JP2016180158A - Film formation method - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for forming a high-purity thick film containing a metal element, and comprising an oxide, a nitride, a carbide or a sulfide, efficiently on the surface of a substrate.SOLUTION: In a film formation method, mist 18 charged positively or negatively is generated by using a raw material solution in which a component derived from a metal element is dissolved in an atmosphere containing gas comprising molecules containing at least one kind selected from an oxygen element, a nitrogen element, a carbon element and elemental sulfur, and the charged mist 18 is supplied continuously to a substrate 20, and the charged mist staying on the surface of the substrate 20 or its periphery is irradiated with a laser beam having a wavelength of 500 nm-11 μm.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a method for efficiently forming a thick film made of an oxide, nitride, carbide or sulfide (hereinafter also referred to as “metal compound”) containing a metal element on the surface of a substrate.

A film made of an oxide, nitride, carbide or sulfide (metal compound) containing a metal element (hereinafter also referred to as “metal compound film”) is protected (oxidation resistance, heat shield, wear resistance, etc.), reflective, As a functional film having an action such as insulation, it is widely used industrially.
As a method for producing a high-purity film made of a metal compound, after dissolving an organic compound or inorganic compound containing a metal element in a medium, the obtained solution is applied to a substrate, heated and baked, Chemical vapor deposition (CVD) in which raw materials are reacted and deposited in a solid state, physical vapor deposition (PVD) in which physical energy is injected into a solid raw material (target), vaporized, and rearranged as an oxide thin film on a substrate ) Etc. are known. Also known are an aerosol deposition method (Patent Document 1) and an electrostatic spray method (Patent Document 2) in which fine particles of metal oxide themselves are deposited.

Japanese Patent Laid-Open No. 2003-166076 Special table 2010-506721 gazette

In the case of chemical vapor deposition (CVD) and physical vapor deposition (PVD), a high-purity metal compound film can be obtained. On the other hand, in order to form a metal compound film having a thickness of more than 100 μm, the film formation speed is high. It was not enough and took a long time. In addition, in the case of depositing fine particles made of a metal compound itself, it is necessary to use high-cost high-purity fine particles having a constant size.
An object of this invention is to provide the method of forming the thick film which consists of a highly purified metal compound efficiently on the surface of a base material.

The present invention is shown below.
1. A molecule containing at least one selected from an oxygen element, a nitrogen element, a carbon element and a sulfur element in a method for forming a film made of an oxide, nitride, carbide or sulfide containing a metal element on the surface of a substrate Using a raw material solution in which a component (M) derived from a metal element is dissolved in an atmosphere containing a gas, a positively or negatively charged mist is generated, and the charged mist is continuously applied to the substrate. The film forming method is characterized by irradiating a charged mist staying on or near the surface of the base material with a laser having a wavelength of 500 nm to 11 μm.
2. 2. The film forming method according to 1 above, wherein the charged mist is formed by electrostatic spraying of the raw material solution so that the charged mist and the substrate have opposite charges.
3. 3. The film forming method according to 1 or 2 above, wherein the substrate is preheated.
4). The component (M) is at least one selected from organic metal complexes, organic acid metal salts, metal alkoxides, halides containing metal elements, nitrates, sulfates, phosphates, carbonates and hydroxides. 4. The film forming method according to any one of 1 to 3.
5. The film forming method according to any one of 1 to 4 above, wherein the concentration of the component (M) contained in the raw material solution is 0.1 to 80% by mass.

According to the present invention, since the charged mist continuously supplied to the substrate has the same charge of either positive or negative, they are not aggregated, and the surface of the substrate or the vicinity thereof does not agglomerate. By irradiating it with a laser, a thermal decomposition reaction occurs, and generation and deposition of a high-purity metal compound are repeated, so that a thick film can be easily formed. In a widely used chemical vapor deposition method (CVD), physical vapor deposition method (PVD) or the like as a conventional manufacturing method, for example, a reduced pressure condition of 0.01 atm or less has been preferable. A thick film made of a metal compound can be produced under atmospheric pressure or a reduced pressure condition close thereto. In addition, a metal compound film having a large area can be manufactured by improving a charging mist supply method, a laser irradiation method, and the like. According to the present invention, for example, when forming a metal oxide film, not only an oxide containing only one kind of metal element but also a composite oxide containing a plurality of kinds can be used in a wide range of fields. is there.
When the raw material solution is electrostatically sprayed so that the charged mist and the substrate have opposite charges, the charged mist can be reliably supplied to the surface of the substrate, and the generated metal compound is Since it becomes easy to grow grains in a regular direction (perpendicular direction or the like) with respect to the surface of the substrate, a thick film can be obtained efficiently.
Further, when the substrate is preheated, it is suitable for forming a film made of a crystalline metal compound.

It is the schematic which shows an example of the film forming apparatus which concerns on the method of this invention. 1 is a schematic view showing a film forming apparatus used in Example 1. FIG. 2 is an image showing a cross section including an α-alumina film obtained in Example 1. FIG. 2 is an X-ray diffraction image showing the α-alumina film obtained in Example 1. FIG.

Hereinafter, the present invention will be described in detail.
The film forming method of the present invention comprises a metal in an atmosphere containing a gas (hereinafter referred to as “reactive gas”) composed of molecules containing at least one selected from oxygen, nitrogen, carbon and sulfur. A method of forming a film (metal compound film) made of an oxide, nitride, carbide, sulfide or a composite compound thereof containing an element on the surface of a substrate, the component derived from the metal element (M), That is, using a raw material solution in which a precursor is dissolved, mist that is charged either positively or negatively is generated, and this charged mist is continuously supplied to the base material, on the surface of the base material or in the vicinity thereof. The staying charged mist is irradiated with a laser having a wavelength of 500 nm to 11 μm.

  The metal element is capable of generating a metal compound (including composites such as composite oxides, oxynitrides, and carbonitrides), and is a compound or a single metal containing metal elements (these are “metal” The element (corresponding to the component (M) derived from the element) is not particularly limited as long as it is soluble in water, an acid, an alkali, or an organic solvent. Preferred metal elements are elements of Groups 1 to 16, and particularly preferred metal elements are Al, Ti, Sn, In, Zn, Co, Ni, Fe, Y, Zr, Li, Cr, Hf, La, Ba , Cu and the like.

In the raw material solution, the component (M) derived from the metal element is dissolved in a medium composed of water (including an acidic aqueous solution and a basic aqueous solution) or an organic solvent.
When the component (M) is a compound containing a metal element, any of an organic compound and an inorganic compound may be used, and an organic metal complex, an organic acid metal salt, a metal alkoxide, a halide containing a metal element, nitrate, sulfate, phosphorus Acid salts, carbonates, hydroxides and the like can be used. These may be used alone or in combination of two or more.

  Examples of organometallic complexes include acetylacetone (= 2,4-pentanedione), 2,4-hexanedione, 3,5-heptanedione, 2,4-heptanedione, 2-methylhexane-3,5-dione, 2 , 4-octanedione, 3,5-octanedione, 6-methylheptane-2,4-dione, 5-methylheptane-2,4-dione, 2,2-dimethylhexane-3,5-dione, 2, 6-dimethylheptane-3,5-dione, 4,6-nonanedione, 2,8-dimethylnonane-4,6-dione, 2,2,6,6-tetramethylheptane-3,5-dione, 1- Phenyl-1,3-butanedione, 1,3-diphenyl-1,3-propanedione, methyl acetoacetate, ethyl acetoacetate, isopropyl acetoacetate, tert-butyl acetoacetate, Methyl pionyl acetate, ethyl propionyl acetate, isopropyl propionyl acetate, tert-butyl propionyl acetate, ethylenediaminetetraacetic acid, 1,2-cyclohexanediaminetetraacetic acid, dihydroxyethylglycine, diaminopropanoltetraacetic acid, diethylenetriaminepentaacetic acid, ethylenediaminediacetic acid, ethylenediamine Propionic acid, hydroxyethylenediaminetriacetic acid, glycol etherdiaminetetraacetic acid, hexamethylenediaminetetraacetic acid, ethylenediaminedi (o-hydroxyphenyl) acetic acid, hydroxyethyliminodiacetic acid, iminodiacetic acid, 1,3-diaminopropanetetraacetic acid, 1 , 2-diaminopropanetetraacetic acid, nitrilotriacetic acid, nitrilotripropionic acid, triethylenetetramine hexaacetic acid, ethylenediamine disuccinic acid, , 3-diaminopropane disuccinic acid, glutamic acid -N, N- diacetic acid, aspartic acid -N, can be used complex obtained with chelating agents such as N- diacetic acid.

Examples of the organic acid metal salt include metal salts such as aliphatic carboxylic acid, alicyclic carboxylic acid, and aromatic carboxylic acid. In each carboxylic acid, a part of hydrogen atoms bonded to carbon atoms in the structure may be substituted with a halogen atom, a hydroxyl group, an amino group, an alkyl ether group or the like.
As the metal alkoxide, a compound containing an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group can be used.
As the halide containing a metal element, fluoride, chloride, bromide, iodide, or the like can be used.
In the present invention, since the component (M) can provide a stable raw material solution and is easily thermally decomposed by a laser, an organometallic complex, a metal alkoxide, a halide containing a metal element, and the like are particularly preferable.

Examples of organometallic complexes containing Al element include aluminum tris (acetylacetonate), aluminum tris (ethylacetoacetate), aluminum monoacetylacetonate bis (ethylacetoacetate), aluminum monoacetylacetonate bis (oleyl acetoacetate), Diisopropoxyaluminum ethyl acetoacetate, aluminum butoxybisethyl acetoacetate, aluminum bisethyl acetoacetate monoacetylacetonate, tris (dipivaloylmethanato) aluminum, 1,1,1-trimethyl-2,4-pentadionato Aluminum, diisopropoxy-dipivaloylmethanatoaluminum, diacetoxy-dipivaloylmethanatoaluminum, tris (benzoyltrimethylacetyl) Asetonato) aluminum, di -o- tolyloxy - dipivaloylmethanate aluminum, di (acetylacetonato) pivaloyl meth isocyanatomethyl aluminum, tris (butanoyl pivaloyl meth isocyanatomethyl) aluminum and the like.
Examples of the organometallic complex containing Ti element include titanium tetraacetylacetonate, titanium tetra-2-ethylhexoxide, dibutoxytitanium bisacetylacetonate, and the like.
Examples of organometallic complexes containing Zr element include di-n-propoxy bis (acetylacetonato) zirconium, di-isopropoxy bis (acetylacetonato) zirconium, di-n-butoxy bis (acetylacetonato) zirconium. Di-tert-butoxy bis (acetylacetonate) zirconium, mono-n-propoxy tris (acetylacetonate) zirconium, mono-isopropoxy tris (acetylacetonate) zirconium, mono-n-butoxy tris ( Acetylacetonato) zirconium, mono-tert-butoxy-tris (acetylacetonato) zirconium, zirconium tetraacetylacetonate, di-n-propoxybis (ethylacetoacetate) zirconium, di-isop Poxy bis (ethyl acetoacetate) zirconium, di-n-butoxy bis (ethyl acetoacetate) zirconium, di-tert-butoxy bis (ethyl acetoacetate) zirconium, mono-n-propoxy tris (ethyl acetoacetate) Zirconium, mono-isopropoxy tris (ethyl acetoacetate) zirconium, mono-n-butoxy tris (ethyl acetoacetate) zirconium, mono-tert-butoxy tris (ethyl acetoacetate) zirconium, zirconium tetraethyl acetoacetate, mono ( Acetylacetonato) tris (ethylacetoacetate) zirconium, bis (acetylacetonato) bis (ethylacetoacetate) zirconium, tris (acetylacetate) Inert) mono (ethyl acetoacetate) zirconium, and the like.

  The medium for dissolving the component (M) can be water or an organic solvent as described above, but an organic solvent is preferable from the viewpoint of equilibrium vapor pressure. The organic solvent is preferably liquid at 25 ° C., and alcohol, ketone, ester, ether, hydrocarbon and the like can be used.

  The concentration of the component (M) contained in the raw material solution is preferably from 0.1 to 80% by mass, more preferably from 1 to 50% by mass, and still more preferably from the viewpoints of charge mist formability and shape retention. Is 5-40 mass%.

In the present invention, the metal compound film is obtained by irradiating a charged mist having a positive or negative charge formed using the raw material solution in an atmosphere containing a reactive gas with a laser. Reactive gas reacts with component (M) or its decomposition product (product immediately after laser irradiation) when laser irradiates charged mist to form oxide, nitride, carbide or sulfide. If it does, it will not specifically limit. In the case of an oxide, oxygen gas, ozone gas, air containing these, or the like can be used. In the case of nitride, nitrogen gas, ammonia gas or the like can be used. In the case of oxynitride, NO gas, NO ₂ gas, N ₂ O gas, or the like can be used. In the case of carbonitride, CN gas, methane-ammonia mixed gas, CO-ammonia mixed gas, CO ₂ -ammonia mixed gas, or the like can be used. In the case of carbide, methane gas, CO gas, CO ₂ gas, or the like can be used. In the case of sulfide, HS gas, SO gas, SO ₂ gas, SO ₃ gas, or the like can be used. An inert gas such as argon gas or helium gas can be used in combination for adjusting the concentration of the reactive gas.

In an atmosphere containing a reactive gas, a plurality of charged mists having the same charge as each other repel each other, but are supplied to the substrate while maintaining substantially equal intervals. When the charged mist staying at or near the surface of the substrate is irradiated with a laser, a film in which the metal compound regularly grows is formed.
The method for preparing the charged mist is not particularly limited.For example, a method of electrostatically spraying the raw material solution, a method of spraying the raw material solution in an atmosphere containing either positive or negative ions generated by an ionizer, and the like, and The method of ultrasonically spraying a raw material solution is mentioned. Of these, the former method is preferable because the charging mist can be generated with a simple configuration. In addition, even if it is the charging mist prepared by any of the above methods, when supplying the charging mist to the substrate, it is easy to use natural fall. However, when preparing the charged mist, when the raw material solution is electrostatically sprayed so that the charged mist and the substrate have opposite charges, the charged mist is supplied to the surface of the substrate by a method other than natural dropping. And the yield can be improved.

A method for electrostatically spraying the raw material solution to generate the charged mist is not particularly limited, but a conventionally known electrostatic spraying device or its principle can be used.
In FIG. 1, inside a chamber 11, a charged mist 18 obtained by electrostatic spraying from a spray nozzle 17 is supplied to the surface of a substrate 20 placed below the spray nozzle 17, and the substrate 20 This is an example of a film forming apparatus for forming a metal compound film by irradiating the charged mist 18 staying at or near the surface of the metal mist 18 with laser from the laser irradiation means 13. By applying a voltage between the spray nozzle 17 for spraying the raw material solution fed from the raw material solution supply means 16 through the pipe and the base material 20, droplets sprayed from the spray nozzle 17 are applied. The charge mist 18 can be generated by applying a positive or negative charge. When a voltage is applied to the spray nozzle 17 or the like, a Coulomb force is applied to the raw material solution sprayed from the spray nozzle 17, and the liquid surface locally rises in a cone shape to form a Taylor cone. When the Taylor cone is formed in this way, electric charges concentrate on the tip of the Taylor cone and the electric field strength in this portion increases. And the Coulomb force which arises in this part becomes large, and also Taylor corn is made to grow. In this way, when the Taylor cone grows and the charge concentrates on the tip of the Taylor cone and the density of the charge increases, the raw material solution at the tip of the Taylor cone gives a large amount of energy (the repulsive force of the high-density charge). Upon receipt, the surface tension is exceeded, splitting and scattering (Rayleigh splitting) and discharging are generated, thereby generating a charged mist 18 having a small size.
The voltage for charging the raw material solution is preferably +2 kV because a stable single cone is formed, a charged mist having a uniform shape and size is formed, and the thickness uniformity of the metal compound film is improved. ~ + 8 kV or -8 kV to -2 kV, more preferably +3 kV to +6 kV or -6 kV to -3 kV.

  As described above, since the charged mist 18 generated by electrostatic spraying of the raw material solution while applying a voltage between the spray nozzle 17 and the substrate 20 and the substrate 20 have opposite charges, Even if the positional relationship between the spray nozzle 17 and the substrate 20 in FIG. 1 is, for example, the horizontal direction or the vertical direction, the charged mist 18 is reliably supplied to the surface of the substrate 20. In the present invention, by arranging the charging mist 18 at a specific position on the surface of the base material 20, the metal compound film can be formed at that position, so that a voltage can be applied only to a specific position of the base material 20. That's fine. In addition, when the base material 20 is large or the distance between the spray nozzle 17 and the base material 20 is long, in order to improve the supply speed of the charging mist 18 and further the film forming speed, for example, A carrier gas or the like can be used.

  The feed rate of the raw material solution for generating the charged mist is preferably 0.01 to 10 ml / min, more preferably a stable single cone is formed and a charged mist having a constant shape and size is formed. Is 0.02 to 5 ml / min, more preferably 0.1 to 3 ml / min. The distance between the spray nozzle 17 and the substrate 20 is not particularly limited, but is preferably 1 to 50 cm, more preferably 10 to 30 cm.

The constituent material of the base material is not particularly limited, but at least the constituent material at the position where the metal compound film is formed is preferably such that the shape, properties, etc. of the base material are not changed by receiving the laser beam. For example, metals, alloys, ceramics and the like are particularly preferable. Therefore, in the case of a base material made of a plurality of materials, it is preferable to form a metal compound film at a specific position made of the above constituent materials.
The shape of the substrate is also not particularly limited, and may be a flat plate shape, a curved plate shape, a rod shape, a cylindrical shape, a lump shape, or a combination thereof.

When charging mist is supplied to the substrate, the substrate is preheated in order to improve the production rate of the metal compound by adjusting the laser reaction smoothly and to adjust the crystallinity of the metal compound to be generated. You may keep it. The preheating temperature is appropriately selected depending on the kind of the metal compound to be generated and the like, but is usually 500 ° C to 1000 ° C.
The method for preheating the substrate is not particularly limited, and infrared lamps, halogen lamps, resistance heating, high frequency induction heating, microwave heating, and the like can be used.

In the present invention, laser irradiation of the charged mist uses a laser having a wavelength of 500 nm to 11 μm in order to smoothly generate a metal compound and to form a film. For example, an Nd-YAG laser, an Nd-YVO laser, an Nd-YLF laser, a titanium sapphire laser, a carbon dioxide gas laser, or the like can be used.
When irradiating a laser, a method of irradiating a laser while scanning the laser or through a light diffusing lens with the substrate fixed, or a method of irradiating a laser with a fixed optical path while moving the substrate Can do.

The laser irradiation conditions are appropriately selected depending on the composition of the charged mist (component (M) or type of solvent), the constituent material of the base material, the preheating temperature of the base material, and the like. Laser power, in terms of smooth generation and grain growth of the metal compound, preferably 40~200W / cm ^2, more preferably a 50~150W / cm ^2.
In the laser irradiation, the pressure inside the chamber 11 in FIG. 1 is not particularly limited, and can be preferably 0.4 to 3.0 atm, more preferably 0.6 to 2.0 atm. The present invention is characterized in that it does not require a reduced pressure condition used in a chemical vapor deposition method (CVD), a physical vapor deposition method (PVD) or the like that is widely applied as a conventional manufacturing method.
The interior of the chamber 11 is an atmosphere containing a reactive gas. The inside of the chamber 11 may be either a closed system or an open system. The interior of the chamber 11 may be heated as long as the supplied charged mist is held until the shape of the charged mist reaches the surface of the substrate.

  According to the present invention, the deposition rate of the metal compound film can be preferably 10 to 3000 μm / hour, more preferably 50 to 1000 μm / hour, and a thick film can be efficiently formed.

An example of the film forming apparatus according to the present invention is shown in FIG. 1, but the configuration is appropriately changed according to the composition (component (M) or type of solvent) of the charging mist, the shape and size of the substrate, and the like. can do.
For example, in FIG. 1, the number of spray nozzles 17 that generate charging mist and the number of laser irradiation means 13 are each set to 1, but may be a plurality.
In addition, when the solvent contained in the charged mist contains an organic solvent, the organic solvent is vaporized simultaneously with the generation of the metal compound by laser irradiation of the charged mist, so that the volatile gas is discharged to the outside of the chamber 11. It is preferable to connect the exhaust pump 29 to the chamber 11 (see FIG. 2).

  Hereinafter, the present invention will be specifically described with reference to production examples of an α-alumina film.

1. Production Raw Material A solution in which aluminum tris (acetylacetonate) was dissolved in acetone was used as a raw material solution for forming charged mist. The concentration of aluminum tris (acetylacetonate) is 10% by mass.
A plate (20 mm × 20 mm × 1.0 mm) made of SUS304 was used as the base material for forming the α-alumina film.

2. Manufacturing apparatus The film forming apparatus 10 shown in FIG. 2 was used. The apparatus 10 continuously generates a negatively charged mist 18 by a spray nozzle 17 inside the chamber 11 and supplies the mist 18 toward a preheated positively charged base material 20, and then the surface of the base material 20. This is a device for forming a film made of α-alumina by irradiating the charged mist 18 convection to the laser with a laser.
In this film forming apparatus 10, a raw material solution storage unit 15 that stores a raw material solution and a raw material solution supply unit 16 are disposed outside the chamber 11, and the raw material solution is supplied from the raw material solution supply unit 16 to a pipe (inner diameter 0). Through a 3 mm stainless steel tube) to the spray nozzle 17 disposed inside the chamber 11. The base material 20 on which the metal compound film is to be formed was placed on the base material support portion 21 with an interval of 25 cm immediately below the spray nozzle 17. While applying a DC voltage to the spray nozzle 17 and grounding the base material 20, the liquid droplets from the spray nozzle 17 are negatively charged, and the generated charged mist 18 is directed toward the positively charged base material 20. did. A laser irradiation means 13 (Nd-YAG laser) that irradiates a laser beam having a wavelength of 1064 nm toward the surface of the substrate 20 through the quartz incident window 14 is disposed outside the chamber 11. The incident angle of the laser to the base material 20 is 45 degrees. In order to promote the production of α-alumina, a means (infrared lamp) 23 for preheating (heating) the base material 20 is provided, and a thermocouple 25 for measuring the temperature of the base material 20 is provided. Set up. Further, in order to suppress the volatilized gas from filling the chamber 11 with the vaporization of acetone contained in the raw material solution, and to maintain the film formation conditions (metal compound generation conditions) from beginning to end, The inside of the chamber 11 was ventilated by supplying air from the upper opening 27 of the chamber 11 and exhausting it using a diaphragm pump 29 connected to the lower side corresponding to the opposite wall. The pressure inside the chamber 11 was 0.8 atm.

3. Example 1 Production and Evaluation of α-Alumina Membrane
While supplying the raw material solution (acetone solution of aluminum triacetylacetonate) from the raw material solution supplying means 16 to the spray nozzle 17 to which a DC voltage of 4.0 V is applied, electrostatic spraying is performed. The charging mist 18 was generated. Then, the charged mist 18 was continuously supplied to the surface of the positively charged substrate 20 previously heated to 750 ° C. by an infrared lamp. Then, the laser irradiation means 13 is driven (output: 60 W / cm ² ), and the laser continues to irradiate the staying charged mist 18 to repeat the generation and deposition of α-alumina. A film made of alumina was formed. The film forming speed was 83 μm / hour.
The SEM image and X-ray diffraction image of the obtained α-alumina film are shown in FIGS. 3 and 4, respectively. FIG. 3 shows that a dense film has been formed.

Example 2
Except that the output was 90 W / cm ² as the laser irradiation condition, the same operation as in Example 1 was performed, and a film made of α-alumina was formed on the entire surface of the substrate 20. The film forming speed was 103 μm / hour.

Comparative Example 1
A raw material solution (acetone solution of aluminum triacetylacetonate) is applied to the surface of the substrate 20 which has not been preheated, and the obtained coating film is irradiated with laser (irradiation density: 60 W / cm ² ). The coating film completely disappeared and no film was formed.

  The present invention is preferably a method of forming a film made of a metal compound on the surface of a heat-resistant substrate, and since a laminated material is obtained, protection (oxidation resistance, heat shielding, wear resistance, etc.), reflection, It is suitable for the production of functional materials or functional articles having an action such as insulation.

  DESCRIPTION OF SYMBOLS 10: Film | membrane formation apparatus, 11: Chamber, 13: Laser irradiation means, 14: Optical window (quartz incident window), 15: Raw material solution storage part, 16: Raw material solution supply means, 17: Spray nozzle, 18: Charging mist 20: base material, 21: base material support part, 23: preheating means (infrared lamp), 25: base material temperature measuring means (thermocouple), 29: exhaust pump.

Claims (5)

In a method of forming a film made of an oxide, nitride, carbide or sulfide containing a metal element on the surface of a substrate,
Using a raw material solution in which the component (M) derived from the metal element is dissolved in an atmosphere containing a gas comprising a molecule containing at least one selected from an oxygen element, a nitrogen element, a carbon element, and a sulfur element The mist charged positively or negatively is generated, the charged mist is continuously supplied to the base material, and the charged mist staying at or near the surface of the base material has a wavelength of 500 nm to 11 μm. A film forming method characterized by irradiating a laser beam.   The film forming method according to claim 1, wherein the charged mist is formed by electrostatic spraying the raw material solution so that the charged mist and the substrate have opposite charges.   The film forming method according to claim 1, wherein the substrate is preheated.   The component (M) is at least one selected from organic metal complexes, organic acid metal salts, metal alkoxides, halides containing the metal elements, nitrates, sulfates, phosphates, carbonates and hydroxides. The film forming method according to any one of claims 1 to 3.   The film forming method according to any one of claims 1 to 4, wherein the concentration of the component (M) contained in the raw material solution is 0.1 to 80% by mass.