JPH0449721B2 - - Google Patents

Description

[Detailed description of the invention]

Industrial application field: The present invention is directed to lead titanium zirconate (hereinafter referred to as "three-component PZT"), which is formed by adding a third component as a solid solution on a substrate.
The present invention relates to a method for producing a thin film dielectric in which a thin film of either lanthanum-containing lead titanium zirconate (hereinafter referred to as "PLZT") is formed. Conventional technology: Thin film dielectrics have traditionally been produced by press-molding a mixture of inorganic metal compounds in the form of powder and sintering at high temperatures to produce dielectric porcelain, which is then polished to the desired thickness. Manufactured using In this method, it is extremely difficult to produce a thin film dielectric that is as thin as 100 microns or less and has a high dielectric constant, which is a condition for an excellent dielectric element. In particular, polishing a highly hard, highly crystalline dielectric ceramic to a desired thickness tends to cause loss of crystal grains and cracks, and requires special equipment. Furthermore, since the sintering temperature is high, it is necessary to use special and expensive metal materials for the electrodes. Methods for manufacturing thin film dielectrics that can be used as excellent dielectric elements are being investigated by sputtering, vacuum evaporation, gas phase reaction, etc., but these methods require In the case of lead-containing dielectrics, the vapor pressure of lead oxide in particular is high and it easily volatilizes, making it difficult to control the stometchiometry, making it extremely difficult to obtain the desired dielectric properties, and preventing conduction. However, it has not yet been put into practical use. JP-A No. 56-28408 discloses that a solution containing an organometallic compound is applied onto a glass substrate by a dropping method or a dipping method, and the solution is coated in air at room temperature for 30 minutes, and then in a constant temperature bath at 110°C for 30 minutes. After drying for a minute to complete the hydrolysis reaction, place it in an electric furnace.
A method of manufacturing a dielectric film has been proposed in which the film is heated and fired at a temperature of 200°C to 300°C while forcing water vapor into the film. However, the solution of the organometallic compound exemplified in this method is extremely unstable and easily hydrolyzed by absorbing moisture in the atmosphere, making it difficult to obtain a homogeneous coating film. Furthermore, it is difficult to control the atmosphere during hydrolysis and calcination, especially the water vapor partial pressure. Furthermore, since it is difficult to decompose and release hydroxyl groups during firing due to the hydrolysis step, conduction occurs and it is impossible to manufacture a practical thin film dielectric. Although this method suggests that a dielectric thin film can be formed on a glass substrate, the publication does not indicate the specific dielectric properties of the obtained thin film, making it difficult to use it as a dielectric element. It has not been confirmed that a possible thin film dielectric could be produced. Japanese Patent Laid-Open No. 58-41723 and Japanese Patent Application No. 57-152739, filed by the applicant of the present invention, also contain a description of manufacturing a thin dielectric thin film on a substrate using a dielectric precursor solution. However, there is no description specifically indicating dielectric properties as a thin film dielectric. Problems to be Solved by the Invention The present invention provides a method for manufacturing a thin film dielectric that can be used as a dielectric element having high dielectric properties, in which a dielectric is formed in the form of a film on a substrate. purpose. Means for Solving the Problems The present invention provides one of the following (a) or (b) on a substrate.
This is a method for manufacturing a thin film dielectric formed by laminating two or more thin films of different dielectric compositions. (a) Compositional formula (1) Pb(Ti _x Zr _y ) _s (M′ _1/3 M″ _2/3 ) _t O ₃ …(1) (Here, M′ is divalent Mg, Co, Fe, Cr,
Zn, Mn, Ni or Cd M'' represents Nb or Ta, X is 0.3 to 0.75, and Y is 0.7 to 0.25 x+y=1 s+t=1 and t≦0.6) Lead titanium zirconate containing the third component (ternary PZT) (b) Compositional formula (2) Pb _1-z Lb _z M _1-z/4 O ₃ ...(2) Here, M is Ti and Lanthanum-containing lead titanium zirconate (PLZT), represented by Zr and z≦0.2. An organic solvent mainly consisting of one or more selected from the group consisting of a magnesium compound, a cobalt compound, an iron compound, a chromium compound, a zinc compound, a manganese compound, a nickel compound, and a cadmium compound. 1, a mixture or reaction product of a tantalum compound or a niobium compound, an organic titanium compound, an organic zirconium compound and a lead compound; or a mixture or reaction product of an organic titanium compound, an organic zirconium compound, a lanthanum compound and a lead compound; A dielectric-forming precursor solution in which one type of dielectric-forming precursor is dissolved is applied onto a substrate and dried to form a coating film of the dielectric-forming precursor. , calcining at a temperature below the crystallization temperature of the dielectric, repeating coating, drying, and calcination of a dielectric forming precursor solution, and then main baking at a temperature above the crystallization temperature of the dielectric to form a dielectric. Alternatively, a dielectric thin film can be formed by repeatedly applying a dielectric forming precursor solution onto a substrate, drying, and firing at a temperature higher than the crystallization temperature of the dielectric. In the thin film dielectric of the present invention, the substrate may include a glass plate, a ceramic plate, a conductive film usable as an electrode, such as gold, platinum palladium, silver, copper, chromium, aluminum, Glass plates and ceramic plates coated with thin films of metals or alloys such as tantalum and nickel-chromium, indium oxide films doped with tin or antimony, tin oxide films doped with antimony, arsenic, etc., and metals. Plate or metal foil such as gold, platinum, silver, copper, nickel,
It is a heat-resistant substrate made of nickel, nickel-chromium, etc., coated with a thin film of nickel-chromium or a platinum group metal. The thin film dielectric of the present invention is a thin film of 3-component PZT or PLZT, which is well known as a dielectric and is expressed by the general formula or compositional formula above, on the substrate.
It is formed by laminating more than one layer to a desired thickness. As a three-component PZT, M′ in the composition formula (3) is Mg,
PZT−PMN where M″ is Nb, M′ is Ni, M″ is Nb
An example of this is PZT-PNN. In the method for producing a thin film dielectric of the present invention, the dielectric forming precursor solution includes β-diketones such as acetylacetone and benzoylacetone, acetoacetic acid,
Ketone acids such as propionylbutyric acid and benzoylformic acid, lower alkyl esters of ketonic acids such as methyl, ethyl, propyl, and butyl, oxyacids such as lactic acid, glycolic acid, α-oxybutyric acid, and salicylic acid, and lower alkyl esters of oxyacids. An organic solvent whose main component is one kind of single solvent or a mixed solvent of two or more kinds selected from the group consisting of oxyketones such as diacetone, alcohol, and acetoin is used. Alcohol solvents and aromatic hydrocarbon solvents can be added to these organic solvents for the purpose of adjusting the viscosity of the dielectric forming precursor solution and other purposes. In the method for producing a thin film dielectric of the present invention, the organic titanium compound and organic zirconium compound used in the dielectric forming precursor solution may be any compound that is soluble in the organic solvent, for example, the following general formula (3) M ( OR) ₄ ......(3) (Here, M is Ti or Zr, and R represents the same type of monovalent hydrocarbon group.) The alkoxides represented by the following general formula are produced by their hydrolysis. (Four) (Here, M and R represent the same meanings as above.) Polymers with a degree of polymerization of 2 to 20 having repeating units, alkoxides, or a part or all of the alkoxy groups of the polymers are replaced by two Examples include compounds substituted with the residue of a chelating agent having a functional group. Specific examples of organic titanium compounds include tetramethoxytitanium, tetraethoxytitanium, tetraisopropoxytitanium, tetraethoxytitanium, didimethoxydiisopropoxytitanium, diethoxydiisopropoxytitanium, diethoxydibutoxytitanium, etc. Titanium alkoxides containing different and similar substituents, polymers produced by hydrolysis of titanium alkoxide, and some or all of the alkoxy groups of these alkoxides or polymers thereof,
β- such as acetylacetone, benzoylacetone, etc.
Diketones, ketonic acids such as acetoacetic acid, propionylbutyric acid, and benzoylformic acid; lower alkyl esters of ketonic acids such as methyl, ethyl, and propyl; oxyacids such as lactic acid, glycolic acid, α-oxybutyric acid, and salicylic acid; Lower alkyl esters, diacetone alcohol, oxyketones such as acetoin, α of glycine, alanine, etc.
- Compounds substituted with the residue of a chelating agent having two functional groups, such as amino acids and amino alcohols such as aminoethyl alcohol, can be mentioned. In addition, as the organic zirconium compound, zirconium alkoxides having the same substituents as the organic titanium compounds exemplified above, polymers thereof, and a part or all of the alkoxy groups of the zirconium alkoxide or the polymer thereof may be used. Examples include compounds substituted with the residue of a chelating agent having a functional group. Regarding Ta compounds and Nb compounds, alkoxides having the same substituents as the organic titanium compounds described above,
Also used are compounds in which part or all of the alkoxy groups of alkoxides are substituted with the residues of the above-mentioned chelating agents having two functional groups. In addition, as magnesium compounds, cobalt compounds, iron compounds, chromium compounds, zinc compounds, manganese compounds, nickel compounds, cadmium compounds, lanthanum compounds and lead compounds, inorganic salts such as oxides, hydroxides and nitrates of the metals, acetic acid Salts, carboxylates such as propionates, butyrates, and alkoxy compounds are used. In the method for producing a thin film dielectric of the present invention, the dielectric forming precursor solution is prepared by adding a mixture or a reaction product of two or more of the metal compounds described above to the organic solvent described above in terms of a metal complex oxide. 5 to 20
It is a solution dissolved at a concentration of 2% by weight. In the method for producing a thin film dielectric of the present invention, the number of repetitions of applying the dielectric forming precursor solution to the substrate, drying, and calcination or main firing is at least 2 times, preferably 3 times or more. . In the method for producing a thin film dielectric of the present invention, the calcination temperature varies depending on the type of metal compound, the type of organic solvent used, etc., but is approximately 200 to 500 °C,
Further, the main firing temperature varies depending on the type of dielectric material, but is usually 450° C. or higher. Function: The thin film dielectric of the present invention is formed by laminating two or more dielectric thin films on a substrate, and the total film thickness is
It is an extremely thin translucent dielectric material with a thickness of 0.1 to 100 μm, and has extremely excellent dielectric properties that are equal to or better than those of dielectric ceramics. If the total thickness of the dielectric is less than 0.1 μm, conduction will be difficult to avoid.
Even if there is no conduction, the durability as a dielectric is poor, which is not preferable. Further, if the thickness exceeds 100 μm, there is no particular problem, but the preferable film thickness range is 0.5 to 50 μm. By increasing the number of laminated layers of dielectric thin films, thin film defects such as pinholes existing in each layer and cracks that occur along grain boundaries are canceled out and repaired, resulting in a non-conductive thin film dielectric. . Therefore, the number of laminated layers of the dielectric thin film is preferably three or more layers, more preferably five or more layers. The thin film dielectric of the present invention can be manufactured by any of the manufacturing methods of the present invention. That is, one of the dielectric forming precursor solutions described above is applied to one of the substrates, dried to form a coating film of a uniform thickness of the precursor, and then coated in an oxygen-containing air stream. Calcination is performed by heating and holding at a temperature above the decomposition temperature of the organic matter in the film and below the crystallization temperature of the dielectric material, and then repeating coating, drying, and calcination of this precursor solution to form a thin film with the desired thickness. After forming the dielectric, a thin film dielectric with a desired thickness is formed by heating and holding at a temperature higher than the crystallization temperature of the dielectric for main firing, or by repeating application of a precursor solution, drying, and main firing. can be manufactured.
Preferably, the former is used because thin film defects such as pinholes and cracks are less likely to occur. The method for applying the dielectric forming precursor solution to the substrate may be any method that can provide a coating film with a uniform thickness, and the dipping method, spray method, spinner method, roll coating method, brush coating method, etc. can be adopted. . In particular, the dipping method is preferably employed because it is easy to obtain a coating film with a uniform thickness with a simple operation and it is easy to process in large quantities. More preferably, the precursor solution is heated at 40 to 95°C so that a coating film with a homogeneous and uniform thickness can be obtained.
The hot-dipping method is used to dip the substrate by heating it to a temperature of . The number of repetitions of applying the dielectric forming precursor solution to the substrate, drying, and calcination or main sintering should be at least as long as possible to eliminate defects such as pinholes and cracks in the formed thin film or conduction through grain boundaries. 2 or more times, preferably 3 or more times, more preferably 5 or more times. If the number of repetitions is too small, conduction may not be resolved, which is not preferable. The dielectric forming precursor solution uses the above-mentioned organic solvents alone or a mixed solvent containing them as main components as a solvent. It not only forms a chelate ring with the metal atoms in the precursor solution to uniformly disperse the metal compounds, but also stabilizes the precursor solution,
Prevents the formation of precipitates due to hydrolysis.
In addition, precursor solutions using these organic solvents have excellent ability to form dielectric thin films on substrates, especially metal substrates, and furthermore, they decompose during firing without leaving any hydroxyl groups. In order to
Prevents conduction caused by residual hydroxyl groups. As the organic solvent, β-diketones, particularly acetylacetone, which is easily available and inexpensive, is preferably used. If the concentration of the dielectric forming precursor solution is too low, 1
This is not preferable because the thickness of the dielectric thin film formed by multiple coating, drying and firing becomes too thin, and the number of repetitions of coating, drying and firing to obtain a thin film dielectric of the desired thickness becomes too large. Also,
If the concentration is too high, the coating film formed by one application becomes too thick, and thin film defects such as pinholes and cracks are likely to occur during baking, which is undesirable. The preferred concentration range of the dielectric forming precursor solution is:
Although it varies depending on the coating method employed, it is 5 to 20% by weight in terms of the metal complex oxide contained in the precursor solution. Below, a method for manufacturing a thin film dielectric having each dielectric composition will be described in more detail. Three-component PZT thin film dielectric: In the PZT dielectric forming precursor solution, further,
A solution obtained by adding and reacting one compound selected from the group consisting of a magnesium compound, a cobalt compound, an iron chromium compound, a zinc compound, a manganese compound, a nickel compound, and a cadmium compound and a tantalum compound or a niobium compound, preferably is a reaction solution, more preferably,
The following compositional formula (5) Pb M _s (M′ _1-3 M″ _2/3 ) _t O ₂ (OR) _j (OCOR゜) _k disclosed by the applicant in the above-mentioned Japanese Patent Application No. 152739/1982 ...(5) (Here, M, M', M'', R, R', s, t, and j+k represent the same meanings as above.) An acetylacetone solution of the reaction product represented by is dielectrically After immersing the substrate heated to approximately the same temperature as the precursor solution in the precursor solution maintained at a temperature of 40 to 95°C, preferably 40 to 50°C. , and is pulled up and dried at a constant speed to form a film of the dielectric forming precursor. Then,
The substrate is heated in the atmosphere at 200 to 500°C, preferably
A thin film is formed by heating and holding at a temperature of 400 to 500°C and calcining. Furthermore, after forming a thin film with a desired thickness by repeating application of the precursor solution, drying and calcination, main firing is performed by heating and holding at a temperature of 650°C or higher, preferably 600 to 800°C. A thin film of three-component PZT with a desired thickness is formed on the substrate,
Three-component PZT thin film dielectrics can be produced. PXZT thin film dielectric: A solution of an organic titanium compound, an organic zirconium compound, a lanthanum compound and a lead compound or a reaction product in the above organic solvent, preferably a β-diketone solution of the reaction product, more preferably a β-diketone solution of the reaction product, more preferably a The present applicant disclosed this in Application No. 152739/1983. The following compositional formula (6) Pb _1-z La _z M _1-z/4 O ₂ (OR) _j (OCOR′) _k …(6) (Here, M′R, R′, z, and j+k are
It has the same meaning as above. ) Using an acetylacetone solution of the reaction product represented by as a dielectric formation precursor solution, the method was similar to that of the three-component PZT thin film dielectric described above.
PLZT thin film dielectrics can be manufactured.
The calcination temperature for PLZT dielectric is 200~500℃,
Preferably, the temperature is 400 to 500°C, and the main firing temperature is
Although it varies depending on the metal atomic ratio, the temperature is 600°C or higher, preferably in the range of 600 to 800°C. Examples: Hereinafter, more preferred embodiments of the present invention will be explained in more detail with reference to Examples and Comparative Examples. However, the scope of the present invention is not limited in any way by the following examples. Example 1 PLZT thin film dielectric and its production In a 200 ml four-necked flask equipped with a thermometer, reflux condenser, and stirrer, lead acetate (Pb) with a purity of 99.1 wt% was placed.
(CH ₃ COO) ₂ 14.85 g (45.3 mmol), purity 95.6 wt% lanthanum acetate: La (CH ₃ COO) ₃ 1.57 g (4.8 mmol),
Purity 86.9wt% Tetrabutoxyzirconium: Zr
( _OC4H9 ) ₄ 14.40g (32.5mmol), purity 99wt _% tetrabutoxytitanium: Ti( _OC4H9 ) _{4 6.02g} (17.5mmol)
and 37 g of xylene were charged, and the temperature was raised while stirring under a nitrogen atmosphere. Butanol and butyl acetate began to distill out at a reaction temperature of about 130°C, and the reaction solution changed from its initial cloudy state to a yellow-brown homogeneous transparent solution. Approximately 25 g of xylene was distilled off under reduced pressure. Next, about 100 g of acetylacetone was added and heated under reflux to obtain a concentration of Pb _0.905 La _0.095 (Zr _0.65 Ti _0.35 ) O ₃ .
A 10wt% candy-colored PLZT dielectric precursor solution was prepared. A 30 mm x 50 mm x 0.2 mm platinum substrate was heated to 60° C. and immersed in the prepared PLZT dielectric precursor solution maintained at 60 to 70° C., and pulled up at a speed of 47 cm/min to remove the precursor. A film was formed. Then,
It was held in an electric furnace heated to a temperature of 500°C for 30 minutes for temporary firing. After repeating dipping into the precursor solution and pre-baking, it was further held in an electric furnace heated to 750° C. for 30 minutes for main firing, and the formed thin film was crystallized. As a result of X-ray diffraction of the obtained thin film, it was confirmed that it was a PLZT thin film. 1 cm x 1 cm on the surface of the obtained PLZT thin film dielectric.
A thin gold film was formed using a sputtering method, and silver paste was applied on top to form an electrode. A 0.1 kHz alternating current was applied between this electrode and the gold thin film, and the dielectric properties were measured. The dielectric properties of the obtained PLZT compound dielectric are shown in Table 1.

[Table] Example 2 Three-component PZT thin film dielectric and its production: In the same reaction vessel as used in Example 1, 16.4 g of lead acetate with a purity of 99.1 wt%: PbCH ₃ COO) ₂
(50mmol), purity 86.6wt% tetrabutoxyzirconium; Zr(OC ₄ H ₉ ) ₄ 3.0g (6.8mmol), purity
99wt% Tetrabutoxytitanium: Zr
(OC ₄ H ₉ ) ₄ 6.3 g (18.3 mmol), 99 wt% purity Magnesium acetate: Mg (CH ₃ COO) ₂ 1.2 ₇ (8.3 mmol), 99.99 wt % purity pentabutoxyniobium: Nb
7.6 g (16.7 mmol) of (C ₄ H ₉ ) ₅ and 30 g of xylene were charged, and the temperature was raised while stirring under a nitrogen atmosphere. Butanol and butyl acetate began to distill out at a reaction temperature of about 130°C, and the reaction solution changed from its initial cloudy state to a yellow-brown homogeneous transparent solution. About 10 g of xylene was distilled off under reduced pressure, and then about 100 g of acetylacetone was added and heated to reflux.
0.135PbZrO ₃ ‥0.365PbTiO ₃ ‥0.500Pb (Mg _1/3
Nb _2/3 ) Three-component system with a concentration of 10wt% converted to O ₃
A PZT dielectric forming precursor solution was prepared. A platinum substrate of 30 mm x 50 mm x 0.2 mm was heated to 60°C and immersed in the prepared three-component dielectric precursor solution, which was maintained at 60 to 70°C, and pulled up at a speed of 48 cm/min. A precursor coating was formed. Then, it was held in an electric furnace heated to a temperature of 500°C for 30 minutes for temporary firing. After repeating dipping into the precursor solution and pre-baking, the thin film was further fired by holding it in an electric furnace heated to 700° C. for 30 minutes to crystallize the formed thin film. As a result of X-ray diffraction of the obtained thin film, 0.135PbZrO ₃
It was confirmed that it was a three-component PZT thin film with a composition of ‥0.365PbTiO ₃ ‥0.500Pb (Mg _1-3 Nb _2/3 )O ₃ . The dielectric properties of the obtained three-component PZT thin film dielectric, which were measured in the same manner as in Example 1, are shown in Table 2.

[Table] Example 3 Three-component PZT thin film dielectric and its production: In the same reaction vessel as that used in Example 1, lead acetate (Pb) with a purity of 99.1wt% was added.
( _CH3COO ) ₂ 16.4g (50mmol), purity 86.6wt% Tetrabutoxyzirconium: Zr( _OC4H9 ) _{4 3.3g}
(7.5mol), purity 99wt% Tetrabutoxytitanium: Zr(OC ₄ H ₉ ) ₄ 6.0g (17.5mmol), purity 98.2wt%
Nickel acetate: Ni (CH ₃ COO) ₂ 3.0g
(16.7 mmol), 15.2 g (33.3 mmol) of pentabutoxyniobium:Nb(OC ₄ H ₉ ) ₅ with a purity of 99.99 wt%, and 30 g of xylene were charged, and the temperature was raised with stirring under a nitrogen atmosphere. Butanol and butyl acetate began to distill out at a reaction temperature of about 130°C, and the reaction solution changed from its initial cloudy state to a yellow-brown, about 100% transparent solution. Approximately 150 g of acetylacetone was added to the reaction solution and heated to reflux to produce 0.15PbZrO ₃ ‥0.35PbTiO ₃ ‥
0.500Pb (Ni _1/3 Nb _2/3 ) Concentration converted to O ₃ is 10wt%
A three-component PZT dielectric precursor solution was prepared. A platinum substrate measuring 30 mm x 50 mm x 0.2 mm was heated to 60°C and immersed in the prepared three-component dielectric precursor solution, which was maintained at 60 to 70°C, and pulled up at a speed of 47 cm/min. A precursor coating was formed. Then, it was held in an electric furnace heated to a temperature of 500°C for 30 minutes for temporary firing. After repeating dipping into the precursor solution and pre-baking, the thin film was further fired by holding it in an electric furnace heated to 700° C. for 30 minutes to crystallize the formed thin film. As a result of X-ray diffraction of the obtained thin film, 0.15bZrO ₃ ‥
It was confirmed that it was a ternary PZT thin film with a composition of 0.35PbTiO ₃ ‥0.500Pb (Ni _1/3 Nb _2/3 ) O ₃ . Table 3 shows the dielectric properties of the obtained three-component PZT thin film dielectric, which were measured in the same manner as in Example 1.

[Table] Example 4 Using the dielectric precursor solution prepared in Example 1, a Sn-doped indium oxide thin film (ITO
A thin film of PLZT was formed on the glass substrate on which the film was formed under the same conditions as in Example 1 to produce a light-transmitting thin film dielectric. Dielectric properties of the obtained PLZT thin film dielectric and
Table 4 shows the direct transmittance of light at a wavelength of 600 nm.

[Table] Comparative Examples 1 to 3 Using a precursor solution in which the solvent for the dielectric forming precursor used in Examples 1 to 3 was replaced with an alcohol-based solvent, the following conditions were the same as those described in each Example. Thin film dielectrics were manufactured under the following conditions. The dielectric properties of the obtained thin film dielectrics were measured by the same method as described in Example 1, but as shown in Table 5, all of them had conductivity and could not be used as thin film dielectrics. .

[Table] Note: In the comparative example, the same substrate as in the control example was used.
Effects of the invention: As shown in the above examples, the thin film dielectric of the present invention has excellent dielectric properties without conduction, as shown in the above examples, even though the dielectric film thickness is extremely thin at 0.1 to 100 μm. It is also transparent. Therefore, it is expected to be used as dielectric elements such as thin film capacitors, piezoelectric materials, and pyroelectric materials. The dielectric properties of the thin film dielectric of the present invention are closely related to its manufacturing method. It is easy to control, the chemical composition of the obtained dielectric thin film is uniform, and by forming the dielectric thin film in two or more layers, thin film defects such as pinholes and cracks in each thin film layer can be avoided. This is due to the loss of continuity after repair. Furthermore, this high dielectric property suggests that the crystal axes of the dielectric material forming the thin film are oriented in a certain direction. In addition, by using the above-mentioned organic solvents as a solvent for the dielectric forming precursor solution, it becomes a highly concentrated precursor solution of metal compounds that is stable against hydrolysis, which facilitates the production of thin film dielectrics. do.
In addition, when baking the substrate coated with the precursor solution,
It has the advantage that organic substances are very easily decomposed, and in particular, hydroxyl groups, which cause conduction, are difficult to remain in the thin film. The present invention provides an extremely thin thin film dielectric having excellent dielectric properties and a method for manufacturing the same, and has extremely great industrial significance.

Claims (1)

[Claims] 1. An organic solvent containing one or more selected from the group consisting of β-diketones, ketonic acids, ketoesters, oxyacids, oxyacid esters, and oxyketones, and a magnesium compound, a cobalt compound, and iron. compound, one selected from the group consisting of a chromium compound, a zinc compound, a manganese compound, a nickel compound, and a cadmium compound, a tantalum compound or a niobium compound, an organic titanium compound, an organic zirconium compound, and a mixture or reaction product of a lead compound or a lanthanum compound A dielectric-forming precursor solution containing a dielectric-forming precursor made of a mixture or reaction product of an organic titanium compound, an organic zirconium compound, and a lead compound is applied onto the substrate and dried to coat the dielectric-forming precursor. After forming the film, it is calcined at a temperature above the decomposition temperature of the organic matter in the coating film and below the crystallization temperature of the dielectric, and then repeating the coating, drying and calcination of the dielectric forming precursor solution, and then A thin dielectric film is formed by main firing at a temperature higher than the crystallization temperature of the substrate, or a dielectric forming precursor solution is applied onto the substrate, dried, and then heated at a temperature higher than the crystallization temperature of the dielectric. 1. A method for producing a thin film dielectric, comprising repeating main firing to form a thin dielectric film.