JP3585406B2 - Method for producing crystallized ceramic film and ceramic film thereof - Google Patents

Description

[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a novel method for producing a crystallized ceramic film. In particular, the present invention relates to a method of obtaining a crystallized ceramic film at a low temperature by heat-treating a ceramic amorphous or partially crystallized precursor film formed by a chemical method or a physical method in a high-pressure gas phase.
[0002]
[Prior art]
Ceramic membranes have various properties and functions, and various applications have been developed. If the surface of the material is covered with a ceramic film, corrosion and wear can be suppressed. Further, since the ceramic film has special electric characteristics, it can be used for various electronic devices and photoelectric devices. Regarding electronic devices, applications to DRAMs, non-volatile RAMs, piezoelectric devices, capacitors, sensors, pyroelectric devices, actuators, and the like have been developed. In addition, the ferroelectric ceramic film can be applied to a nonvolatile RAM due to spontaneous polarization, or can be applied to a DRAM due to the high dielectric constant of the ferroelectric. Regarding photoelectric devices, applications of non-linear optical devices, conductive films, photoelectric switches, surface acoustic waves, optical waveguides, pyrosensors, photoelectric displays, reflective films, or antireflective films have been developed.
[0003]
Various manufacturing methods have been developed for manufacturing ceramic membranes. These methods are generally divided into chemical and physical methods. Chemical methods include chemical vapor deposition, spin coating, dipping, and sol-gel methods. Examples of the physical process include an evaporation method, an ion beam method, a molecular beam method, an electron beam method, sputtering, and laser sputtering. Generally, a film formed on a substrate at a low temperature is almost amorphous or partially crystallized. In order to obtain a crystallized film, high-temperature treatment during film formation or high-temperature heat treatment after film formation is required. Since the reaction between the ceramic film and the substrate is likely to occur in the high-temperature heat treatment, the properties of the film are greatly affected. In the field of semiconductors, a frequently used substrate for ferroelectric ceramic films is a silicon substrate. The silicon is easily oxidized by the high-temperature heat treatment, and the components of the silicon and the ceramic film are easily diffused, so that the interaction and the interface reaction between the silicon and the ceramic film are likely to occur. Due to such an interfacial reaction, the components of the ceramic film tend to come off, and silicon diffuses into the ceramic film, so that the properties of the ceramic film and the substrate are significantly deteriorated. Furthermore, since the high-temperature heat treatment easily causes the particles of the film to grow, the surface roughness of the film increases, which hinders subsequent processing such as etching.
[0004]
Several processes have been developed to remedy the disadvantages of conventional high temperature heat treatment. Among them, a hydrothermal process or an electrochemical hydrothermal process is a method in which a substrate is put into a reaction solution and a film is formed by a chemical reaction between the solution and the substrate. In such a process, since the substrate and the reaction solution come into direct contact with each other, when a strong acid solution and a strong alkali solution are used, the substrate is easily corroded, which is disadvantageous for a semiconductor device. Although treatment with a laser, an ion beam, an electron beam, a molecular beam, or the like can lower the crystallization temperature of the ceramic film, it has a difficulty in manufacturing a large-area film because the beam size is small. When a scanning device is used in combination, it is possible to form a large-area film, but there is a limitation on the scanning speed, which is disadvantageous for mass production. Alternatively, since the energy of a laser, an ion beam, a molecular beam, and an electron beam is high, the structure of the ceramic film is easily broken, defects easily occur, and the properties of the film are greatly affected.
[0005]
[Problems to be solved by the invention]
In order to solve the above problems, the researchers of the present invention have conducted a series of experiments, and as a result, have invented a novel method for crystallizing a ceramic film, and have realized a low-temperature manufacturing process of a crystallized ceramic film.
[0006]
It is an object of the present invention to provide a method for crystallizing a ceramic amorphous or partially crystallized precursor film at a low temperature.
[0007]
Another object of the present invention is to provide a crystallized ceramic film manufactured by the above method.
[0008]
[Means for Solving the Problems]
In order to solve the above problems, the present invention has, on a substrate to form or by physical methods to chemical methods ceramic amorphous or partially crystallized precursor film, the precursor film of more than 5 atmospheric pressure A method for producing a crystallized ceramic film characterized by being crystallized by heat treatment in a high-pressure gas phase.
[0009]
The high-pressure gas phase of the present invention can be realized by the following method, but is not limited to the following method. That is, a method of generating a high-pressure gas phase by a vapor pressure of a volatile substance or a method of generating a high-pressure gas phase by a high-pressure gas jet can be used.
[0010]
Ceramics are inorganic non-metallic compounds. Oxides, nitrides, borides, carbides, halides, hydrides and the like can be mentioned depending on the type of anion. The structure of ceramics is rock salt type, zinc blende type, wurtzite type, perovskite type, composite perovskite type, layered perovskite type, pyrochlore type, corundum type, ilmenite type, rutile type, spinel type, reverse spinel type, olivine type, Examples include a fluorite type, a reverse fluorite type, a calcium chloride type, a tungsten bronze type, a lithium niobate type, a stomium tantalate type, a silicate type and a mixed type thereof.
[0011]
The method of the present invention is not limited to a particular ceramic membrane component or crystal structure. As a result of a series of experiments, it was confirmed that the present invention can effectively suppress the crystallization temperature of the ceramic film regardless of the components and the crystal structure of the ceramic film.
[0012]
The method of the present invention can produce, but is not limited to, ceramic membranes having the following structures: rock salt type, zinc blende type, wurtzite type, perovskite type, composite perovskite type, layered perovskite type, pyrochlore type , Corundum type, ilmenite type, rutile type, spinel type, reverse spinel type, olivine type, fluorite type, reverse fluorite type, calcium chloride type, tungsten bronze type, lithium niobate type, lithium niobate type, stotium tantalate type, silica Acid salt type and its mixed type.
[0013]
Films that can be produced by the present invention include, for example, SrBi ₂ Ta ₂ O ₉ , BaBi ₂ Ta ₂ O ₉ , (Sr, Ba) Bi ₂ Ta ₂ O ₉ , SrBi ₂ (Ta, Nb) ₂ O ₉ , Pb (Zr, Ti) O ₃ , Sr ₂ (Ta, Nb) ₂ O ₇ , PbTiO ₃ , Pb ₃ Nb ₄ O ₁₃ , Ta ₂ O _{5 and the} like, but the method of the present invention is not limited to the above films. The film includes a ferroelectric film and a paraelectric film.
[0014]
A key feature of the present invention is to promote the formation of a crystallized ceramic film in a high pressure gas phase environment. The pressure is above 5 atmospheres, more preferably from 10 to 400 atmospheres. Due to the high pressure heat treatment, the process of forming the crystallized ceramic film can take place at low temperatures. According to the present invention, the crystallized ceramic film and the heat treatment temperature can be suppressed to 600 ° C. or less. A preferred heat treatment temperature is 550 ° C or less, and a more preferred heat treatment temperature is 500 ° C or less. Further, after the high-pressure heat treatment, another heat treatment at a normal pressure at a temperature of 100 ° C. to 600 ° C. further improves the properties of the film.
[0015]
The ceramic film can be formed by a chemical method or a physical method. Chemical methods include chemical vapor deposition, spin coating, dipping, and sol-gel methods. Examples of the physical method include an electrodeposition method, an electrophoresis method, an evaporation method, an ion beam method, a molecular beam method, an electron beam method, a sputtering method, and a laser method.
[0016]
The crystallization method of the present invention can produce a large-area ceramic film without requiring complicated installation of a laser, an ion beam, an electron beam, and the like. In the example, a crystallized Pb (Zr, Ti) O ₃ film could be formed at 300 ° C. The process of the present invention can effectively reduce the temperature of the conventional crystallization process significantly and can be combined with the semiconductor process, and can be applied to a DRAM (Dynamic Random Access Memory) or a non-volatile RAM (Non-Volatile Random Access Memory). Enable application. In a low-temperature process, oxidation of the substrate or metal wiring can be suppressed, or an interface reaction between the film and the substrate can be suppressed. Alternatively, the microstructure of the film is improved, the particle diameter of the film is reduced, and the flatness of the film can be improved.
[0017]
The substrate used in the present invention is not particularly limited. Examples include silicon, glass, ceramics, polymers, metals, and composites thereof. Materials with low melting points (eg, glass and polymers) that cannot normally be used in high temperature crystallization processes can also be used in the present invention. Further, the substrate is not limited to a flat substrate, and a substrate having a curved surface can be used.
[0018]
The volatile substance used to generate the high-pressure gas phase of the present invention may be any volatile substance that can generate steam by heating. In the case of a gas, examples of the volatile substance include oxygen, nitrogen, hydrogen, argon, water vapor, carbon dioxide, carbon monoxide, nitrogen oxide, ozone, and a mixture thereof. In the case of nitride and carbide films, the inert gas is preferably, for example, nitrogen or argon. When using a volatile liquid, an organic or inorganic solvent (eg, hydrogen peroxide, alcohol, ketone, ether, aromatic compound), an organic or inorganic alkali (eg, ammonia, amine, amide), an organic or inorganic acid ( For example, nitric acid, hydrochloric acid, acetic acid, and sulfuric acid), a metal salt solution, and a mixture thereof. If a solution is used as the vapor pressure source, the amount of the solution must be at least sufficient to create a sufficient vapor pressure at the heating temperature. However, the amount of solution must be limited before heating so that it does not come into direct contact with the membrane. High pressure gas jets can also promote crystallization of the film. Gas jets include those composed of oxygen, hydrogen, nitrogen, argon, water vapor, carbon dioxide, carbon monoxide, ozone, nitric oxide, and mixtures thereof.
[0019]
【Example】
Example 1
Based on the stoichiometry of SrBi ₂ Ta ₂ O ₉ , strontium 2-ethylhexanoate, bismuth 2-ethylhexanoate and tantalum ethoxide were mixed to prepare a precursor of SrBi ₂ Ta ₂ O ₉ . The mixed precursor was spincoated on Pt / Ti / _SiO 2 / Si substrate. After drying the resulting film at 150 ° C., it was heat-treated again at 350 ° C. for 10 minutes to evaporate the organic solvent. As a result of analyzing the film by X-ray diffraction, an amorphous film was confirmed. The membrane was placed in a high pressure chamber and distilled water was placed in the chamber. The amount of distilled water charged was such that it did not directly contact the membrane before heating. Subsequently, heat treatment was performed at 260 ° C. and 300 ° C. for 2 hours. The vapor pressure at 260 ° C. was 47.6 atm, and the vapor pressure at 300 ° C. was 78.9 atm. After heat treatment at 260 ° C., the film only partially crystallized, but when heat treated at 300 ° C., an X-ray diffraction pattern showing good crystallization was observed as shown in FIG. This example demonstrated the formation of a crystallized film under high pressure.
Comparative Example 1
As in Example 1, a precursor of SrBi ₂ Ta ₂ O ₉ was prepared, and then spin-coated on a Pt / Ti / SiO ₂ / Si substrate. The resulting film was heat-treated at 300 ° C. for 2 hours in an electric furnace. After heating at 300 ° C., the film remained amorphous. The X-ray diffraction diagram of the film is shown in FIG.
[0020]
After heating the film to 700 ° C. in an electric furnace, a film having the same crystallinity as in Example 1 was obtained. Therefore, the crystallization temperature of Example 1 was 400 ° C. lower than that of Comparative Example 1. According to AFM observation, the particle diameter of the film of Example 1 was smaller than that of the comparative example, or the flatness of the film of Example 1 was better than that of the film of Comparative Example 1. According to the SIMS analysis, bismuth was remarkably diffused into the substrate in the film heat-treated at 700 ° C. in Comparative Example 1, but the phenomenon was not observed in the film of Example 1. Thus, this high pressure treatment effectively reduced the crystallization temperature of the film, suppressed interdiffusion between the film and the substrate, or improved the microstructure of the film.
Example 2
A precursor of SrBi ₂ Ta ₂ O ₉ was made as in Example 1. The mixed precursor was spincoated on Pt / Ti / _SiO 2 / Si substrate. After drying the resulting film at 150 ° C., it was heat-treated again at 350 ° C. for 10 minutes to evaporate the organic solvent. As a result of analyzing the film by X-ray diffraction, an amorphous film was confirmed. The membrane was placed in a high pressure chamber, and aqueous ammonia (pH = 12) was placed in the chamber. The amount of the added ammonia water was such that it did not come into direct contact with the membrane before heating. During the heating, the vapor pressure increased due to the evaporation of the ammonia. Upon heating to 300 ° C., the pressure reached 89.4 atm. The pressure is higher than in Example 1. After heat treatment at 300 ° C. for 2 hours, an X-ray diffraction pattern showing good crystallization was observed as shown in FIG. This example proved that the high pressure due to the ammonia water vapor pressure promoted the formation of the crystallized film .
Example 3
A film of SrBi ₂ Ta ₂ O ₉ was formed on a Pt / Ti / SiO ₂ / Si substrate by RF-sputtering. The target was made by a solid-state reaction method, the distance between the target and the substrate was 3 cm, and the sputtering time was 30 minutes. The resulting film was placed in a high pressure chamber and heat treated at 56.5 atmospheres and 280 ° C. for 2 hours. The X-ray diffraction diagram of the resulting film is shown in FIG. As can be seen from this figure, it was confirmed that the heat treatment in the high-pressure vapor phase promoted the crystallization of the film formed by sputtering.
Example 4
A mixture of strontium 2-ethylhexanoate, barium 2-ethylhexanoate, bismuth 2-ethylhexanoate, and tantalum ethoxide was used to form a precursor of (Sr _0.5 Ba _0.5 ) Bi ₂ Ta ₂ O ₉ . And This precursor was spin-coated on a Pt / Ti / SiO ₂ / Si substrate. After drying the resulting film at 150 ° C., it was heat-treated again at 350 ° C. for 10 minutes to evaporate the organic solvent. As a result of analyzing the film by X-ray diffraction, an amorphous film was confirmed. Further, the membrane was placed in a high-pressure chamber, and distilled water was placed in the chamber. The amount of distilled water charged was such that it did not directly contact the membrane before heating. After heat treatment at 280 ° C. for 2 hours, the pressure was 56.5 atm. After heat treatment at 280 ° C., an X-ray diffraction pattern showing good crystallization was observed. This example demonstrated that high pressure promoted the formation of a crystallized SrBi ₂ Ta ₂ O ₉ solid solution film.
Example 5
A precursor of Pb (Zr _0.5 Ti _0.48 ) O ₃ was prepared by mixing lead 2-ethylhexanoate, zirconium n-propoxide and tetraisopropyl orthotitanate. The mixed precursor was spincoated on Pt / Ti / _SiO 2 / Si substrate. The resulting film was dried at 150 ° C., and then heat-treated at 350 ° C. for 10 minutes to evaporate the organic solvent. As a result of analyzing the film by X-ray diffraction, an amorphous film was confirmed. The membrane was placed in a high pressure chamber and distilled water was placed in the chamber. The amount of distilled water charged was such that it did not directly contact the membrane before heating. Heat treatment was performed at 300 ° C. for 4 hours. The air pressure at that time was 77.6 atmospheric pressure. After the heat treatment, an X-ray diffraction pattern showing good crystallization was observed as shown in FIG. This example demonstrated that high pressure heat treatment promoted the formation of a crystallized Pb (Zr _0.52 Ti _0.48 ) O ₃ film.
Comparative Example 2
As in Example 5, a precursor of Pb (Zr _0.52 Ti _0.48 ) O ₃ was generated and then spin-coated on a Pt / Ti / SiO ₂ / Si substrate. The resulting film was heat-treated at 300 ° C. for 4 hours in an electric furnace. After heating at 300 ° C., the film remained amorphous. The X-ray diffraction diagram of the film is shown in FIG. As compared with Example 5, it was confirmed that the formation of the crystallized Pb (Zr _0.52 Ti _0.48 ) O ₃ film was promoted by the high-pressure heat treatment of the present invention.
Example 6
Based on the stoichiometry of PbTiO _3, a mixture of 2-ethylhexanoic San'namarishio and tetraisopropyl orthotitanate, it created a precursor of PbTiO _3. The mixed precursor was spincoated on Pt / Ti / _SiO 2 / Si substrate. The resulting film was dried at 150 ° C., and then heat-treated at 350 ° C. for 10 minutes to evaporate the organic solvent. As a result of analyzing the film by X-ray diffraction, an amorphous film was confirmed. The membrane was placed in a high pressure chamber and distilled water was placed in the chamber. The amount of distilled water charged was such that it did not directly contact the membrane before heating. Heat treatment was performed at 300 ° C. for 2 hours. The air pressure at that time was 77.6 atmospheric pressure. After the heat treatment, as shown in FIG. 7, an X-ray diffraction pattern showing good crystallization was observed. This example demonstrated that high pressure heat treatment promoted the formation of a crystallized PbTiO ₃ film.
Example 7
Based on the stoichiometry of Pb ₃ Nb ₄ O _13, a mixture of 2-ethylhexanoic San'namarishio and niobium ethoxide _to prepare a precursor of Pb ₃ Nb _{4 O 13.} The mixed precursor was spincoated on Pt / Ti / _SiO 2 / Si substrate. The resulting film was dried at 150 ° C., and then heat-treated at 350 ° C. for 10 minutes to evaporate the organic solvent. As a result of analyzing the film by X-ray diffraction, an amorphous film was confirmed. The membrane was placed in a high pressure chamber and distilled water was placed in the chamber. The amount of distilled water charged was such that it did not directly contact the membrane before heating. Heat treatment was performed at 300 ° C. for 2 hours. The air pressure at that time was 77.6 atmospheric pressure. After the heat treatment, as shown in FIG. 8, an X-ray diffraction pattern showing good crystallization was observed. This example demonstrated that high pressure heat treatment promoted the formation of a crystallized Pb ₃ Nb ₄ O ₁₃ film.
Comparative Example 3
As in Example 7, a precursor of Pb ₃ Nb ₄ O ₁₃ was prepared, and then spin-coated on a Pt / Ti / SiO ₂ / Si substrate. The resulting film was heat-treated at 300 ° C. for 2 hours in an electric furnace. After heating at 300 ° C., the film remained amorphous. The X-ray diffraction diagram of the film is shown in FIG. In comparison with Example 7, the present invention confirmed that the formation of the crystallized Pb ₃ Nb ₄ O ₁₃ film was promoted by the high-pressure heat treatment.
Example 8
Based on the stoichiometry of Pb ₃ Nb ₄ O _13, a mixture of 2-ethylhexanoic San'namarishio and niobium ethoxide _to prepare a precursor of Pb ₃ Nb _{4 O 13.} The mixed precursor was dipped on a Pt / Ti / SiO ₂ / Si substrate. The moving speed of the film when dipping was 0.3 cm / sec. The resulting film was dried at 150 ° C., and then heat-treated at 350 ° C. for 10 minutes to evaporate the organic solvent. As a result of analyzing the film by X-ray diffraction, an amorphous film was confirmed. The membrane was placed in a high pressure chamber and distilled water was placed in the chamber. The amount of distilled water charged was such that it did not directly contact the membrane before heating. Heat treatment was performed at 300 ° C. for 2 hours. The air pressure at that time was 77.6 atmospheric pressure. After the heat treatment, an X-ray diffraction pattern showing good crystallization was observed. This example demonstrated that high pressure heat treatment promoted the formation of a crystallized Pb ₃ Nb ₄ O ₁₃ film.
Example 9
Tantalum ethoxide was used as a precursor of Ta ₂ O ₅ . The precursor was spin-coated on a Pt / Ti / SiO ₂ / Si substrate. The resulting film was dried at 150 ° C., and then heat-treated at 350 ° C. for 10 minutes to evaporate the organic solvent. As a result of analyzing the film by X-ray diffraction, an amorphous film was confirmed. The membrane was placed in a high pressure chamber and distilled water was placed in the chamber. The amount of distilled water charged was such that it did not directly contact the membrane before heating. Heat treatment was performed at 350 ° C. for 2 hours. At that time, the atmospheric pressure was 156.4 atmospheric pressure. After the heat treatment, an X-ray diffraction pattern showing good crystallization was observed. This example demonstrated that high pressure heat treatment promoted the formation of a crystallized Ta ₂ O ₅ film.
[0021]
【The invention's effect】
In the present invention, since the ceramic film can be crystallized at a low temperature, the energy of the heat treatment can be reduced, and the interface reaction between the film and the substrate caused by the high-temperature heat treatment can be suppressed. Further, the grain size of the film obtained at a low temperature is small, the roughness of the film is reduced, and the flatness of the film is increased.
[0022]
The present invention does not require expensive and complicated equipment of high energy, for example, equipment such as a laser, an ion beam, and an electron beam, and can keep equipment costs low.
[0023]
Films manufactured by the present invention are used for DRAMs, nonvolatile RAMs, multilayer capacitors, actuators, piezoelectric devices, pyroelectric devices, sensors, photoelectric display devices, photoelectric switches, non-linear optical devices, conductive films, reflective films and anti-reflective films, etc. Can be applied.
[Brief description of the drawings]
FIG. 1 is an X-ray diffraction diagram of a crystallized film obtained by subjecting a SrBi ₂ Ta ₂ O ₉ precursor film obtained by spin coating in Example 1 to a heat treatment at 78.9 atmospheric pressure and 300 ° C. for 2 hours. .
FIG. 2 is an X-ray diffraction diagram of a film obtained by subjecting a SrBi ₂ Ta ₂ O ₉ precursor film obtained by spin coating in Comparative Example 1 to a heat treatment at 300 ° C. for 2 hours at normal pressure.
FIG. 3 is an X-ray diffraction pattern of a film obtained by subjecting a SrBi ₂ Ta ₂ O ₉ precursor film obtained by spin coating to a heat treatment at 89.4 atmospheric pressure and 300 ° C. for 2 hours using ammonia water in Example 2. FIG.
FIG. 4 is an X-ray diffraction diagram of a film obtained by subjecting a SrBi ₂ Ta ₂ O ₉ precursor film obtained by RF sputtering in Example 3 to heat treatment at 56.5 atmospheric pressure and 280 ° C. for 2 hours.
FIG. 5 is a cross-sectional view of a film obtained by subjecting a Pb (Zr _0.52 Ti _0.48 ) O ₃ precursor film obtained by spin coating in Example 5 to heat treatment at 77.6 atmospheric pressure at 300 ° C. for 4 hours. FIG.
6 is an X-ray diffraction diagram of a film obtained by subjecting a Pb (Zr _0.52 Ti _0.48 ) O ₃ precursor film obtained by spin coating in Comparative Example 2 to a heat treatment at 300 ° C. for 4 hours.
FIG. 7 is an X-ray diffraction diagram of a film obtained by subjecting a PbTiO ₃ precursor film obtained by spin coating in Example 6 to heat treatment at 77.6 atmospheric pressure and 300 ° C. for 2 hours.
FIG. 8 is an X-ray diffraction diagram of a film obtained by subjecting a Pb ₃ Nb ₄ O ₁₃ precursor film obtained by spin coating in Example 7 to a heat treatment at 77.6 atmospheric pressure and 300 ° C. for 2 hours.
FIG. 9 is a film X-ray diffraction diagram obtained by subjecting a Pb ₃ Nb ₄ O ₁₃ precursor film obtained by spin coating in Comparative Example 3 to a heat treatment at 300 ° C. for 2 hours.

Claims (18)

A method for producing a crystallized ceramic film, comprising forming a ceramic amorphous or partially crystallized precursor film on a substrate by a chemical method or a physical method, and then forming the precursor film at 10 to 400 atm . A method for producing a crystallized ceramic film, characterized by crystallizing by heat treatment in a high-pressure gas phase. The method according to claim 1, wherein the high pressure is derived from a vapor pressure of the volatile substance. The volatile substance, oxygen, hydrogen, nitrogen, argon, water vapor, ozone, carbon dioxide, carbon monoxide, nitric oxide, hydrogen peroxide, organic solvent, inorganic solvent, organic acid, inorganic acid, organic alkali, inorganic alkali, 3. The production method according to claim 2, which is a metal salt solution or a mixture thereof. The method of claim 1, wherein the high pressure is derived from a high pressure gas jet. 5. The method according to claim 4, wherein the gas jet comprises oxygen, hydrogen, nitrogen, argon, water vapor, carbon dioxide, carbon monoxide, ozone, nitrogen oxide or a mixture thereof. The method according to claim 1, wherein the chemical method is a chemical vapor deposition, a spin coating, a dipping, or a sol-gel method. 2. The method according to claim 1, wherein the physical method is a sputtering, an electrodeposition method, an electrophoresis method, an evaporation method, an ion beam method, an electron beam method, a molecular beam method, or a laser method. The method according to claim 1, wherein the temperature of the heat treatment is 600 ° C. or less. The method according to claim 8 , wherein the temperature of the heat treatment is 550 ° C. or less. The method according to claim 9 , wherein the temperature of the heat treatment is 500 ° C. or less. 2. The method according to claim 1, wherein the ceramic film is ferroelectric or paraelectric. The ceramic film, SrBi ₂ Ta ₂ O ₉ , BaBi ₂ Ta ₂ O ₉ , (Sr _x Ba _1-x ) Bi ₂ Ta ₂ O ₉ , (Sr _x Ba _1-x ) (Ta _y Nb _1-y ) ₂ O ₉ , selected from the group consisting of Pb (Zr _x Ti _1-x ) O ₃ and Sr ₂ (Ta _x Nb _1-x ) ₂ O ₇ (where x and y range from 0 to 1) a ferroelectric ceramic film manufacturing method of claim 1 1, wherein that. The ceramic membrane, Ta ₂ O ₅ and Pb ₃ Nb ₄ The process according to claim 1 1, wherein the paraelectric ceramic film selected from the group consisting of O _13. The crystal structure of the ceramic film is rock salt type, zinc blende type, wurtzite type, perovskite type, composite perovskite type, layered perovskite type, pyrochlore type, colangum type, ilmenite type, rutile type, spinel type, reverse spinel type. 2. The method according to claim 1, which is of a olivine type, a fluorite type, a reverse fluorite type, a calcium chloride type, a tungsten bronze type, a lithium niobate type, a strontium tantalate type, a silicate type, or a mixed type thereof. . The crystal structure of the ceramic film is perovskite type, composite perovskite type, layered perovskite type, pyrochlore type, spinel type, reverse spinel type, fluorite type, reverse fluorite type, tungsten bronze type, or a mixed type thereof. 1 4 the method according. The method according to claim 1, wherein the substrate is made of silicon, glass, ceramics, metal, polymer, or a composite thereof. The method according to claim 1, wherein after the heat treatment, the ceramic film is further heat-treated at a temperature of 100 ° C. to 600 ° C. at normal pressure. A crystallized ceramic film obtained by the method of claim 1, 2, 4, or 17 .

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