Atomizing device and film-forming device

Abstract

[Problem] To provide an atomizing device that has an excellent atomization volume and excellent atomization controllability. [Solution] This atomizing device, provided with an ultrasonic-wave transmission liquid at the top of an ultrasonic vibrator, is equipped with: a feedstock barrier wall in which a feedstock liquid for atomization is accommodated; an ultrasonic-wave transmission liquid tank in which the ultrasonic-wave transmission liquid is accommodated; and the ultrasonic vibrator which is in a base surface section of the ultrasonic-wave transmission liquid tank and radiates ultrasonic waves toward a base surface section of the feedstock barrier wall. The base surface section of the feedstock barrier wall is closed off by an ultrasonic-wave-permeable base material. The ultrasonic vibrator is surrounded by a guide barrier wall up to the ultrasonic-wave-permeable base material. The atomizing device is useful for producing mists, and can be used to advantage, for instance, in a film-forming semiconductor device or the like.

Description

Atomization equipment and film forming equipment.

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

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

[0003] In recent years, a nebulization device has been described that includes a piezoelectric element made of piezoelectric ceramics and an insulating resin film covering a surface of the piezoelectric element, including a liquid-facing surface that faces the liquid, and that is arranged 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, and that this device has high chemical resistance and is stable against many chemical solutions, thereby reducing the restrictions on the liquid that can be used (Patent Document 1). However, these nebulization devices have problems such as difficulty in cleaning the gap between the ultrasonic vibrator and the surface after use because the surface is fixed, and the liquid level drops over long periods of use, reducing the amount of atomization and reducing atomization efficiency, and the need to maintain a constant liquid level in order to maintain atomization efficiency increases the amount of solution used, making them unfriendly to the environment. In addition, a nebulization device has been proposed that includes an outer container with an ultrasonic vibrator fixed to its bottom, a 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 portion facing the ultrasonic vibrator, and a liquid to be atomized. The number of inner containers required for the nebulization device corresponds to the type of liquid to be atomized, and cleaning is not required each time the liquid is changed (Patent Document 2). However, these nebulization devices have problems, such as insufficient degassing, resulting in air remaining, and reduced atomization of the liquid in the inner container, 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. Patent Document 3 describes an nebulization device in which the bottom of a bottomless cylindrical body is sealed with an ultrasonically transparent substrate, providing excellent atomization efficiency and mist controllability. However, these nebulization devices have problems, such as the ultrasonic waves transmitted to the liquid surface being scattered due to uneven concentration, resulting in insufficient atomization volume and atomization efficiency. Furthermore, when used for a long time, the liquid level drops, which reduces the amount of atomization and the atomization efficiency, and there are also problems such as the need to repeatedly add the solution. Therefore, an atomization device with excellent atomization amount and atomization controllability has been desired.

[0004] Japanese Patent No. 4512850 Japanese Patent Publication No. 2012-011360 Japanese Patent No. 6680433

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

[0006]

[0006] As a result of intensive research to achieve the above object, the present inventors have found that an atomization device comprising an ultrasonic transducer having an ultrasonic transmission liquid disposed above it, a raw material partition wall containing a raw material liquid to be atomized, an ultrasonic transmission liquid tank containing the ultrasonic transmission liquid, and an ultrasonic transducer disposed at the bottom of the ultrasonic 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 the ultrasonic transducer being surrounded by a guide partition wall up to the ultrasonically transparent substrate, has good atomization controllability and a good atomization amount, and is useful in semiconductor film production devices, etc., and has found that such an atomization device can solve all of the above-mentioned conventional problems at once. Furthermore, after obtaining the above-mentioned finding, the present inventors have conducted further research and have 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 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 an ultrasonically transparent substrate, wherein 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 wall has a substantially cylindrical shape. [3] The atomization device according to [1], wherein the guide partition wall has a truncated cone shape. [4] The atomization device according to [1], wherein the guide partition wall is perforated. [5] The atomization device according to [1], wherein the guide partition wall is detachably configured. [6] The atomization device according to [1], wherein the guide partition wall is made of metal or a 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 wall is cylindrical or approximately cylindrical, or polygonal or approximately polygonal cylindrical.

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

[12] A film production device comprising at least a film production chamber and an atomization device, wherein the atomization device is the atomization device according to

[11] .

[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.

[0009] 1 is an example of a schematic configuration diagram of a film forming apparatus preferably used in the present invention. FIG. 2 is a diagram schematically showing an atomization apparatus preferably used in the present invention. FIG. 3 is a diagram showing XRD diffraction results in Example 1. FIG. 4 is a diagram showing XRD diffraction results in Example 2. FIG. 5 is a diagram showing an AFM image in Example 2. FIG. 6 is a diagram showing an SEM image in Example 2. FIG. 7 is a diagram showing an EDS image in Example 2. FIG. 8 is a diagram showing XRD diffraction results in Example 3. FIG. 9 is a diagram showing an SEM image in Example 3. FIG. 10 is a diagram showing an EDS image in Example 3. FIG. 11 is a diagram showing the atomization state (atomization state after 30 minutes) of an atomization apparatus according to the present invention. FIG. 12 is a diagram showing the atomization state (atomization state after 60 minutes) of an atomization apparatus according to the present invention. FIG. 13 is a diagram showing the atomization state (atomization state after 30 minutes) of a commercially available atomization apparatus according to Comparative Example 3. FIG. 14 is a diagram showing the atomization state (atomization state after 60 minutes) of a commercially available atomization apparatus according to Comparative Example 3. FIG. 15 is a diagram schematically showing a cross-sectional side view of an atomization apparatus preferably used in the present 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, 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 such a 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 gallium, germanium, titanium, tin, niobium, vanadium, antimony, bismuth, tantalum, aluminum, and indium. In the present invention, the atomization source liquid is preferably a film-forming source liquid, and more preferably a mist CVD source liquid, because this provides an excellent film-forming effect. The atomization source liquid may be one type or two or more types. For example, when two or more types of source liquids are used, at least one may be a source liquid containing an inorganic compound, and the other may be a source 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 also includes 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 any 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 these preferred ranges, ultrasonic waves can be more efficiently transmitted to the atomization raw material, thereby increasing the atomization amount.

[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.

[0020] Example 1 Figure 1 is a diagram showing 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 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 production chamber 27, a heater 28, and an atomization device 30. The atomization device 30 is composed of a raw material partition 24, a raw material liquid to be atomized 24a, an ultrasonically transparent 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. Figure 2 is a diagram showing 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 source liquid for atomization 24a, an ultrasonically transparent substrate 24b, a base 24c, a guide partition 31, a dilution gas supply pipe 33, a carrier gas supply pipe 34, an ultrasonically transparent liquid tank 35, and an ultrasonically transparent liquid 36. The sample stage 21 is made of quartz, and the surface on which the sample 20 to be deposited is placed is inclined from the horizontal. By making both the film formation chamber 27 and the sample stage 21 out of quartz, impurities originating from the device are prevented from being mixed into the thin film formed on the sample 20 to be deposited. The source liquid 24a is contained in the mist generation source 24. The guide partition 31 is in contact with the ultrasonically transparent substrate 24b. The sample stage 21 is made of quartz, and the surface on which the sample 20 to be deposited is placed is inclined from the horizontal. Both the film deposition 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 deposition sample 20. The raw material solution 24a is contained in the mist generation source 24. The guide partition 31 is in contact with the ultrasonically transparent substrate 24b. The atomization device 30 in Figure 14 consists of the raw material partition 24, the ultrasonically transparent substrate 24b, the stage 24c, the ultrasonic vibrator 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 emitted from the ultrasonic vibrator 26 are transmitted more efficiently to the raw material partition 24 by using the guide partition 31.

[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 the sample stage 21 as the film deposition sample 20, and the heater 28 was operated to raise the temperature inside the film deposition 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 deposition chamber 27. After the atmosphere inside the film deposition 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 and generating 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 a carrier gas, reacted in the film deposition chamber 27, and formed α-Fe on the film deposition sample 20 by a CVD reaction on the film deposition surface of the film deposition sample 20. ２ O ３ A crystalline film having a thickness of 1.39 μm was formed.

[0023] The obtained crystalline film was measured using an X-ray diffractometer. The XRD diffraction results are shown in FIG. 3. As is clear from FIG. 3, the obtained crystalline film is α-Fe. ２ O ３ It is a crystalline film of α-Fe with good crystallinity on a c-plane sapphire substrate. ２ O ３ A single crystal film of SiO2 was formed.

[0024] Example 2 Figure 1 is a diagram showing 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 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 production chamber 27, a heater 28, and an atomization device 30. The atomization device 30 is composed of a raw material partition 24, a raw material liquid to be atomized 24a, an ultrasonically transparent 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. Figure 2 is a diagram showing 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 transparent substrate 24b, a base 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. 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 solution 24a is contained in the mist generating source 24. The guide partition wall 31 is in contact with the ultrasonically transparent 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, the ultrasonically transparent substrate 24b, a base 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 emitted from the ultrasonic vibrator 26 are transmitted to the raw material partition 24 more efficiently.

[0025] Next, as the film formation sample 20, a 10 mm square Si(111) substrate on which a 900 nm average thickness 3C-SiC(111) thin film was laminated was placed on the sample stage 21, and the heater 28 was operated to raise the temperature inside the film formation 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 formation chamber 27. After the atmosphere inside the film formation 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. These 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 tetragonal GeO on the film formation sample 20 by a CVD reaction on the film formation surface of the film formation sample 20. ２ A crystal film having a thickness of 1.2 μm was formed.

[0027] Film formation was carried out in the same manner as in Example 1, except that bis[2-carboxyethylgermanium(IV)]sesquioxide was used as the raw material solution 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. ２ The crystalline film was measured using an X-ray diffractometer. The XRD diffraction results are shown in Figure 4. As is clear from Figure 4, the obtained crystalline film is GeO having a tetragonal rutile structure with a (111) orientation. ２ The half-width of 2θ-ω was 68 arcsec, and GeO with good crystallinity was grown on a 3C-SiC(111) thin film grown on a Si(111) substrate. ２ A crystalline film was formed.

[0028] The obtained GeO ２ When the surface of the 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 FIG. 5, indicating excellent surface smoothness.

[0029] The obtained GeO ２ The surface of the crystalline film was observed using an SEM. The SEM image is shown in Figure 6. As is clear from Figure 5, the GeO film has excellent surface smoothness and good crystallinity. ２ The surface of the obtained crystalline film was evaluated using EDS, and as shown in FIG. 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 as the substrate. 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 GeO having a (111)-oriented tetragonal rutile structure. ２ The film was a single crystal. GeO with good crystallinity on a Si(100) substrate. ２ Crystals were formed. The film thickness was 1.5 μm.

[0031] The surface of the obtained crystalline film was observed using an SEM. The SEM image is shown in Figure 9. As is clear from Figure 9, the GeO film had excellent surface smoothness and good crystallinity. ２ The surface of the obtained crystalline film was evaluated using EDS, and as shown in FIG. 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. From these results, it can be seen that the atomization device of the present invention is capable of atomization for a long period of time, and that even when atomization is carried out for a long period of time, the atomization efficiency and mist controllability are better.

[0033] Comparative Example 1: α-Fe was prepared in the same manner as in Example 2, except that the atomizing device was changed to a commercially available atomizing device. ２ O ３ When a crystalline film was formed, α-Fe ２ O ３ The thickness of the crystal film was 0.84 μm. These results show that the atomization device of the present invention has a larger atomization amount and improved atomization efficiency than commercially available atomization devices, 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: GeO was prepared in the same manner as in Example 1, except that the atomizer was replaced with a commercially available atomizer.２ When a crystalline film was formed, 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 crystalline film than commercially available atomization devices.

[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. Fig. 13 shows the atomization state inside the cylindrical body of the atomization 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 has better atomization efficiency, mist controllability, and atomization time even when atomized for a long period of time, and can supply mist more stably.

[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.

[0037] 19 Film-forming apparatus 20 Film-forming sample 21 Sample stage 22a Carrier gas source 22b Dilution gas source 23a Flow rate control valve 23b Flow rate control valve 24 Raw material partition 24a Raw material liquid for atomization 24b Ultrasonic transmitting substrate 24c Stand 26 Ultrasonic vibrator 27 Film-forming chamber 28 Heater 30 Atomization device 31 Guide partition 33 Dilution gas supply pipe 34 Carrier gas supply pipe 35 Ultrasonic transmitting liquid tank 36 Ultrasonic transmitting liquid 37 Film-forming chamber

Claims

1. An atomization device comprising: an ultrasonic transmission liquid provided above an ultrasonic vibrator; a raw material partition 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, the bottom of the raw material partition being closed by an ultrasonically transparent base material; and the ultrasonic vibrator being surrounded by a guide partition up to the ultrasonically transparent base material.

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

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

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

5. The atomizing device according to claim 1, wherein the guide partition is constructed so as to be detachable.

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

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

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

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

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

11. 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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