an atomizing device 30. The atomizing device 30 is composed of a raw material partition 24, a raw material liquid for atomization 24a, an ultrasonic transmission base material 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 is a diagram showing an example of another preferred embodiment of a film-forming apparatus when the atomizing device of the present invention is used as a film-forming atomizing stage. The atomizing device 30 is composed of a raw material partition wall 24, a raw material liquid for atomization 24a, an ultrasonic transmission substrate 24b, a stand 24c, an ultrasonic vibrator 26, a guide partition wall 31, an ultrasonic transmission liquid tank 35, and an ultrasonic transmission 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 plane. By making both the film-forming chamber 27 and the sample stage 21 from quartz, it is possible to prevent impurities from the device from being mixed into the crystal film formed on the film-forming sample 20. The raw material solution 24a is contained in the mist generating source 24. The guide partition wall 31 is in contact with the ultrasonic transmission substrate 38. Figure 14 is a schematic diagram showing a cross-sectional view of the atomizing device used in the present invention as seen from the side. The atomizing device 30 in Figure 14 is composed of a raw material partition wall 24, an ultrasonic transmission substrate 24b, a stand 24c, an ultrasonic vibrator 26, a guide partition wall 31, and an ultrasonic transmission 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 generated by the ultrasonic transducer 26 are transmitted to the raw material partition 24 more efficiently.

[0025] Next, a Si(111) substrate with a square shape of 10 mm on each side and a 3C-SiC(111) thin film having an average thickness of 900 nm was placed on the sample stage 21 as the film-forming sample 20, and the heater 28 was operated to raise the temperature in the film-forming chamber 27 to 750° C. Next, the flow rate control valve 23 was opened to supply carrier gas from the carrier gas source 22 into the film-forming chamber 27, and after the atmosphere in the film-forming chamber 27 was sufficiently replaced with the 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, the ultrasonic vibrator 26 was vibrated at 3.0 MHz, and the vibration was propagated to the raw material solution 24a through the ultrasonic transmitter 25a, thereby atomizing the raw material solution 24a to generate raw material fine particles. The raw material fine particles were introduced into the film formation chamber 27 by the carrier gas, reacted in the film formation chamber 27, and formed a tetragonal GeO2 crystal film on the film formation sample 20 by the CVD reaction on the film formation surface of the film formation sample 20. The film thickness was 1.2 μm.

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

[0028] In addition, 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. The surface of the obtained crystal film was also evaluated using EDS, and 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 above-mentioned formation area was formed.

[0030] Example 3 A film was formed 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 diffraction device. Figure 8 shows the XRD diffraction results. As is clear from Figure 8, the obtained crystalline film was a GeO2 single crystal film having 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 crystal film was observed using SEM. Figure 9 shows an SEM image. As is clear from Figure 9, a GeO2 crystal film with excellent surface smoothness and good crystallinity was formed. The surface of the obtained crystal film was also evaluated using EDS, and as shown in Figure 10, the crystal film was found to be 100 μm thick over the entire surface. 2 It was found that the above-mentioned formation area was formed.

[0032] Example 4 A prototype of the atomizing device of the present invention was produced and atomization was carried out. Figure 11 shows the atomization state in the raw material partition of the atomizing device after 30 minutes. Figure 12 shows the atomization state in the raw material partition of the atomizing device after 60 minutes. From these results, it can be seen that the atomizing device of the present invention is capable of atomization for a long time, and that the atomization efficiency and mist controllability are better even when atomizing for a long time.

[0033] Comparative Example 1 Except for using a commercially available atomizer instead of the atomizer, the α-Fe2O3 crystal film was formed in the same manner as in Example 2, and the thickness of the α-Fe2O3 crystal film was 0.84 μm. From these results, the atomizer of the present invention can generate a better mist suitable for film formation and can increase the growth rate of the crystal film because the atomizer of the present invention has a larger amount of atomization and improved atomization efficiency compared to the commercially available atomizer.

[0034] Comparative Example 2 Except for using a commercially available atomizing device, the formation of a GeO2 crystal film was carried out in the same manner as in Example 1, and only fine particles were formed on a portion of the substrate surface. From these results, it can be seen that the atomizing device of the present invention can form a better crystal film than the commercially available atomizing device.

[0035] Comparative Example 3 As Comparative Example 3, atomization was performed using a commercially available atomizing device, and Fig. 12 shows the atomization state inside the cylindrical body of the atomizing device after 30 minutes, and Fig. 13 shows the atomization state inside the cylindrical body of the atomizing device after 60 minutes. From these results, it can be seen 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 atomizing 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 atomizing device of the present invention is useful for producing mist, and is preferably used, for example, in a semiconductor device 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 transducer 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. An atomization device comprising: an ultrasonic transmission liquid provided on the top of an ultrasonic vibrator; a raw material partition wall in which raw material liquid to be atomized is contained; an ultrasonic transmission liquid tank in which ultrasonic transmission liquid is contained; and an ultrasonic vibrator at the bottom of the ultrasonic transmission liquid tank for irradiating ultrasonic waves to the bottom of the raw material partition wall, the bottom of the raw material partition wall being closed by an ultrasonically transparent substrate; and the ultrasonic vibrator being surrounded by a guide partition wall up to the ultrasonically transparent substrate.

2. 2. The atomizing device according to claim 1, wherein the guide partition has a substantially cylindrical shape.

3. 2. The atomizing device according to claim 1, wherein said guide partition has a shape of a truncated cone.

4. 2. The atomizing device according to claim 1, wherein the guide partition is perforated.

5. 2. The atomizing device according to claim 1, wherein the guide partition is configured to be detachable.

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

7. The atomization device according to claim 1 , wherein the raw material for atomization contains a metal.

8. 2. The atomizing device according to claim 1, wherein the ultrasonic transmission liquid is water.

9. 2. The atomizing device according to claim 1, wherein the ultrasonically transparent substrate is a polymer film.

10. 2. The atomization device according to claim 1, wherein the raw material partition has a cylindrical or substantially cylindrical shape, or a polygonal or substantially polygonal cylindrical shape.

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

12. A film forming apparatus comprising at least a film forming chamber and an atomizing device, the atomizing device being the atomizing device according to claim 11.

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