Barium introduction agent for chemical vapor deposition, coating solution for chemical vapor deposition, barium-containing film, and method for forming a barium-containing film by chemical vapor deposition.

Abstract

To provide a barium introduction agent for chemical vapor deposition (CVM) that enables the production of barium-containing films with less variation in barium content at low temperatures. [Solution] A barium introduction agent for chemical vapor deposition containing barium hydroxide.

Description

Technical Field

[0001] The present invention relates to a barium introducing agent for chemical vapor deposition, a coating liquid for chemical vapor deposition, a barium-containing film, and a method for forming a barium-containing film by chemical vapor deposition.

Background Art

[0002] Ceramic films containing barium are widely used in the electronic information field as high dielectric materials and piezoelectric materials. In the electronic information field, since fluctuations in dielectric constant and piezoelectric effect greatly affect the performance of devices, it is necessary to control the barium content on the order of percent.

[0003] This barium-containing film is conventionally obtained by mixing barium-containing powder obtained by a liquid phase method or the like with a solvent, a binder, etc. to form a slurry, applying it on a substrate by spin coating or the like, and then firing it. However, this firing requires a high temperature of about 1000 °C, and there is a problem that film formation is limited only to substrates with high heat resistance.

[0004] In Non-Patent Document 1, by using a spray pyrolysis method as a method for producing barium-containing powder, fine particles with a particle diameter of about 1 μm are produced, and a barium-containing film with a minimum film thickness of about 5 μm is formed using these fine particles as raw materials. However, in this process, it is difficult to make the film thickness less than the particle diameter of the raw material particles, and it is difficult to obtain a thin film.

[0005] On the other hand, chemical vapor deposition (hereinafter referred to as "CVD") has been developed as a well-known method for forming a metal oxide film. CVD is a method of feeding a gas containing a component serving as a raw material for a thin film onto the surface of a substrate and forming a film by a chemical reaction, and heat, plasma, or the like is used to advance the chemical reaction. In Patent Document 1, a barium oxide film is obtained by thermal CVD using a barium complex, but the film formation rate is as low as about 1 nm / min. Also, in Patent Document 2, a barium titanate film is obtained by thermal CVD using a barium complex, but there is no description regarding the film composition.

[0006] Patent Document 3 discusses mist CVD, a type of CVD that enables film deposition at low temperatures in the atmosphere without requiring vacuum equipment, but there are no examples of actual studies on film deposition of barium-containing films. [Prior art documents] [Patent Documents]

[0007] [Patent Document 1] International Publication No. 2005 / 087697 [Patent Document 2] Japanese Patent Application Publication No. 4-134044 [Patent Document 3] International Publication No. 2018 / 043503 [Non-patent literature]

[0008] [Non-Patent Document 1] Kunpeng Li, Hiroyuki Shimada, Yasunobu Mizutani, Yuji Okuyama, Takuto Araki, Energy Conversion and Management, 296 (2023) [Overview of the Initiative] [Problems that the invention aims to solve]

[0009] This invention has been made in view of the above problems, and aims to provide a barium introduction agent for chemical vapor deposition (CVA) for producing barium-containing films with less variation in barium content at low temperatures.

[0010] Furthermore, the present invention aims to provide a coating solution for chemical vapor deposition containing the above-mentioned barium introduction agent for chemical vapor deposition, a barium-containing film formed from the coating solution, and a method for forming a barium-containing film by chemical vapor deposition using the coating solution. [Means for solving the problem]

[0011] The present invention relates to a barium introduction agent for chemical vapor deposition containing [1] barium hydroxide.

[0012] Furthermore, the present invention relates to a barium introduction agent for chemical vapor deposition described in [1] above, which comprises a β-diketone compound represented by the following formula (1), wherein the molar ratio of barium hydroxide to the β-diketone compound is preferably 1.0:0.01 to 1.0:100. [ka] (In formula (1), R1 and R2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R3 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

[0013] Furthermore, the present invention relates to a coating solution for chemical vapor deposition, comprising [3] the barium introduction agent for chemical vapor deposition described in [2] above, and a solvent.

[0014] Furthermore, the present invention relates to a coating solution for chemical vapor deposition described in [3] above, which comprises a complex, salt, or alkoxide having divalent to tetravalent metal atoms other than [4] barium, and preferably the molar ratio of barium atoms in barium hydroxide to metal atoms contained in the complex, salt, or alkoxide is 1.0:0.01 to 1.0:1000.

[0015] Furthermore, the present invention relates to a barium-containing film obtained by forming a coating solution for chemical vapor deposition described in [3] or [4] above by chemical vapor deposition.

[0016] Furthermore, the present invention relates to a method for forming a barium-containing film by chemical vapor deposition, comprising: [6] a misting step of atomizing the coating liquid for chemical vapor deposition described in [3] or [4] above; and a mist supply step of supplying mist to a heated substrate surface and allowing it to react on the substrate.

[0017] Furthermore, the present invention relates to a method for forming a barium-containing film by chemical vapor deposition, comprising: a two-tank atomization step of separately atomizing the coating liquid for chemical vapor deposition described in [7] above and the metal source solution containing a complex, salt or alkoxide having a divalent to tetravalent metal atom excluding barium; and a plurality of mist supply steps of supplying each atomized mist to the surface of a heated substrate and reacting them on the substrate.

[0018] Furthermore, the present invention relates to the method for forming a barium-containing film by chemical vapor deposition according to [7] above, wherein it is preferable to supply the mist to the surface of the heated substrate so that the molar ratio of the barium atoms contained in the mist to the divalent to tetravalent metal atoms excluding barium is 1.0:0.01 to 1.0:1000.

Advantages of the Invention

[0019] The barium introducing agent of the present invention has high solubility in a solvent and can stably supply raw materials, so that a barium-containing film with little variation in barium content can be produced in CVD. In addition, by making the barium introducing agent into a solution, the barium introducing agent is well dispersed, the chemical reaction proceeds easily, and barium introduction at a low temperature can be performed.

Brief Description of the Drawings

[0020] [Figure 1] It is a schematic diagram of a film forming apparatus for a barium-containing film in the method for forming a barium-containing film according to an embodiment of the present invention. [Figure 2] It is a schematic diagram of a film forming apparatus for a barium-containing film in the method for forming a barium-containing film according to an embodiment of the present invention. [Figure 3] It is a schematic diagram of a film forming apparatus for a barium-containing film in the method for forming a barium-containing film according to an embodiment of the present invention. [Figure 4] It is a schematic diagram of an atomizer in a film forming apparatus for a barium-containing film in the method for forming a barium-containing film according to an embodiment of the present invention. [Figure 5]This is a schematic diagram of a mixing tank in a barium-containing film deposition apparatus for a method of forming a barium-containing film according to one embodiment of the present invention. [Figure 6] This is a schematic diagram of the film deposition section in a barium-containing film deposition apparatus for a method of forming a barium-containing film according to one embodiment of the present invention. [Modes for carrying out the invention]

[0021] The following describes, with reference to diagrams as necessary, a barium introduction agent, coating solution, barium-containing film, and film formation method for chemical vapor deposition according to one embodiment of the present invention.

[0022] <Barium introduction agent> The barium introduction agent of the present invention is used for forming barium-containing films by chemical vapor deposition and contains barium hydroxide. Barium hydroxide includes barium anhydride, barium hydroxide octahydrate, and the like. Compared to other barium compounds, such as barium salts like barium acetate, barium hydroxide has higher solubility in solvents, allowing for more efficient barium introduction when used as a barium introduction agent.

[0023] Furthermore, the barium introducing agent may also contain a β-diketone compound represented by the following formula (1). The β-diketone compound used in the present invention is thought to facilitate the chemical change from barium hydroxide to a metal oxide by causing addition to barium hydroxide during the gas-phase reaction. When halogen atoms such as fluorine or electron-withdrawing substituents are present in the β-diketone compound, a gradual reaction with metal atoms occurs in the film-forming coating solution. In particular, when complexes, salts, or alkoxides containing other metal atoms are present in the film-forming coating solution, the variation (variation) in the barium content of the barium-containing film obtained with each film formation tends to increase. [ka] (In formula (1), R1 and R2 each independently represent a hydrocarbon group having 1 to 6 carbon atoms, and R3 represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

[0024] When used as a coating liquid for film formation in mist CVD, the efficiency of atomization by ultrasound is high, so R1 and R2 in formula (1) are preferably each independently a hydrocarbon group having 1 to 4 carbon atoms, and R3 is preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Furthermore, if a high film formation rate is desired, the total number of carbon atoms in R1, R2, and R3 in formula (1) is preferably 4 to 10.

[0025] When using the above-mentioned β-diketone compound, the molar ratio of barium hydroxide to the β-diketone compound is preferably 1.0:0.01 to 1.0:100, more preferably 1.0:0.1 to 1.0:50, and even more preferably 1.0:0.1 to 1.0:20, from the viewpoint of minimizing variation in the barium content of the resulting barium-containing film.

[0026] <Coating solution for chemical vapor deposition> The coating solution for chemical vapor deposition according to the present invention comprises the barium introducing agent and a solvent.

[0027] <Solvent> Any solvent that can dissolve the barium introducing agent may be used as the solvent. However, when used in mist CVD, from the viewpoint of mist generation efficiency, a solvent with a boiling point of 40°C to 150°C and a viscosity of 1.3 mPa·sec or less at 25°C is preferred, a solvent with a viscosity of 0.1 mPa·sec to 1.0 mPa·sec is more preferred, and a solvent with a viscosity of 0.3 mPa·sec to 1.0 mPa·sec is even more preferred. Examples of solvents include lower alcohols such as methanol, polar solvents such as nitrile solvents such as acetonitrile and water, and nonpolar solvents such as aromatic solvents such as toluene. Two or more of these solvents may be used in mixture form. Among these solvents, polar solvents are preferred, and lower alcohols and water are more preferred in that they can fully achieve the effects of the present invention by acting as an oxidation source. Here, the oxidation source is a source of oxygen atoms to convert the barium introducing agent into an oxide.

[0028] <Complexes, salts, or alkoxides containing divalent to tetravalent metal atoms other than barium> Furthermore, the coating solution for chemical vapor deposition may contain a complex, salt, or alkoxide having divalent to tetravalent metal atoms other than barium in order to obtain a barium-containing composite oxide film. Any metal element that can form a metal oxide film by chemical vapor deposition can be used as the metal element constituting the complex, salt, or alkoxide, but examples include Al, Zr, and Ti. Specific compounds include, for example, metal complexes such as aluminum tris(acetylacetonate), zirconium tetra(acetylacetonate), and titanium tetra(acetylacetonate), as well as aluminum isopropoxide, zirconium propoxide, and titanium tetraisopropoxide. When using the complex, salt, or alkoxide, the molar ratio of barium atoms in barium hydroxide to metal atoms contained in the complex or salt is preferably in the range of 1.0:0.01 to 1.0:1000, and more preferably in the range of 1.0:0.01 to 1.0:100, from the viewpoint of minimizing variation in barium content.

[0029] <Barium-containing membrane> The barium-containing film of the present invention is obtained by forming the coating solution for chemical vapor deposition by chemical vapor deposition, and the film thickness is preferably 0.1 μm or more and 30 μm or less. From the viewpoint of good expression of film properties, the film thickness of the barium-containing film is preferably 0.1 μm or more, and films with a film thickness exceeding 30 μm are prone to cracking. The barium-containing film may contain other metal atoms to control film properties such as dielectric properties and piezoelectric properties depending on the application. Furthermore, from the viewpoint of exhibiting properties derived from the barium element, such as high dielectric properties and high refractive index, the barium content of the barium-containing film of the present invention is preferably 0.5 at% to 60 at% relative to the total elements in the film, and more preferably 0.5 at% to 40 at%. Also, from the viewpoint of stable production with respect to the designed performance of the device, the standard deviation of the barium content of the present invention is preferably 2.0 or less, and more preferably 1.7 or less.

[0030] <Method for forming barium-containing films by chemical vapor deposition> The method for forming the barium-containing film can be any chemical vapor deposition method, and from the viewpoint of film formation temperature and film formation rate, mist CVD is preferred over thermal CVD.

[0031] Examples of mist CVD include a method for forming a barium-containing film by chemical vapor deposition (hereinafter also referred to as "one-component coating method") comprising a misting step of atomizing the coating solution for chemical vapor deposition and a mist supply step of supplying mist to a heated substrate surface and allowing it to react on the substrate, and a method for forming a barium-containing film by chemical vapor deposition (hereinafter also referred to as "multiple-component coating method") comprising a two-tank misting step of separately atomizing the coating solution for chemical vapor deposition and a metal source solution containing a complex, salt, or alkoxide having divalent to tetravalent metal atoms other than barium, and a multiple mist supply step of supplying each mist to a heated substrate surface and allowing it to react on the substrate. Here, the complex, salt, or alkoxide having divalent to tetravalent metal atoms other than barium contained in the metal source solution is exemplified by the complex, salt, or alkoxide that may be contained in the barium introduction agent for chemical vapor deposition. Furthermore, the metal source solution may contain the above-mentioned β-diketone compounds and solvents.

[0032] Figure 1 shows a schematic diagram of a film deposition apparatus (1) for thermal CVD. The film deposition apparatus (1) consists of a vaporizer, a film deposition section, and a vacuum pump connected by piping.

[0033] Figure 2 shows a schematic diagram of the film deposition apparatus (2) in the film deposition method using the multi-component coating solution described above. The film deposition apparatus (2) consists of two misting units, a mixing tank, and a film deposition machine (film deposition unit) connected by piping.

[0034] Figure 3 shows a schematic diagram of the film deposition apparatus (3) in the film deposition method using the one-component coating solution described above. The film deposition apparatus (3) consists of a misting unit and a film deposition machine (film deposition section) connected by piping.

[0035] Figure 4 shows a schematic diagram of a misting apparatus in a barium-containing film deposition system. The misting apparatus consists of a container for the raw material and an ultrasonic generator equipped with an ultrasonic transducer. The container is a glass cylinder with a Teflon® lid and a bottom made of polyethylene or tetrafluoroethylene-hexafluoropropylene copolymer film. Two glass pipes are provided to pass through the lid. The first pipe is provided to send a carrier gas (nitrogen) for transporting the mist into the container, and the second pipe is provided to send the mist generated in the container and the carrier gas to the film deposition machine. The container is placed in the ultrasonic generator along with water, and ultrasonic waves generated by the ultrasonic transducer are transmitted to the raw material via the water and film such as polyethylene, causing the raw material to be atomized.

[0036] Figure 5 shows a schematic diagram of the mixing tank in a barium-containing film deposition apparatus. The mixing tank is a glass container with a Teflon® lid. Three glass pipes are provided to pass through the lid. Two of the three pipes are connected to two atomizers by piping, and the central pipe is connected to the film deposition section by piping. The mist generated in the atomizers is transported to the film deposition section via the mixing tank. This mixing tank is mainly used to mix the mist generated in separate atomizers.

[0037] Figure 6 shows a schematic diagram of the film deposition section in a barium-containing film deposition apparatus. The film deposition section consists of a metal jig and a hot plate connected to a misting unit or mixing tank. The jig is connected to the misting unit or mixing tank by a silicone tube and is provided to heat the mist and substrate. As the heated mist passes over the substrate, a chemical reaction occurs on the substrate to form a barium-containing film. Also, as shown in Figure 5, if a jig with a large internal space is used, film deposition is possible not only on plate-shaped substrates but also on three-dimensional substrates. The hot plate is provided to heat the jig.

[0038] In mist CVD, oxidizing agents such as ozone, oxygen, and hydrogen peroxide may be used as oxygen sources, but ozone is more preferred. Furthermore, to prevent ignition of the atomized coating solution, water, alcohol, etc., may be used as oxygen sources. Here, the oxygen source refers to the source of oxygen atoms necessary to form a metal oxide film from the barium introducer and the complex, salt, or alkoxide having 2-4 valent metal atoms other than barium.

[0039] As the carrier gas, an inert gas that does not contain more than 10,000 ppm (by volume) of oxygen is preferred in order to suppress oxidation of the substrate surface. Furthermore, it is preferable to set the carrier gas flow rate to 20 m / min to 700 m / min on the substrate, and even more preferable to set it to 100 m / min to 500 m / min from the viewpoint of film deposition rate. The carrier gas flow rate is calculated using the following formula when forming a film in a closed system.

number

[0040] In CVD, when mist CVD is applied, it is preferable to form a barium-containing film by heating and reacting a mist of raw materials on a substrate in a temperature atmosphere of 200°C to 600°C, and it is even more preferable to form the film at 300°C to 500°C. [Examples]

[0041] The present invention will be described below with reference to examples, but the present invention is not limited to these examples.

[0042] <Example 1> <Preparation of coating solution for chemical vapor deposition> A coating solution for chemical vapor deposition was prepared using the raw materials and proportions listed in Table 1. <Formation of barium-containing film on substrate> A barium-containing film was formed on a substrate using the film deposition apparatus (thermal CVD apparatus) shown in Figure 1 by the following method. A coating solution for chemical vapor deposition was placed in a vaporizer (glass ampoule), vaporized by heating with a heater, and supplied to the film deposition section along with nitrogen gas. The pressure in the film deposition section was controlled by opening and closing a valve before the vacuum pump, and the reactor was heated with a heater. The coating solution introduced into the reactor underwent a chemical reaction on the substrate (30 mm × 30 mm) heated to 700°C in the center of the reactor, forming a metal oxide film on the substrate. The nitrogen gas flow rate was 5.0 L / min, and the cross-sectional area of ​​the mist path on the substrate was 20 cm². 2 The film deposition time was set to 10 minutes.

[0043] <Examples 2-9, 14-17, 19-21, Comparative Example 2> <Preparation of coating solution for chemical vapor deposition> A coating solution for chemical vapor deposition was prepared using the raw materials and proportions listed in Tables 1-3 and 5-8. <Formation of barium-containing film on substrate> A barium-containing film was formed on a substrate using the film deposition apparatus (mist CVD apparatus) described in Figures 3, 4, and 6, by the following method. A polyethylene or tetrafluoroethylene-hexafluoroethylene copolymer film was fixed to a glass cylinder (13 cm in diameter, 15 cm in height) 1 cm from the bottom using an O-ring and sealant. The top of the cylinder was fitted with a Teflon® lid, and two holes were drilled in the lid to insert glass pipes for nitrogen gas supply and mist transport. The glass tube for mist transport with a branch pipe was placed 1-2 cm away from the metal material on the hot plate, and the branch pipe was connected to a silicone tube for nitrogen gas supply. The cylinder was immersed in a water bath, and an ultrasonic transducer (ultrasonic atomization unit HMC-2401; manufactured by Honda Electronics Co., Ltd.) was placed directly below the polyethylene or tetrafluoroethylene-hexafluoropropylene copolymer film. The hot plate was placed inside a box filled with nitrogen, and film deposition was started only after the oxygen concentration dropped to below 1%. The above-mentioned film-forming coating solution was placed in a cylinder, and an ultrasonic transducer was activated. Ultrasound was transmitted to the film-forming coating solution via water in a tank and a polyethylene or tetrafluoroethylene-hexafluoroethylene copolymer film, causing a portion of the coating solution to be atomized. The atomized film-forming coating solution was transported onto the substrate (30 mm x 30 mm) using nitrogen gas. The substrate was heated to 450°C by the hot plate, and it was confirmed that the atomized film-forming coating solution had reached the substrate. A barium-containing film was then formed through a chemical reaction. The film thickness of the barium-containing film was measured using the following method. The nitrogen gas flow rate was 7.0 L / min, and the cross-sectional area of ​​the mist path on the substrate was 0.3 cm². 2 The film deposition time was 10 minutes, the ultrasonic transducer frequency was 2.4 MHz, the voltage was 24 V, and the current was 0.6 A.

[0044] <Examples 10-13, 18, 22> Examples 10-13, 18, and 22 were two-tank systems in which a coating solution for chemical vapor deposition and a metal source solution were prepared using the raw materials and proportions listed in Table 4-6. <Formation of barium-containing film on substrate> A barium-containing film was formed on a substrate using the film deposition apparatus (mist CVD apparatus) shown in Figure 2, 4-6, by the following method. A polyethylene or tetrafluoroethylene-hexafluoroethylene copolymer film was fixed to a glass cylinder (13 cm in diameter, 15 cm in height) 1 cm from the bottom using an O-ring and sealant. The top of the cylinder was fitted with a Teflon® lid, and two holes were drilled in the lid to insert glass pipes for nitrogen gas supply and mist transport. A glass tube for mist transport with a branch pipe was placed 1-2 cm from a metal material on a hot plate, and the branch pipe was connected to a silicone tube for nitrogen gas supply. The cylinder was immersed in a water bath, and an ultrasonic transducer (ultrasonic atomization unit HMC-2401; manufactured by Honda Electronics Co., Ltd.) was placed directly below the polyethylene or tetrafluoroethylene-hexafluoropropylene copolymer film. The hot plate was placed inside a nitrogen-filled box, and film deposition was started only after the oxygen concentration dropped to below 1%. The above-mentioned film-forming coating solution and metal source solution were placed separately in two cylinders, and an ultrasonic transducer was activated. Ultrasound was transmitted to the film-forming coating solution and metal source solution via water in a tank and a polyethylene or tetrafluoroethylene-hexafluoroethylene copolymer film, causing a portion of the liquid to be atomized. The atomized film-forming coating solution and metal source solution were transported onto the substrate (30 mm x 30 mm) using nitrogen gas. The substrate was heated to 450°C by the hot plate, and it was confirmed that the atomized film-forming coating solution had reached the substrate. A barium-containing film was formed through a chemical reaction. The film thickness of the barium-containing film was measured using the following method. The nitrogen gas flow rate was 11 L / min, and the cross-sectional area of ​​the mist path on the substrate was 0.3 cm². 2 The film deposition time was 10 minutes, the ultrasonic transducer frequency was 2.4 MHz, the voltage was 24 V, and the current was 0.6 A.

[0045] <Comparative Example 1> <Preparation of coating solution for film formation> A coating solution for film formation was prepared using the raw materials and proportions listed in Table 8. <Formation of barium-containing film on substrate> A film-forming coating solution prepared with the composition shown in Table 8 was applied to a substrate by spin coating, and then heated in a furnace heated to 1200°C to obtain a barium-containing film.

[0046] The samples obtained above were evaluated as follows. The results are shown in Table 1-8.

[0047] <Measurement of film thickness of barium-containing films> The film thickness of the barium-containing film was measured by forming the film on a 30 x 30 mm silicon wafer, which served as the substrate, and measuring the film thickness using a surface shape measuring instrument (DektakXT-S: manufactured by Bruker Japan Co., Ltd.). On the surface of the resulting barium-containing film laminate, the shape was measured from 3.5 mm from the edge to the edge, and the difference in height from the substrate surface was measured. Measurements were taken at a total of 10 spots at both ends, and the average value was taken as the film thickness.

[0048] <Film formation speed> The film deposition rate was determined as the film thickness that could be deposited per minute (nm / min) from the film thickness measured using the film thickness measurement method and the deposition time.

[0049] <Measurement of the composition of barium-containing membranes> The number ratios per unit volume of barium atoms, 2- to 4-valent metal atoms excluding barium, oxygen atoms, and carbon atoms were calculated using Dynamic SIMS (PHI ADEPT: Ulvac-PHI). The conditions for Dynamic SIMS were as follows: Primary ion species: Cs+, Primary acceleration voltage: 5.0 kV, Detection area: 45 × 45 μm. As a sample, a silicon wafer was used as the substrate, and a 1 μm barium-containing film was formed on the substrate. Measurements were taken in the depth direction of the sample center, and the depth of the point where silicon was detected was defined as 1 μm. The elemental ratios of the four atoms were calculated from the secondary ion intensity, relative sensitivity coefficient, and atomic weight of each of the barium atoms, 2- to 4-valent metal atoms excluding barium, oxygen atoms, and carbon atoms.

[0050] <Evaluation of variability in barium content> The variability in barium content was evaluated based on values ​​calculated from the composition measurements of the barium-containing membranes described above. For barium content variability, the standard deviation of the barium content ratio was calculated for n=5, and a standard deviation of 2.0 or less was considered acceptable.

[0051] [Table 1]

[0052] [Table 2]

[0053] [Table 3]

[0054] [Table 4]

[0055] [Table 5]

[0056] [Table 6]

[0057] [Table 7]

[0058] [Table 8]

[0059] In Table 1-8, Barium hydroxide is barium hydroxide octahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.); Acetylacetone is manufactured by Kishida Chemical Co., Ltd. 3-Ethyl-2,4-pentanedione is manufactured by Tokyo Chemical Industry Co., Ltd. Dibenzoylmethane is manufactured by Tokyo Chemical Industry Co., Ltd. 3,5-Heptanedione is manufactured by Tokyo Chemical Industry Co., Ltd. 2,6-dimethyl-3,5-heptanedione is manufactured by Tokyo Chemical Industry Co., Ltd. Trifluorodimethylhexanedione is 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (manufactured by Sigma-Aldrich); Zirconium acetylacetonate is zirconium(IV) acetylacetonate (manufactured by Tokyo Chemical Industry Co., Ltd.); Titanium acetylacetonate is a titanium(IV) acetylacetonate solution (approximately 63% isopropyl alcohol solution) manufactured by Tokyo Chemical Industry Co., Ltd. Aluminum acetylacetonate is aluminum tris(acetylacetonate) ("Aluminum Chelate A" (manufactured by Kawaken Fine Chemical Co., Ltd.)); Aluminum isopropoxide is manufactured by Fujifilm Wako Pure Chemical Industries, Ltd. Titanium tetraisopropoxide is manufactured by Tokyo Chemical Industry Co., Ltd. Barium trifluorodimethylhexanedinate was prepared using 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione (manufactured by Sigma-Aldrich), barium hydroxide octahydrate (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.), and methanol (manufactured by Kishida Chemical Co., Ltd.) by the method described in Patent Document 2; Ba(NO3)2 is manufactured by Fujifilm Wako Pure Chemical Corporation. MeOH is methanol (manufactured by Kishida Chemical Co., Ltd.); Toluene refers to toluene (manufactured by Kishida Chemical Co., Ltd.).

[0060] The barium-containing films obtained in Examples 1-22 were formed using a barium introduction agent for chemical vapor deposition containing barium hydroxide, and satisfied the requirements for variation in barium content.

[0061] The barium-containing films obtained in Examples 3-19, 21, and 22 were formed using a barium introduction agent for chemical vapor deposition, which contained barium hydroxide and a β-diketone compound represented by formula (1), with a molar ratio of barium hydroxide to the β-diketone compound of 1.0:0.01 to 1.0:100, and satisfied the variability of the barium content.

[0062] The barium-containing films obtained in Examples 8-14, 17-19, 21, and 22 satisfied the variability in barium content even when the coating solution contained complexes, salts, or alkoxides having 2- to 4-valent metal atoms other than barium.

[0063] The barium-containing films obtained in Examples 10-13, 18, and 22 were formed using the multi-liquid coating method described above, and satisfied the requirements for variation in barium content.

[0064] The barium-containing film obtained in Comparative Example 1 was not produced using a barium introduction agent for chemical vapor deposition, nor was it produced by chemical vapor deposition. Therefore, it did not satisfy the requirement for variability in barium content.

[0065] The barium-containing film obtained in Comparative Example 2 was formed without using the barium introduction agent for chemical vapor deposition of the present invention, and therefore did not satisfy the requirement for variability in barium content.

Claims

1. A barium introduction agent for chemical vapor deposition containing barium hydroxide.

2. A barium introduction agent for chemical vapor deposition according to claim 1, comprising a β-diketone compound represented by the following formula (1), wherein the molar ratio of barium hydroxide to the β-diketone compound is 1.0:0.01 to 1.0:

100. 【Chemistry 1】 (In formula (1), R １ and R ２ Each is independently a hydrocarbon group having 1 to 6 carbon atoms, R ３ (This represents a hydrogen atom or a hydrocarbon group having 1 to 6 carbon atoms.)

3. A coating solution for chemical vapor deposition, comprising the barium introducing agent for chemical vapor deposition described in claim 2 and a solvent.

4. The complex, salt, or alkoxide contains divalent to tetravalent metal atoms other than barium. The coating solution for chemical vapor deposition according to claim 3, wherein the molar ratio of barium atoms in barium hydroxide to metal atoms contained in the complex, salt, or alkoxide is 1.0:0.01 to 1.0:1000.

5. A barium-containing film obtained by forming a coating solution for chemical vapor deposition according to claim 3 or 4 by chemical vapor deposition.

6. A misting step for atomizing the coating liquid for chemical vapor deposition according to claim 3 or 4, A method for forming a barium-containing film by chemical vapor deposition, comprising a mist supply step of supplying mist to a heated substrate surface and allowing it to react on the substrate.

7. A two-tank misting step in which a coating liquid for chemical vapor deposition according to claim 3 or 4 and a metal source solution containing a complex, salt, or alkoxide having divalent to tetravalent metal atoms other than barium are separately misted, A method for forming a barium-containing film by chemical vapor deposition, comprising a multiple mist supply step of supplying different mists to the heated surface of a substrate and allowing them to react on the substrate.

8. A method for forming a barium-containing film by chemical vapor deposition according to claim 7, wherein mist is supplied to a heated substrate surface such that the molar ratio of barium atoms to 2- to 4-valent metal atoms other than barium contained in the mist is 1.0:0.01 to 1.0:1000.

Images