JP6906220B2 - Processing method - Google Patents

Description

The present invention relates to a treatment method useful for manufacturing semiconductor devices, electronic devices, and the like, and more specifically, to a method of treating an object to be treated by reacting a mist or droplets containing a raw material solution on a substrate. ..

A technique is known in which a liquid material is used to perform processing such as etching, cleaning, surface modification, and film formation on a substrate or a material to be treated such as a semiconductor film or an insulating film, and for example, a spray method or the like is used. Treatment methods such as etching treatment and film formation treatment using a coating method or the like are generally known. Among them, a method of performing etching treatment, surface modification treatment, film formation treatment, etc. on an object to be treated by using an atomized liquid raw material (mist) has been studied, and in particular, a mist CVD method is used. A method of performing a film forming process or the like has been studied (Patent Documents 1 to 5).

Regarding the mist CVD method, Patent Document 1 describes a tube furnace type mist CVD apparatus. Patent Document 2 describes a fine channel type mist CVD apparatus. Patent Document 3 describes a linear source type mist CVD apparatus. Further, Patent Document 4 describes a mist CVD apparatus which is a rotating stage in which a substrate is installed above a mist generator and a susceptor is provided on a hot plate.

By the way, the silicon oxide film is widely used as an insulating film for a gate insulating film of a MOS transistor and the like, and plays an important role in the electronic device industry. However, when such a silicon oxide film is formed by using a conventional mist CVD apparatus such as a fine channel type, the substrate size depends on the size of the mold, and the shape other than the flat plate is formed. There was a problem that the membrane was difficult. Further, in _{the film formation of a SiO 2} thin film or the like, the mist CVD method has a problem that the film formation rate is low. Other methods have the same problem, and a film forming method by the mist CVD method, which can obtain a good quality film regardless of the type of the substrate and has an excellent film forming rate, has been desired.

Patent No. 5397794 Japanese Unexamined Patent Publication No. 2005-307238 Japanese Unexamined Patent Publication No. 2012-46772 Japanese Unexamined Patent Publication No. 2014-63973

An object of the present invention is to provide a treatment method and a treatment apparatus capable of efficiently treating a substrate even in a treatment using mist.

As a result of diligent studies to achieve the above object, the present inventors adjusted the nozzle angle by using the mist deposition method, and set the nozzle angle within the range of 1 ° to 30 ° with respect to the vertically downward direction. It was found that the substrate can be processed efficiently when the film formation is performed, and in particular, it is found that the film formation process can be efficiently performed at a high film formation rate. .. Further, they have found that such a processing method and a processing apparatus can solve the above-mentioned conventional problems at once.
In addition, after obtaining the above findings, the present inventors have further studied and completed the present invention.

That is, the present invention relates to the following invention.
[1] A treatment method in which a raw material solution is atomized or dropletized, the obtained mist or droplet is conveyed to a substrate by a carrier gas, and the mist or droplet discharged from the nozzle is reacted on the substrate. Therefore, the processing method is characterized in that the nozzle angle is in the range of 1 ° to 30 ° with respect to the vertical downward direction.
[2] The processing method according to the above [1], wherein the nozzle angle is in the range of 16 ° to 28 °.
[3] The treatment method according to the above [1] or [2], wherein the atomization or droplet formation is performed using ultrasonic vibration.
[4] Any of the above [1] to [3], wherein the raw material solution contains an etching agent, a surface modifier or a film forming raw material, and the treatment is an etching treatment, a surface modification treatment or a film forming treatment, respectively. The processing method described in Crab.
[5] The treatment method according to any one of [1] to [4], wherein the raw material solution contains a film-forming raw material and the treatment is a film-forming treatment.
[6] The treatment method according to any one of [1] to [5], wherein the reaction is carried out under atmospheric pressure.
[7] The treatment method according to any one of the above [1] to [6], wherein the reaction is a thermal reaction.
[8] The treatment method according to the above [7], wherein the thermal reaction is carried out at a temperature of 200 ° C. or lower.
[9] An atomizing / droplet atomizing section for atomizing or dropletizing a raw material solution, a transport section for transporting the obtained mist or droplet to a substrate with a carrier gas, the mist or the droplet discharged from a nozzle. A processing device including a reaction unit for reacting the above-mentioned substrate, wherein the nozzle angle is in the range of 1 ° to 30 ° with respect to the vertically downward direction.
[10] The processing apparatus according to the above [9], wherein the nozzle angle is in the range of 16 ° to 28 °.
[11] The processing apparatus according to the above [9] or [10], wherein the atomizing / droplet atomizing portion is provided with an ultrasonic vibrator, and the atomizing or droplet forming is performed by using ultrasonic vibration. ..
[12] The processing apparatus according to any one of the above [9] to [11], which is an etching processing apparatus, a surface modification processing apparatus, or a film forming processing apparatus.
[13] The processing apparatus according to any one of the above [9] to [12], which is a film forming processing apparatus.
[14] The processing device according to any one of [9] to [13] above, which is not provided with a vacuum device or a decompression device.
[15] The processing apparatus according to any one of [9] to [14] above, wherein the reaction unit is provided with a heating means.

According to the treatment method of the present invention, the substrate can be treated efficiently in an industrially advantageous manner.

It is a schematic block diagram of the film forming apparatus used in an Example. It is a figure explaining the nozzle angle in the reaction part as one aspect of this invention. It is a figure which shows the relationship between the nozzle angle and the film thickness in an Example.

In the treatment method of the present invention, the raw material solution is atomized or dropleted (atomization / droplet atomization step), and the obtained mist or droplet is conveyed to the substrate by carrier gas (transport step) and discharged from the nozzle. It is a treatment method for reacting the mist or the droplets on the substrate (reaction step), and is characterized in that the nozzle angle is in the range of 1 ° to 30 ° with respect to the vertical downward direction.

(Raw material solution)
The raw material solution contains a treatment agent for treating an object to be treated, and is not particularly limited as long as it can be atomized or dropletized. The treatment agent may be in a liquid state, a solid state, or a gaseous state. It may be in the form of a gel or in the form of a sol. Further, the raw material solution may contain an inorganic material or an organic material. The treatment agent is not particularly limited as long as it can treat the substrate, and may be a known one. Examples of the treatment agent include an etching agent, a surface modifier, and a film-forming raw material. In the present invention, the treatment agent is preferably a film-forming raw material.

The etching agent is not particularly limited and may be a known etching agent as long as the object of the present invention is not impaired. Examples of the etching agent include known acids and alkalis. Examples of the acid include phosphoric acid, hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid, acetic acid, carbonic acid, formic acid, benzoic acid, chloric acid, hypochlorous acid, sulfite, hyposulfite, nitrite, hyponitrite, and sulphate. Examples thereof include protonic acids such as phosphoric acid and hypophosphorous acid, or mixtures thereof. Examples of the alkali include sodium hydroxide, potassium hydroxide, calcium hydroxide, or a mixture thereof. Other etching agents that have been used for etching metals such as gold, silver, copper, palladium, and platinum (eg, ferric chloride-based etching agents, cyanate / oxygen-based etching agents, ferrocyanic acid). Examples thereof include a salt / ferricyanate-based etching agent, a thiourea-based etching agent, and a potassium iodide / iodine-based etching agent (KI / I2; “triiodide”) or a combination thereof). In the present invention, the etching agent may be used alone or in combination of two or more in the raw material solution. The content of the etching agent in the raw material solution is not particularly limited, but is preferably 0.001% by weight to 80% by weight, and more preferably 0.01% by weight to 80% by weight.

The surface modifier is not particularly limited and may be a known one as long as the object of the present invention is not impaired. Examples of the surface modifier include anionic / cationic surfactants, nonionic surfactants, amphoteric surfactants, polymer surfactants, pigment dispersants, alcohols, fatty acids, amines, and amides. , Iimides, metal soap, fatty acid oligomer compounds, silane coupling agents, titanate coupling agents, aluminate coupling agents, phosphoric acid-based coupling agents, carboxylic acid-based coupling agents, fluorosurfactants, boron-based surfactants Activators and the like can be mentioned. The raw material solution may contain the surface modifier alone or in combination of two or more. The content of the surface modifier in the raw material solution is not particularly limited, but is preferably 0.001% by weight to 80% by weight, and more preferably 0.01% by weight to 80% by weight.

The film-forming raw material may be a known film-forming raw material, and may be an inorganic material or an organic material as long as the object of the present invention is not impaired. In the present invention, the film-forming raw material preferably contains a metal or a metal compound, and gallium, iron, indium, aluminum, vanadium, titanium, chromium, rhodium, nickel, cobalt, zinc, magnesium, calcium, yttrium, and strontium. It is more preferable to contain one or more metals selected from, barium and silicon, and most preferably a silicon-containing compound. The silicon-containing compound is not particularly limited as long as it is a compound containing at least one silicon. Examples of the silicon-containing compound include silane, siloxane, silazane, polysilazane and the like. Examples of the silane include monosilane (SiH ₄ ) and alkoxysilane. Examples of the alkoxysilane include tetraethoxysilane (TEOS), tetramethoxysilane, tetrapropoxysilane, tetrabutoxysilane, tetraamyloxysilane, tetraoctyloxysilane, tetranonyloxysilane, dimethoxydiethoxysilane, and dimethoxydiiso. Examples thereof include propoxysilane, diethoxydiisopropoxysilane, diethoxydibutoxysilane, diethoxyditrityloxysilane, and mixtures thereof. Examples of the siloxane include hexamethyldisiloxane, 1,3-dibutyltetramethyldisiloxane, 1,3-diphenyltetramethyldisiloxane, 1,3-divinyltetramethyldisiloxane, hexaethyldisiloxane and 3-glycid. Examples thereof include xipropylpentamethyldisiloxane. Examples of the silicate include hexamethyldisilazane and hexaethyldisilazane. Further, in the present invention, it is also preferable that the film-forming raw material contains the metal in the form of a complex or a salt. Examples of the form of the complex include an organic complex and the like, and more specific examples thereof include an acetylacetonate complex, a carbonyl complex, an ammine complex, a hydride complex, a quinolinol complex and the like. Examples of the form of the salt include halides and the like, and more specifically, for example, metal chloride salt, metal bromide salt, metal iodide salt and the like. The content of the film-forming raw material in the raw material solution is not particularly limited, but is preferably 0.001% by weight to 80% by weight, and more preferably 0.01% by weight to 80% by weight.

In the present invention, it is preferable that the raw material solution contains an etching agent, a surface modifier or a film forming raw material, and the treatments are an etching treatment, a surface modification treatment or a film forming treatment, respectively. Contains a film-forming raw material, and it is more preferable that the treatment is a film-forming treatment.

The raw material solution may further contain a solvent. The solvent is not particularly limited, and may be an inorganic solvent such as water, an organic solvent, or a mixed solvent of an inorganic solvent and an organic solvent. In the present invention, the solvent preferably contains an organic solvent, and more preferably an organic solvent. Examples of the organic solvent include ester solvents (eg, ethyl acetate, propyl acetate, butyl acetate, ethyl propionate, propyl propionate, butyl propionate, etc.), ether solvents (eg, diethyl ether, tert-butyl methyl ether, etc.). Diglime (eg, diethylene glycol dimethyl ether, diethylene glycol dibutyl ether, diethylene glycol diethyl ether), 1,2-dimethoxyethane, tetrahydrofuran, etc.), amide solvent (eg, N, N-dimethylformamide, N, N-dimethylacetamide, N-methylpyrrolidone) , 1,3-dimethyl-2-imidazolidinone, etc.), ketone solvent (eg, methylisobutylketone, methylethylketone, cyclohexanone, cyclopentanone, etc.), nitrile solvent (eg, acetonitrile, propionitrile, etc.), alcohol solvent (eg, acetonitrile, propionitrile, etc.) For example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, etc., halogenated solvents (eg, methylene chloride, chloroform, etc.), aromatic solvents (eg, toluene, xylene, chlorobenzene, nitrobenzene, etc.) Etc.) and so on.

(Atomization / droplet formation process)
The atomizing means or the droplet forming means is not particularly limited as long as the raw material solution can be atomized or dropletized, and may be a known means. In the present invention, atomizing means or droplet forming means using ultrasonic vibration is preferable. The mist or droplet obtained by using ultrasonic vibration is preferable because it has a zero initial velocity and floats in the air. For example, instead of spraying it like a spray, it floats in space and is transported as a gas. Since it is a mist that can be used, there is no damage due to collision energy, and it is easy to control the flow path direction of the mist, which is very suitable. The size of the mist droplets is not particularly limited and may be about several mm, but is preferably 50 μm or less, and more preferably 100 nm to 10 μm.

(Transport process)
In the transfer step, the mist or the droplet is transferred to the substrate by using a carrier gas and, if desired, a supply pipe or the like.
The carrier gas is not particularly limited as long as the object of the present invention is not impaired, and for example, an inert gas such as oxygen, ozone, nitrogen or argon, or a reducing gas such as hydrogen gas or forming gas is a suitable example. Can be mentioned. Further, the type of the carrier gas may be one type, but may be two or more types, and a diluted gas having a reduced flow rate (for example, a 10-fold diluted gas) or the like is further used as the second carrier gas. May be good. Further, the carrier gas may be supplied not only at one location but also at two or more locations. The flow rate of the carrier gas is not particularly limited, but is preferably 0.01 to 20 L / min, and more preferably 1 to 10 L / min. In the case of a diluting gas, the flow rate of the diluting gas is preferably 0.001 to 20 L / min, more preferably 0.1 to 10 L / min.

(Hypokeimenon)
The substrate is not particularly limited as long as it can support the object to be treated. The material of the substrate is not particularly limited as long as it does not impair the object of the present invention, and may be a known substrate, an organic compound, or an inorganic compound. It may be a porous structure. The shape of the substrate may be any shape and is effective for any shape, for example, plate-like, fibrous, rod-like, columnar, prismatic, such as a flat plate or a disk. Cylindrical, spiral, spherical, ring-shaped and the like can be mentioned, but in the present invention, a substrate is preferable. The thickness of the substrate is not particularly limited in the present invention, but is preferably 10 μm to 100 mm, more preferably 100 μm to 10 mm.

The substrate is not particularly limited as long as it has a plate shape and can be processed by reacting the mist or the droplets. The material of the substrate is not particularly limited as long as it does not interfere with the object of the present invention, and may be a known material. It may be an insulator substrate, a semiconductor substrate, a metal substrate, or a conductive substrate. Further, in the present invention, a substrate in which at least one of a metal film, a semiconductor film, a conductive film and an insulating film is formed on a part or all of the substrate is also suitable as the substrate. Can be used. As the constituent metal of the metal film, for example, one selected from gallium, iron, indium, aluminum, vanadium, titanium, chromium, rhodium, nickel, cobalt, zinc, magnesium, calcium, silicon, yttrium, strontium and barium, or one of them. Two or more kinds of metals and the like can be mentioned. Examples of the constituent materials of the semiconductor film include elemental substances such as silicon and germanium, compounds having elements of groups 3 to 5 and groups 13 to 15 of the periodic table, metal oxides, and metal sulfides. , Metal selenium, metal nitride, perovskite and the like. Examples of the constituent material of the conductive film include tin-doped indium oxide (ITO), fluorine-doped indium oxide (FTO), zinc oxide (ZnO), aluminum-doped zinc oxide (AZO), and gallium-doped zinc oxide (GZO). , Tin oxide (SnO ₂ ), indium oxide (In ₂ O ₃ ), tungsten oxide (WO ₃ ) and the like. Examples of the constituent materials of the insulating film include aluminum oxide (Al ₂ O ₃ ), titanium oxide (TiO ₂ ), silicon oxide (SiO ₂ ), silicon nitride (Si ₃ N ₄ ), and silicon oxynitride (Si _4). Examples thereof include O ₅ N ₃ ), and an insulating film made of an insulating oxide is preferable, and a titania film is more preferable.

The means for forming the metal film, the semiconductor film, the conductive film and the insulating film is not particularly limited and may be a known means. Examples of such forming means include a mist CVD method, a sputtering method, a CVD method (vapor deposition method), an SPD method (spray thermal decomposition deposition method), a vapor deposition method, an ALD (atomic layer deposition) method, and a coating method ( For example, dipping, dripping, doctor blade, inkjet, spin coating, brush coating, spray coating, roll coater, air knife coating, curtain coating, wire bar coating, gravure coating, inkjet coating, etc.).

In the present invention, it is also preferable that a concavo-convex portion composed of a concave portion or a convex portion is formed on the substrate directly or via another layer. The concavo-convex portion is not particularly limited as long as it is composed of a convex portion or a concave portion, and may be a concavo-convex portion composed of a convex portion, a concavo-convex portion composed of a concave portion, or a convex portion and a concave portion. It may be an uneven portion. Further, the uneven portion may be formed from a regular convex portion or a concave portion, or may be formed from an irregular convex portion or a concave portion. In the present invention, it is preferable that the uneven portion is formed periodically, and it is more preferable that the uneven portion is periodically and regularly patterned. The shape of the uneven portion is not particularly limited, and examples thereof include a striped shape, a dot shape, a mesh shape, and a random shape. In the present invention, the striped shape or the dot shape is preferable. When forming the uneven portion in a dot shape, for example, a triangle, a quadrangle (for example, a square, a rectangle, or a trapezoid) is periodically and regularly arranged at a grid position such as a square grid, an oblique grid, a triangular grid, or a hexagonal grid. Etc.), polygonal shapes such as pentagons and hexagons, and concavo-convex parts such as circles and ellipses can be arranged. The cross-sectional shape of the concave or convex portion of the uneven portion is not particularly limited, and is, for example, U-shaped, U-shaped, inverted U-shaped, corrugated, or triangular, quadrangular (for example, square, rectangular, trapezoidal, etc.). ), Polygons such as pentagons and hexagons, etc.

When the raw material solution contains an etching agent and the treatment is an etching treatment, the constituent material of the substrate is preferably a solid material such as a semiconductor material, an insulator material, or a metal material. Examples of the semiconductor material include silicon (single crystal silicon, polycrystalline silicon, amorphous silicon, etc.), germanium, silicon germanium, silicon carbide (SiC), gallium arsenide, gallium aluminum arsenide, indium phosphide, indium antimony, gallium nitride, and the like. Examples include aluminum nitride and gallium oxide. Examples of the insulator material include metal oxides such as zirconium oxide, hafnium oxide, tantalum oxide, aluminum oxide, titanium oxide and chromium oxide, silicates thereof, silicon oxides such as silicon dioxide and quartz, and silicon nitride. Examples include sapphire. Examples of the metal material include gold (Au), silver (Ag), platinum (Pt), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), palladium (Pd), and cobalt (Pd). Examples thereof include one or more metals selected from Co), rhodium (Rh), ruthenium (Ru), chromium (Cr), molybdenum (Mo), tungsten (W) and aluminum (Al).

When the raw material solution contains a surface modifier and the treatment is a surface modification treatment, the substrate constituent material is preferably, for example, silicon rubber, fluororubber, natural rubber, neoprene rubber, chloroprene. Rubbers such as rubber, urethane rubber, acrylic rubber, various polyethylene resins, polypropylene resins, modified polypropylene resins, polymethylpentene resins, polyester resins, polycarbonate resins, epoxy resins, phenol resins, cyanate resins, urea resins, guanamine resins, etc. Polymer materials, aluminum, magnesium, stainless steel, nickel, chromium, tungsten, gold, copper, iron, silver, zinc, tin, lead and other metal materials, titanium oxide, zirconium oxide, zinc oxide, indium oxide, tin oxide, silica , Rubber, calcium carbonate, lime, zeolite, solder, glass, ceramic materials and the like.

When the raw material solution contains a film-forming raw material and the treatment is a film-forming treatment, the constituent material of the substrate is preferably, for example, an inorganic material such as quartz, glass, sapphire, or titania, polyethylene terephthalate, or the like. Polyethylene naphthalate, polyether sulfone, polyimide, nylon, polystyrene, polyvinyl alcohol, ethylene vinyl alcohol copolymer, fluororesin, vinyl chloride, polyolefins such as polyethylene, cellulose, polyvinylidene chloride, aramid, polyphenylene sulfide, polyurethane, polycarbonate , Organic materials such as polyarylate, polynorbornene, epoxy resin, paper materials such as paper and synthetic paper, composite materials coated or laminated with layers that impart insulation to metals such as stainless steel, titanium and aluminum. ..

(Reaction process)
In the reaction step, the mist or the droplets discharged from the nozzle are reacted on the substrate. Here, the nozzle angle is in the range of 1 ° to 30 ° with respect to the vertical downward direction, but in the present invention, the film formation rate is further improved, so that the nozzle angle is in the range of 2 ° to 29 °. It is preferably in the range of 10 ° to 29 °, more preferably in the range of 16 ° to 28 °, and most preferably in the range of 16 ° to 28 °. Further, in the present invention, the nozzle angle is preferably in the range of 20 ° to 27 °, preferably in the range of 20 ° to 25 °, from the viewpoint of further significantly improving the film formation rate. Is more preferable. The nozzle angle is an angle formed by a vertically downward direction and a flow direction of the mist or droplets flowing together with the carrier gas toward the substrate in the nozzle. FIG. 2 shows an example of the nozzle angle. FIG. 2 shows an aspect of a reaction unit in the reaction apparatus of the present invention. The reaction section of FIG. 2 includes a nozzle 7, a hot plate 8, a substrate 10, a stage 11, and a support column 12. The support column 12 stands in the vertically downward direction, and the angle formed by the mist or the droplet flowing in the nozzle 7 together with the carrier gas is the nozzle angle. In FIG. 2, the nozzle angle is indicated by θ.

The shape of the nozzle is not particularly limited, but it is preferable that the shape is such that directivity can be given to the flow of the mist or the droplet and the mist or the droplet can be uniformly conveyed to the substrate. .. For example, a linear source type nozzle and the like can be mentioned.

The reaction may be a physical reaction or a chemical reaction as long as the mist or droplets react on the substrate. Although it may be a reaction by drying, a thermal reaction by heat is preferable, and the thermal reaction may be any reaction as long as the mist or droplets react with heat, and the reaction conditions and the like are particularly limited as long as the object of the present invention is not impaired. Not done. In the present invention, the thermal reaction is usually carried out at 650 ° C. or lower, but in the present invention, 200 ° C. or lower is preferable, and 75 ° C. or lower is more preferable. In the present invention, the substrate can be efficiently treated even at such a low temperature. The lower limit is not particularly limited as long as the object of the present invention is not impaired, but 60 ° C. or higher is preferable. Further, the reaction may be carried out in any of a vacuum, a non-oxygen atmosphere, a reducing gas atmosphere and an oxygen atmosphere as long as the object of the present invention is not impaired, but the reaction may be carried out in a non-oxygen atmosphere or oxygen. It is preferably performed in an atmosphere. Further, it may be carried out under any conditions of atmospheric pressure, pressurization and depressurization, but in the present invention, it is preferably carried out under atmospheric pressure. When the process is a film forming process, the film thickness of the film to be formed can be set by adjusting the film forming time.

By treating as described above, the substrate can be treated efficiently in an industrially advantageous manner.

In the present invention, each of the above steps is discharged from an atomization / droplet atomization unit that atomizes or droplets the raw material solution, a transport unit that transports the obtained mist or droplets to the substrate with a carrier gas, and a nozzle. Using a processing device including a reaction unit for reacting the mist or the droplets on the substrate, the nozzle angle of which is in the range of 1 ° to 30 ° with respect to the vertical downward direction. It is preferable to do so. Hereinafter, the processing apparatus of the present invention will be specifically described with reference to an example in which a film forming process is performed using a film forming material.

Hereinafter, examples of the present invention will be described, but the present invention is not limited thereto.

(Example 1)
1. 1. Processing apparatus The film forming apparatus 1 used in this embodiment will be described with reference to FIG. The film forming apparatus 1 includes a carrier gas supply source 2a for supplying a carrier gas, a flow control valve 3a for adjusting the flow rate of the carrier gas sent out from the carrier gas supply source 2a, and a carrier for supplying the carrier gas (diluted). A gas (diluted) supply source 2b, a flow control valve 3b for adjusting the flow rate of the carrier gas (diluted) sent out from the carrier gas (diluted) supply source 2b, and a mist generation source 4 containing the raw material liquid 4a. , A container 5 in which water 5a is placed, an ultrasonic transducer 6 attached to the bottom surface of the container 5, a hot plate 8, a substrate 10 mounted on the hot plate 8, and a mist source 4 to a nozzle 7 It is provided with a supply pipe 9 for connecting the above and a nozzle 7 for connecting the supply pipe 9 and the vicinity of the substrate 10. The nozzle angle of the nozzle 7 was set to 20 °.

2. Preparation of raw material solution A polysilazane solution diluted by mixing polysilazane with butyl acetate was prepared, and a solution was prepared by adding 6% by volume of hydrogen peroxide solution, which was used as a raw material solution.

3. 3. Preparation for film formation 2. The raw material solution 4a obtained in 1 above was housed in the mist source 4. Next, as the substrate 10, a glass substrate was placed on the hot plate 8 and the hot plate 8 was operated to raise the temperature of the substrate 10 to 75 ° C. Next, the flow rate control valves 3a and 3b are opened to reduce the flow rate of the carrier gas supplied from the carrier gas supply source 2a to 3.0 L / min, and the carrier gas (dilution) supplied from the carrier gas (dilution) supply source 2b. ) Was adjusted to 2.0 L / min. Nitrogen was used as the carrier gas.

4. Film formation treatment Next, the ultrasonic vibrator 6 was vibrated at 2.4 MHz, and the vibration was propagated to the raw material liquid 4a through water 5a to atomize the raw material liquid 4a to generate mist. This mist 4b is conveyed to the substrate 10 by the carrier gas through the supply pipe 9 and the nozzle 7, and the mist 4b is reacted in the vicinity of the substrate 10 at 75 ° C. under atmospheric pressure to be placed on the substrate 10. A silicon oxide film was formed. The film formation treatment time was 15 minutes, and the film thickness was 8.6 μm.

(Example 2)
The film formation process was performed in the same manner as in Example 1 except that the nozzle angle of the nozzle 7 was set to 25 °. The film thickness of the obtained film was 15.68 μm.

(Comparative Example 1)
The film formation process was performed in the same manner as in Example 1 except that the nozzle angle of the nozzle 7 was set to 0 °. The film thickness of the obtained film was 1.0 μm.

(Example 3)
The film formation process was performed in the same manner as in Example 1 except that the nozzle angle of the nozzle 7 was set to 5 °. The film thickness of the obtained film was 6.7 μm.

(Example 4)
The film formation process was performed in the same manner as in Example 1 except that the nozzle angle of the nozzle 7 was set to 10 °. The film thickness of the obtained film was 3.4 μm.

(Example 5)
The film formation process was performed in the same manner as in Example 1 except that the nozzle angle of the nozzle 7 was set to 15 °. The film thickness of the obtained film was 6.3 μm.

(Example 6)
The film formation process was performed in the same manner as in Example 1 except that the nozzle angle of the nozzle 7 was set to 30 °. The film thickness of the obtained film was 2.1 μm.

FIG. 3 shows the relationship between the nozzle angle and the film thickness in Examples 1 to 6 and Comparative Example 1. As is clear from FIG. 3, it can be seen that the film forming speed is excellent in each of Examples 1 to 6, and the film forming process can be efficiently performed.

Since the processing method of the present invention can efficiently process the substrate in an industrially advantageous manner, it can be used in various manufacturing fields such as semiconductor devices and electronic devices.

1 Formation device 2a Carrier gas supply source 2b Carrier gas (dilution) source 3a Flow control valve 3b Flow control valve 4 Mist source 4a Raw material solution 4b Mist 5 Container 5a Water 6 Ultrasonic transducer 7 Nozzle 8 Hot plate 9 Supply Tube 10 Board 11 Stage 12 Strut

Claims (15)

The raw material solution was atomized or liquid droplets, the carrier gas is supplied to the suspended mists or droplets, transporting the mist or the droplets to the substrate in the carrier gas, the mist or the liquid discharged from the nozzle A treatment method for reacting droplets on the substrate, wherein the nozzle angle is in the range of 1 ° to 30 ° with respect to the vertically downward direction. The processing method according to claim 1, wherein the nozzle angle is in the range of 16 ° to 28 °. The processing method according to claim 1 or 2, wherein the atomization or droplet formation is performed by using ultrasonic vibration. The treatment method according to any one of claims 1 to 3, wherein the raw material solution contains an etching agent, a surface modifier, or a film-forming raw material, and the treatment is an etching treatment, a surface modification treatment, or a film-forming treatment, respectively. .. The treatment method according to any one of claims 1 to 4, wherein the raw material solution contains a film-forming raw material, and the treatment is a film-forming treatment. The treatment method according to any one of claims 1 to 5, wherein the reaction is carried out under atmospheric pressure. The treatment method according to any one of claims 1 to 6, wherein the reaction is a thermal reaction. The treatment method according to claim 7, wherein the thermal reaction is carried out at a temperature of 200 ° C. or lower. Atomized-solution droplets unit for raw material solution was atomized or dropletizer suspended, the carrier gas is supplied to the floating mist or droplets, transporting the mist or the droplets to the substrate in the carrier gas conveying A processing device including a part, a reaction part for reacting the mist or the droplets discharged from the nozzle on the substrate, and the nozzle angle is in the range of 1 ° to 30 ° with respect to the vertical downward direction. A processing device characterized by the fact that. The processing apparatus according to claim 9, wherein the nozzle angle is in the range of 16 ° to 28 °. The processing apparatus according to claim 9 or 10, wherein the atomizing / droplet atomizing unit is provided with an ultrasonic vibrator, and the atomizing or droplet atomizing is performed by using ultrasonic vibration. The processing apparatus according to any one of claims 9 to 11, which is an etching processing apparatus, a surface modification processing apparatus, or a film forming processing apparatus. The processing apparatus according to any one of claims 9 to 12, which is a film forming processing apparatus. The processing apparatus according to any one of claims 9 to 13, which is not provided with a vacuum apparatus or a decompression apparatus. The processing apparatus according to any one of claims 9 to 14, wherein the reaction unit includes a heating means.

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