TWI286996B - Coating solutions for use in forming bismuth-based paraelectric or ferroelectric thin films, and bismuth-based paraelectric or ferroelectric thin films - Google Patents

Abstract

This invention is to disclose a coating liquid for forming a Bi-based dielectric thin film showing paraelectric or ferroelectric property in compliance with applications of semiconductor memories. This coating liquid for forming a Bi-based dielectric thin film showing paraelectric or ferroelectric property contains a composite metal oxide expressed by the formula: (Bi(4-x), (Laz.B(1iVz)x)n(Ti(3-y),Ay)O(12+alpha) (in which A is a metal element such as Ge; B is a rare earth element except lanthanum or a metal element such as Ca or Sr; 0 <= x < 4, 0 <= y <= 0.3, 0 < z <= 1; n=0.7 to 1.4; alpha is a valence determined by the metal composition ratio) and contains a composite metal alkoxide formed from at least two metal alkoxides, i.e., oxides of Bi and Ti. The coating liquid is preferably a sol-gel liquid obtained by hydrolysis or partial condensation reaction treatment using water or water and a catalyst. Preferably, the coating liquid contains an alkanolamine.

Description

1286996 * « (1) IX. Description of the Invention [Technical Fields of the Invention] α The present invention relates to a coating liquid for forming a lanthanide dielectric film which is usually dielectric or ferroelectric, and is formed using the same The invention of a tantalum dielectric film. The coating liquid of the present invention can be widely used in the field of utilizing pyroelectricity, high dielectric property, and ferroelectricity, so that a normal dielectric forming material or a ferroelectric forming material can fully exhibit its function. In particular, it is suitable for the characteristics required for a single capacitor device (film capacitor) or a semiconductor device such as a drain or a nonvolatile memory capacitor. [Prior Art] In recent years, with the increase in the capacity of semiconductor memory, DRAM ( = Dynamic Random Access Memory) has been used as a capacitor for accumulating electric power. Electrically, dielectrically or strongly dielectric dielectric film. Further, in the non-volatile memory, a dielectric thin film having a high dielectric property of high residual polarization has been widely used, or a hysteresis or the like is used. Or developing a dielectric thin film material for the memory element, and a film forming method of the thin film, etc., in the semiconductor memory device, which can be used in combination with the use thereof, and is in the form of a dielectric constant to a strong dielectric property. Appropriate materials are used in the electric film. Memory elements such as DRAM or SRAM (= Static Random Access Memory) are technical fields that are particularly highly advanced in semiconductors, and are designed to greatly suppress software errors (s 〇fterr 〇r ) to ensure reliability -5 - (2) 1286996 Sex, it is generally necessary to ensure that the capacitor in the memory-cell is maintained above a certain level. In the past, the three-dimensional structure was used to ensure the capacitor area', and the container was made by using a SixNy film or a SiOx/SixNy laminated film to solve the problem. Among them, the SixNy film has a high dielectric property and a film which has a specific dielectric constant (£) of about 4 to 7, so that it is necessary to have a three-dimensional structure in order to sufficiently charge the charge. • However, the three-dimensional structure imposes a great burden on the planarization of the interlayer insulating film. Moreover, in terms of reducing the current leakage, the thin film of the capacitor has approached the critical point, so in the generation of 25 6M-DRAM and 1 G·DRAM, there is a breakthrough in innovative technology. Further, in semiconductor elements other than the memory such as logic elements, there are still many components in which capacitors are present, and the above-mentioned elements are also the same, and technical breakthroughs are still required. In the foregoing situation, high dielectric film ® , which is a capacitor structural material, has received increasing attention. High dielectric film, known as Ta205 (oxidation giant: ε = 20 * 35) or a perovskite-type unit crystal lattice structure, which exhibits a common oxidization, piezoelectricity, and pyroelectricity. Ceramics. The composite oxide ceramic is known, for example, as BST (barium titanate: ε = 400 or more) ΡΖΤ (lead titanate chromate: ε = 1 〇〇〇 or more). When the high dielectric constant film is used as a structural material of a capacitor, even if a sufficient capacity can be obtained under the planar capacitor structure, the device can be easily manufactured and the reliability of the device can be improved. The amount of electricity, the amount of electricity, and the storage of electricity have also been found to the electrical or for the -6- (3) 1286996 Especially when making laminated ceramic capacitors, currently, BTO (barium titanate oxide) powder siltation After slurrying, it is a general method to form a film after firing, but it is not easy to make the film thickness thinner. To make the necessary capacitor capacity, it is necessary to laminate hundreds of layers, but in the case of using high-medium In the case of a power film, a relatively high capacity can be obtained without using the above-described multilayering. Further, the relationship between the electrostatic capacitance (C) and the dielectric constant (?) can be expressed by the following formula. _ C = ε · S/D (where ε = ηΕ ) (where C is the electrostatic capacity, &lt; 6 is the dielectric constant, 8 is the electrode area, D is the film thickness, and n is the dielectric constant under vacuum (8.854187816 E'12), Ε is the specific dielectric ratio) It is known from the above formula that in addition to the method of decreasing D (film thickness), increasing S (electrode area), and increasing C (electrostatic capacity), There is also a method of increasing ε (dielectricity) to increase C (electrostatic capacity). In order to avoid the problems caused by the above-mentioned three-dimensional structure, it is generally effective to increase the ε, that is, to use a high dielectric material. Among the above-mentioned high dielectric materials, a donor dielectric such as lanthanum (lead titanate) has high residual polarization and the like, and is highly suitable as a ferroelectric material, but in recent years, it has been cherished for environmental protection. Ascension has gradually sought an alternative material that does not contain lead. A ferroelectric material other than a lead-based ferroelectric material is known, for example, strontium strontium sulphate (SBT) (see, for example, JP0140965A, JP08-91841A), and one of the secrets of the BIT is replaced by La by barium titanate.铋(BLT) (please refer to for example) 2003- 1 9243 1 8, 】 2003 - 82470A, JP2002-265 224A, JP2002-255 5 7A) 铋 (Bi) (4) 1286996 is a strong dielectric material, etc. report. BIT is a material with a higher residual enthalpy than SBT. It has been reported that BLT has a higher residual enthalpy than BIT, and has received great attention in recent years. The method for forming the lanthanide-based ferroelectric thin film is, for example, a sputtering method, a 嘈CYD method, or a coating type film formation method, but a lanthanum-based ferroelectric thin film is formed by an oxide of a metal element constituting the film. Therefore, the thin film formation method by the sputtering method or the CVD method requires a large cost because it requires a high-priced device, and is not suitable for controlling the composition of the dielectric film required and is not easy to manage. Easy to use on large diameter substrates. On the other hand, the coating type film formation method does not require the use of a high-priced device, and the cost of film formation is relatively low, and it is easy to control the contents of the dielectric film composition required and easy to manage, etc., and is extremely promising. Technology. The coating liquid for forming a lanthanoid-based dielectric thin film used in the coating film formation method is known, for example, a carboxylic acid having a medium-chain hydrocarbon group such as 2-ethylhexanoic acid and a constituent metal element of the film and An organic metal compound such as a salt or an alkoxide metal compound formed by an alcohol such as ethanol, methoxyethanol or methoxypropanol and a constituent metal element of the film, dissolved in an organic solvent to obtain a coating Liquid, etc. However, in order to stabilize the metal composition ratio in the coating liquid, it is necessary to find a way to prevent the loss of the metal composition ratio in the film due to the loss of the metal (Bi or the like) which is high in sublimation when the film is formed. phenomenon. Therefore, in the coating type material, it is highly desirable to have a material having a stable metal composition and suppressing a change in the metal composition ratio in the film to form a PTFE-based or BLT-based ferroelectric thin film. -8- (5) (5) 1286996 And in the use of semiconductor memory, there is also a need for constant dielectric technology. Therefore, it is also extremely necessary to develop a dielectric property with low dielectric current. Dielectric rate material. Further, in JP10-258252A and JP10-2590 07A, there is also disclosed a phenomenon in which an attempt is made to combine an alkoxide metal to stabilize a metal composition ratio to suppress a change in a metal composition ratio in a film, but the details are described in the aforementioned documents. The material is only the content of the coating liquid for forming a SBT-based ferroelectric thin film, and the content of the coating liquid for forming a strong dielectric thin film for BIT or BLT system or a coating liquid for forming a normal dielectric film. There is no such thing as a summary of the present invention. It is an object of the present invention to provide a ferroelectric lanthanide dielectric film which has a stable metal composition ratio and which can suppress a change in the metal composition ratio in a film. The coating liquid ^, another object of the present invention, according to the use thereof, provides a dielectric property and a low bleed current in a technical field which is superior to the dielectric property and the dielectric property. A high dielectric form coating liquid of a ferroelectric lanthanide dielectric film. In order to attain the above object, the present invention provides a coating liquid which is a coating liquid for forming a ferroelectric lanthanide dielectric film containing a composite metal oxide represented by the following formula (I), which is characterized by a composite courtyard oxygen metal containing at least two alkoxymetals of Bi and Ti, (Laz, B!-z) x}n(Ti3-y, Ay)〇i2 + a (I) - 9- (6) 1286996 (where A is V, Cr, Μη, Si, Ge, Zr, Nb, Ru,

At least one metal element selected from the group consisting of Sn, Ta, and W, and B is at least one metal element selected from the group consisting of rare earth elements not containing germanium, Ca, Sr, and Ba, and X, y, and z are each 0Sx&lt;lt;;4,0SyS0.3,0&lt;ζ$1 « The number shown, η is Ο · 7 to 1 · 4, α is the valence determined by the metal composition ratio). Further, the present invention is a coating liquid which is a coating liquid for forming a dielectric material of a dielectric material which is usually dielectric, and is characterized by a compound hospital comprising at least two kinds of oxymetals of Bi and Ti. An oxymetal, or a mixed alkoxy metal obtained by mixing at least a hospital oxide Bi or an alkoxylated Ti. Wherein, the coating liquid may be a dielectric material formed by forming a composite metal oxide represented by the above formula (I) (wherein A, B, X, y, y, η, α are as defined above) It is preferred that the coating of the dielectric film is a dielectric film. Further, the present invention provides a method for forming a dielectric film of a dielectric film of a dielectric material, which is applied to a substrate by applying a coating liquid for forming a dielectric film of a normal dielectric film. Under heat and drying treatment, heat treatment (first heat treatment) at 500 to 700 ° C is performed to form a coating film, and the above-mentioned coating is repeated several times to heat treatment (1st) The step before heating is treated to form a laminate layer of the coating film, and secondly, heat treatment at 600 to 700 ° C (second heat treatment) is performed. Further, the present invention provides a dielectric film of a normal dielectric lanthanide dielectric film which is applied to an electrode by forming a coating liquid for forming a dielectric film of a lanthanoid dielectric film which is formed into a dielectric material, and is fired. And got it. -10- (7) 1286996 Π.] A coating liquid for forming a dielectric film of a dielectric-based dielectric film (hereinafter referred to as "coating liquid for forming a lanthanum-based dielectric"). The coating liquid for forming a lanthanoid-based dielectric thin film of the present invention is a coating liquid for forming an lanthanoid-based ferroelectric thin film containing a composite gold oxide represented by the following formula (I), {Bi4.x ' ( La2 &gt; B,.z) x}n ( Ti3.y ' Ay ) 012+α ( I) In the above formula, 'A is V, Cr, Μη, Si, Ge, Zr, Nb, Ru, Sii, Ta, At least one metal element selected from W. The coating liquid for forming a strong dielectric film is preferably the one in which A is used. B is at least one metal element selected from the group consisting of rare earth elements not containing cerium, Ca, Sr and Ba. Among them, lanthanoid elements are preferred, and in particular, the use of praseodymium (Pr), cerium (Ce), and cerium (Nd) is preferred. X is a number represented by 〇Sx&lt;4, preferably 〇&lt;x&lt;4, y is a number shown by 〇SyS〇.3, preferably 〇&lt;y^〇.3. Further, when Ge is used for the A metal, y is preferably y = 0.05 to 0.20, particularly preferably y = 〇·10 to 0·15 〇z is 0 &lt; ζ$1, preferably 0 &lt; ζ &lt; 1. η is a number from 0.7 to 1.4. α is the valence determined by the metal composition ratio. Preferably, it is -5 ^ a S 5 , more preferably -2S α 刍 2 〇, and the coating liquid is a composite alkoxy metal containing at least two kinds of alkoxymetals of Bi and Ti, preferably used. The gel-sol liquid obtained by hydrolysis-partial condensation treatment of water or water and a catalyst. That is, in the method for producing a coating liquid of the present invention, ?11-(8) 1286996 t is contained in the coating liquid.

'Bi' Ti is a combination of alkoxide and alkoxides as the starting material. La'A metal element and B metal element (in which case there is also no A metal alkaloid or B metal element) to use alkoxide respectively. The metal 乍 乍 $ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ Μ $ 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 金属 。 Its content is not limited by the examples. In the present invention, it is preferable to use a metal acetate (barium acetate) from the viewpoint of easy availability and good properties. A metal element and B metal element are preferably used in combination with the alkoxy metal. Specific examples are as follows (in the case where A metal element, .B metal is included), but the present invention is not limited by the following examples. (a) A state in which a BiTi complex alkoxide metal, an alkoxide oxide (or acetate), an A alkoxide metal (or an acetate), a B alkoxy metal (or an acetate), or the like is contained. (b) Containing a BiTiLa complex alkoxy metal, an Alkoxy metal (or a salt, etc.), a B alkoxy metal (or an acetate, etc.). ((1) Containing BiTiLaA metal complex alkoxide, B alkoxy metal (or acetate, etc.). (d) Containing WTiLaA metal B metal complex alkoxide equivalent. $ g in the sun and the moon, the metal element The above (d) state of the compound courtyard oxide _ stomach stomach. The above two or more kinds of dissimilar metals are used as a composite ruthenium metallization knot $ 5 $ Stomach% inhibits the precipitation (segregation) and burning of individual metal elements. 12-(9) 1286996 The complex alkoxy metal referred to in the present invention is, for example, alumtenium alkoxide, titanium, and other metal elements (La, A metal element, B metal alkoxide, acetate, yS · diketone metal) In a solvent of an isocratic state, under a heating condition of 30 to 100 t: a compound obtained by refluxing 2 to 15 #. The end point of the reaction is a liquid discoloration, and the brownish liquid is so long that the liquid is completely discolored at the end point. The composite alkoxy metal obtained by the above method, for example, the manufacturing technology and application of the glass-ceramic of the gel-sol method (published by the publishing company, issued on June 4, 1989) 46 46 to 47 Specifically, for example, Ti Bi ( OR ) 4 ( OR ) 3, (OR) 3 (OR) 4(0 R) a ' LaTiBiA ( OR ) 3 ( (OR) 3 ( 〇R ) m, LaTiBiB (OR) 3 ( OR ) 4 ( (OR ) n ' LaTiBiAB ( OR ) 3 ( OR ) 4 ( OR ) 3 ( (OR ) n (where A and B are as defined above; m is the valence of A; n is the metal of B) The valence; R is an alkyl group having 1 to 6 carbon atoms, and the like, but the present invention is not limited thereto. In the present invention, Bi is compounded with Ti by using Bi which is highly sublimable as a necessary &lt; Therefore, it is possible to approach the ratio of the raw material fed to the film. The alcohol forming the alkoxy metal or the complex alkoxy metal is preferably the one shown by using (II).

Ri〇H ( II ) (wherein R! is a saturated or unsaturated hydrocarbon having a carbon number of 1 to 6; a specific example of the aforementioned alcohol, such as methanol, ethanol, propanol or butyl oxide) In the hour, the final reaction is LaTiBi OR defined by the condensation technology. 4 OR ) 3 OR ) m The metal ruthenium is independently defined under the metal element to form the following formula. Alcohol, pentane-13-1286996 • Brewing do Alcohol, cyclohexanol, etc. Alcohols other than the above alcohols, for example, R 1 is further substituted with alkoxy groups having 1 to 6 carbon atoms, specifically, for example, methoxymethanol, methoxyethanol, and B. Oxylethanol, ethoxyethanol, etc. The alkoxy metal, the complex alkoxy metal, etc., and a part of the alkoxy group thereof can be described as a chain amine, a residual anhydride, a diacetic acid monoacetate, a stone The ketone may be substituted with a diol or the like. The coating liquid of the present invention may be subjected to hydrolysis-partial condensation using a coating liquid containing the above-mentioned composite bismuth metal, water or water and a catalyst. It is preferred to treat the obtained gel/sol solution. Hydrolysis reaction, for example, adding water or water and a catalyst to the coating liquid at 20 to 50 The mixture is stirred for several hours to several days at ° C. The catalyst is known, for example, as a known substance for the hydrolysis reaction of an alkoxy metal, such as an inorganic acid such as hydrochloric acid, sulfuric acid or nitric acid, or an organic acid such as acetic acid, propionic acid or butyric acid. Catalyst, inorganic or organic base catalysts such as sodium hydroxide, potassium hydroxide, ammonia, monoethanolamine, diethanolamine, tetramethylammonium hydroxide, etc. Among them, inorganic bases such as sodium hydroxide and barium hydroxide If a metal ion such as sodium or potassium remains in the coating liquid, there is a concern that the electrical properties of the film may be affected. Further, a nitrogen-containing k-base such as ammonia or an amine may have a boiling point after the hydrolysis reaction. In the case of a higher nitride, there is a concern that the film may be densified during the firing step, so in the present invention, it is preferred to use an acid catalyst. The hydrolysis reaction is to apply the coating liquid to the electrode. Thereafter, the surface of the film is exposed to a humidifying environment, for example, at 50 to 120 ° C for 10 to 60 minutes, preferably at 50 to 100% humidity. -14- (11) 1286996 or more, Can be used in conjunction with the use of the film for appropriate selection, and The above-mentioned content is not limited to the above. The hydrolysis treatment can reduce the content of the organic component in the entire coating film after the drying step, and the complex bond of each metal can be formed, so that the precipitation and burning of the metal such as ruthenium can be controlled. The reason is that various organic metal compounds have organic groups which are contained in the structure, and are often desorbed by an organic group such as an alkoxy group by hydrolysis treatment, and can be reattached to a metal complex bond I having higher inorganicity. When the organic group is separated, an alcohol or a glycol having a low boiling point is formed, and remains in the coating liquid or the film, and evaporates simultaneously with the solvent in the drying step, so that the inorganicity of the film before the baking step can be improved, and Further, a dense film can be formed. Further, by the formation of a composite or metal complex bond, the bonding strength between the metal elements is increased, and precipitation (segregation), burning, and the like of a metal element such as ruthenium are suppressed, and the bleed current is reduced. A film having excellent hydrogen heat treatment resistance and pressure resistance is formed. Further, the coating liquid of the present invention is preferably one in which an alkanolamine is added. In particular, it has an effect of improving coatability by using an alkanolamine. Alkanolamines, such as triethanolamine, diethanolamine, dibutylethanolamine, diethylethanolamine, and the like. Among them, triethanolamine is preferred from the viewpoint of improving coatability and the like. The amount of the alkanolamine added is, for example, 1 mol of the composite metal oxide shown in the above formula (I) (wherein the definitions of A, B, X, y, z, η, and α are the same as those described above). 〇· 5 to 2 0 Mo, especially 1 to 1 〇 Mo range. When it exceeds the above range, even if an alkanolamine is added, there is a tendency that a sufficient effect cannot be obtained, which is not preferable. • 15-(12) (12)1286996 Further, the addition of the alkanolamine is preferably carried out after the hydrolysis treatment in the above hydrolysis treatment. Further, in the present invention, a conventionally known stabilizer can be added. The stabilizer is preferably one which can improve the storage stability of the coating liquid. For example, a carboxylic anhydride, a dicarboxy monoester, a/5-diketone, a glycol or the like is preferably used. The carboxylic acid anhydride is, for example, a carboxylic anhydride represented by the following formula (III) R 2 ( C0 ) 20 ( III ) (wherein R 2 is a divalent carbon number of 1 to 6 saturated or unsaturated hydrocarbon group) At least one of the selected ones is preferred. The acid anhydrides are specifically, for example, maleic anhydride, citraconic anhydride, isaconic anhydride, succinic anhydride, methyl succinic acid, glutaric anhydride, α-methyl glutaric anhydride, dimethyl glutaric anhydride, Trimethyl glutaric anhydride or the like. Dicarboxylic acid monoesters, for example, by the following formula (IV) R3OCOR4COOH (IV) (wherein R3 is a saturated or unsaturated hydrocarbon group having a carbon number of 1 to 6; and R4 is a divalent carbon number of 1 to 6 The saturated or unsaturated hydrocarbon group is preferably at least one selected from the group consisting of the dicarboxylic acid monoesters shown. The dicarboxylic acid monoester, specifically, for example, a dibasic acid can be reacted with an alcohol to form a semi-esterified one, which may be oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, Pimelic acid, suberic acid, azelaic acid, sebacic acid, maleic acid, miconic acid, isoconic acid, methyl succinic acid, α-methyl glutaric anhydride, α,α-dimethylpentane An acid anhydride, trimethyl glutaric anhydride to -16- (13) (13) 1286996 one less, with methyl alcohol, ethyl alcohol, propyl alcohol, butyl alcohol, pentyl alcohol, hexyl alcohol, B At least one of glycol monomethyl ether and propylene glycol monomethyl ether is synthesized by esterification according to a known method. The cold-diketones are, for example, those containing the formula (V) r5cocr6hcor7 (V) wherein R5 is a saturated or unsaturated hydrocarbon group having a carbon number of 1 to 6; r6 is hydrazine or CH3; R7 is a carbon number of 1 At least one selected from the yS-diketones of the cold-diketone esters represented by an alkyl group or an alkoxy group of 6 is preferred. The yS-diketones used in the present invention are specifically, for example, acetophenone, 3-methyl-2,4-pentanedione, benzoquinone or the like. Further, a ketone ester such as ethyl acetonate or diethyl malonate is used. It may also be used as a complex forming agent of samarium, but dimethyltrimethyl ethane methane or its THF adduct, or a blister-forming agent such as a metal halide of hexafluoroacetamidine. It is not suitable for use in the coating liquid of the present invention because it forms a metal complex having high sublimation or volatility. The diol is, for example, at least one selected from the group consisting of diols represented by the following (VI) HOR8OH (VI) (wherein Rs is a divalent carbon number of 1 to 6 or a saturated or unsaturated hydrocarbon group) It is better. The diols used in the present invention are specifically, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol, pentanediol, hexanediol, 2·ethylethoxy di-, glycerin. One _ wait. The above-mentioned monools are particularly effective when used as a θ·dione as a stabilizer of -17-(14) 1286996, which can improve the stability of the liquid after the hydrolysis reaction. The above stabilizers are all short-chains having a carbon number of 1 to 6, and it is preferred from the viewpoint of improving the inorganicity of the film after the drying step. Further, a substituted or unsubstituted lower single-residual acid such as acetic acid, propionic acid, diethyl hexane, butyric acid or valeric acid is also suitable as a stabilizer. The complex alkoxy metal is used for carboxylate, dimethyl ketone, and kneading using a carboxylate, a dicarboxylic acid monoester, a j-diketone, a glycol, or a lower monocarboxylic acid. By treating the result, a product having polarity and excellent stability can be obtained, and the hydrolyzability can be improved, and the practical solubility in a polar solvent can be improved. As a result, the polycondensation reaction by the gel-sol method in the coating liquid can be further sufficient, and the inorganic bond (metal complex) obtained by the metal-oxygen atom can be formed, and the specific metal element such as ruthenium can be reduced. The amount of precipitation (segregation) and the amount of burnout are increased, and the inorganicization of the entire coating liquid is improved. Further, the stabilization treatment and the hydrolysis treatment of the above stabilizer may be carried out either first or simultaneously. The hydrolysis treatment and the stabilization treatment can improve the storage stability, workability, low-temperature decomposition, high density, and coatability of the coating liquid, and can improve the solubility in a practical organic solvent. The solvent of the coating liquid for forming a lanthanoid-based dielectric thin film, for example, a saturated aliphatic solvent, an aromatic solvent, an alcohol solvent, a glycol solvent, an ether solvent, a ketone solvent, an ester solvent, or the like . The alcohol solvent is, for example, methanol, ethanol, propanol, butanol, pentanol, cyclohexane-18-(15) 1286996 alcohol, methylcyclohexanol or the like. Glycol-based solvents such as ethylene glycol monomethyl ether, ethylene glycol monoacetate, diethylene glycol monomethyl ether, diethylene glycol monoacetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether , propylene glycol monoacetate, propylene glycol dimethyl ether, propylene glycol diethyl ether, propylene glycol dipropyl ether, dipropylene glycol monoethyl ether, 3-methoxy-1. butanol, 3-methoxy- 3-methylbutanol, 3,3'-dimethylbutanol, and the like. The Φ ether solvent is, for example, methylal, diethyl ether, dipropyl ether, dibutyl ether, dipentyl ether, diethyl acetal, dihexyl ether, trioxane, dioxane or the like. Ketone solvents such as acetone, methyl ethyl ketone, methyl ketone, methyl isobutyl ketone, methyl amyl ketone, methyl cyclohexyl ketone, diethyl ketone, ethyl butyl ketone, trimethyl Mercapto ketone, acetonitrile acetone, dimethyl oxide, phorone, cyclohexyl alcohol, diacetone alcohol, and the like. Ester solvent, such as ethyl formate, methyl acetate, ethyl acetate, butyl acetate, cyclohexyl acetate, methyl propionate, ethyl acetate, ethyl oxoisobutyrate, ethyl acetate Ethyl lactate, methoxybutyl acetate, diethyl oxalate, diethyl malonate, triethyl citrate, tributyl citrate, and the like. Further, in the gelation and stabilization treatment of the hydrolysis, the present invention is not limited to the low-boiling alcohol solvent used in the past, and may be used in combination with an aromatic compound (such as toluene or xylene) or a high-boiling diol. . The solvent may be used alone or in combination of two or more. The solvent other than the alcohol solvent may be used in the case of the coating property at the time of film formation or the stability of the coating liquid, etc., in the invention, -19-(16), (16)1286996. In particular, it is preferred to use an ethylene glycol solvent. In the coating liquid for forming a lanthanide-based ferroelectric thin film, Bi, Ti, and A metal elements (calculated as A = 0 when A is not contained) are Bi : (Ti + A) = 1·〇7 to 1.15. : 1 (Morbi) ratio is better. When the molar ratio of each component in the coating liquid is adjusted to the above range, a film having excellent ferroelectricity and a high fraction (Pr) can be formed. Next, a method for producing a ferroelectric thin film and a ferroelectric memory (strong dielectric member) using the coating liquid for forming a lanthanide-based ferroelectric thin film of the present invention will be described. However, the invention is not limited thereto. First, a substrate such as a germanium wafer is oxidized to form a tantalum oxide film on the upper portion of the substrate, and a metal such as Pt, Ir, Ru, Re, or 〇s is formed thereon by a sputtering method or a vapor deposition method, and a metal oxide thereof. The conductive metal oxide is used to form the lower electrode. Subsequently, the coating liquid of the present invention is applied to the lower electrode by a known coating method such as a spin coating method or a dip coating method, and further at 50 to 4.0 ° C, preferably 150 to 300 °. The first heat treatment (drying) was carried out at a temperature of C to form a coating film. Next, the processing steps from coating to drying are repeated several times in accordance with the required standard to achieve the desired film thickness. Next, in the oxygen atmosphere, the main sintering is carried out at a temperature of 600 to 750 ° C to form a ferroelectric thin film having a crystal structure. In the main boiling step, for example, the temperature may be raised from the room temperature to a temperature of 5 to 20 ° C /min to the temperature of the main cooking, and then maintained at the main cooking temperature for about 10 to 80 minutes. The furnace is heated to a temperature of 50 to 150 ° C / sec at room temperature to a final boiling temperature, and then maintained at a temperature of -20 - (17) 1286996 liters for 0.5 to 3 minutes. It is selected and used in various cooking methods such as the RPT method of burning left and right. When the coating is carried out by the present invention, the temperature of the main burning (crystallization of the film composition) can be carried out at a low temperature of 600 to 700 °C. Next, an electrode (upper electrode) was formed on the above-described ferroelectric thin film. For the upper electrode, for example, a metal or a metal oxide exemplified as a material for the lower electrode can be used, and the material can be formed on a ferroelectric thin film by a sputtering method, a vapor deposition method, or the like, and is exposed to an oxygen atmosphere. , burned at 00 to 700 C to make strong dielectric memory. At this time, the upper electrode may be made of a material different from the lower electrode, for example, the lower electrode may use Ir, and the upper electrode may use RU. Further, in the case where the hydrolysis reaction is carried out in a humidified environment, it is preferably carried out at a temperature of 50 to 100%, preferably 70 to 100%, and at a temperature of 50 to 120 ° C for 10 to 60 minutes before the pre-firing. In the production of the coating liquid, in particular, when it is composited or inorganicized by β-hydrolysis, the bonding between the metals can be enhanced, and precipitation (segregation), burning, and the like of the metal element can be suppressed, and the current leakage can be suppressed. It can improve the properties of ferroelectrics such as crystallinity, hydrogen heat treatment resistance and pressure resistance. Further, after the upper electrode is formed, a protective film (passivation) such as SiO 2 or an aluminum wiring is formed, and in particular, it has excellent hydrogen heat treatment resistance. Therefore, when a passivation film is formed and an aluminum wiring is formed, a strong dielectric can be reduced. The problem of deterioration of characteristics is achieved, and the practical use of a ferroelectric memory using a BLSF film is achieved. Further, the above-mentioned gel-sol method (hydrolysis method) is obtained by using a coating liquid which is completely unhydrolyzed by the inorganic coating solution of the inorganic coating, which is obtained by the gel-sol method (hydrolysis method), when the coating film is formed on the substrate. After the film is exposed to a humidified environment for a certain period of time before being baked, the film can be inorganicized by hydrolysis polycondensation, and further formed into a dense film. The hydrolysis treatment in the coating liquid may cause the viscosity-gelation of the coating liquid when it is excessively performed, or may cause a storage change or the like, so that the hydrolysis treatment at the time of forming the film is also effective. . • [II·] A coating liquid for forming a dielectric film of a ruthenium-based dielectric film (hereinafter referred to as a coating liquid for forming a ruthenium-based dielectric film). The ruthenium-based dielectric film of the present invention The coating liquid for formation is a composite alkoxy metal containing at least two kinds of alkoxymetals of Bi and Ti, or a mixed alkoxy metal obtained by mixing at least an alkoxide and a titanium alkoxide. It is a coating liquid for a dielectric film. The alkoxide is mixed, for example, by adding an alkoxide or a titanium alkoxide in an alcohol solution, and mixing it. As the alcohol of the alkoxide metal, for example, the alcohols listed in the above [I.] item can be used. The complex alkoxy metal can be obtained, for example, by the method described in the above [I.] item. The coating liquid for forming a normal dielectric film of the present invention obtained in this manner also includes the effect of reducing the bleed current when the BIT-based coating liquid contains a mixed alkoxide. When the composite alkoxide metal is used, the film is excellent in compactness. The coating liquid for forming a lanthanoid-based dielectric thin film is preferably formed, for example, to form a normally dielectric lanthanide dielectric film (ie, a BLT film) containing the composite metal oxide described in the above item [I.]. It is better. In the formula, A, B, -22- (19) (19) 1286996 x, y, ζ, η, α are defined as described above. Among them, the normal dielectric film also contains a mixed alkoxide obtained by mixing an alkoxylated hafnium or a titanium oxide. It may be a complex alkoxy metal containing cerium and titanium. The difference between the content of the formation of the dielectric film and the content of the formation of the ferroelectric film, for example, when the compound represented by the above formula (I) is contained, is mainly a difference in composition and a difference in film formation conditions. When the method for forming a film represented by the formula (Ϊ) is exemplified, for example, a coating liquid for forming a ferroelectric thin film, as described in the item [I.] above, the ratio of the metal element in the coating liquid, Bi, The Ti and the base metal element are preferably adjusted to a ratio of Bi : ( Ti + A ) = 1.07 to 1 · 1 5 : 1 (mole ratio). Further, it is preferable to use Ge as the A metal element. On the other hand, in the coating liquid for forming a normal dielectric thin film, B1, Ti and A metal halogen are adjusted to B i : ( Ti + A ) = 〇 · 9 〇 to 1 · 〇 6 : 1 (Mo The ratio of ear to ear is better. Further, in the case of the coating liquid for forming a normal dielectric film, when the A metal bismuth is Ge or B element, Sr, Ba., Pr, Er, Y or the like is preferably used. The formation conditions of the coating liquid for forming a normal dielectric film are as follows. When the coating liquid is adjusted to the composition of Bi : ( Ti + A ) = 0.90 to 1.06 : 1 (mole ratio), it is not necessary to define a special formation method, and the conventional dielectric film formation method can be used to form a conventional medium. Electrical film. Further, in a suitable formation method, for example, coating the coating liquid on the substrate, and then performing the first heat treatment at a temperature of 50 to 400 ° C, preferably 15 to 30 ° C. (Drying) to form a coating film. Next, in combination with the required standard, the treatment step from coating to drying is repeated several times to form a layer of -23-(20) (20)1286996 film, and secondly, at 600 to 700 ° C, preferably A second heat treatment (roasting treatment) at 600 to 670 ° C to form a film or the like. According to this method, a dielectric film having a dielectric constant and a high dielectric constant can be obtained. Further, when the coating liquid is not adjusted to a combination of Bi : ( Ti + A ) = 0.90 to 1.06 : 1 (mole ratio), it is preferred to use the following method in forming a suitable dielectric film. For example, the coating liquid is applied onto the substrate, and the first heat treatment (pre-roasting) is performed at a temperature of 500 to 700 ° C, preferably 550 to 650 ° C, without drying by heating. A coating film is formed. Next, in combination with the required standard, the processing steps from coating to drying are repeated several times to form a laminate of the coating film, and secondly, at 60 to 700 ° C, preferably 600 to 670 The second heat treatment (sintering treatment) at ° C to form a film or the like. According to this method, a dielectric film having a dielectric constant and a high dielectric constant can be formed. Further, the above-mentioned drying treatment refers to a heat treatment (for example, a temperature near a normal temperature) in which the coating film is dried without performing a substantial heat treatment, and the organic component in the coating film is not decomposed. In the foregoing process. The components which can be added to the coating liquid for forming a normal dielectric film (for example, a solvent, a stabilizer, an alkanolamine, etc.), the conditions for forming a dielectric element, etc. are as described in the above [I.] item. content. Further, the content of Bi, Ti, La, A metal element component and b metal element component in the coating liquid for forming a lanthanum-based dielectric film is used according to the coating liquid of the invention-24-(21) 12869.96 There are various changes in the location, conditions, etc., such as the type of device (for FRAM, DRAM, MFS, MFIS, MFMIS, etc.) or the type, thickness, composition, and barrier of the upper and lower electrodes used. The type of layer, the thickness, or the presence or absence of the alignment film, etc., can be selected in accordance with the situation. The amount of the organometallic compound added, the kind and amount of the residual alkoxy group, the carbonyl addition ratio, the degree of complexation, the hydrolysis rate, etc., or the polycondensation degree, the composite enthalpy oxidation degree, etc. can be coated with the present invention. The use and conditions of the liquid (drying, temperature, time, environment, temperature rising method, etc.) are appropriately selected. The embodiments of the present invention shown in the following examples are various technical fields applicable to the present invention. The examples are illustrative, but the invention is not limited by the following examples. [Embodiment] EXAMPLES Hereinafter, the present invention will be described in more detail by way of examples, but the present invention is not limited by the following examples. [Coating liquid for forming a lanthanide-based dielectric thin film] Synthesis Example 1 [In the above formula (I), a coating liquid represented by n = 1.0250, X = 0.7317 'y = 0 'z = 1, α = 0.1500 (Bi: (Ti + A) = 1.12 : 1 (mole ratio))] In the methoxy-2-propanol, add 0.075 0 moles of yttrium acetate, -25- (22) 1286996 • « Ο · After 3 〇〇 耳 耳 tetrabutoxy titanium, it was placed in an eggplant flask and heated and stirred at 8 °C. 0.33 50 mol of tributoxy fluorene was added thereto, and the mixture was heated and stirred at 60 ° C to synthesize three kinds of complex alkoxy metal (BLT-based composite liquid) of Bi-Ti-La. Adding 0.3 000 mol of stabilizer to 2-ethylhexanoic acid in the above BLT-based composite solution, stirring at room temperature, adding 0.2000 mol of stabilizer, triethanolamine, and then 6 (TC) The mixture was heated and concentrated to obtain a coating liquid for forming a film of barium titanate (BLT) film in which methoxy-2-propanol was substituted with U-dimethoxy-propane. Synthesis Example 2.

[In the above formula (I), the coating liquid represented by η = 1.0250, x = 0.7317, y = 〇, ζ = 1, α = 0.1 5 00 (Bi : ( Ti + A ) = ι·.ΐ 2 : 1 (Morby))] After adding 0.075 0 mol of yttrium acetate and 〇·3 000 mol of tetrabutoxytitanium to 1-methoxy-2-propanol, it was placed in an eggplant flask. , stir and stir at 8 °C. To this, 0.33 50 moles of tributyloxy, hydrazine was added, and the mixture was heated and stirred at 60 ° C to synthesize three kinds of complex alkoxymetals (BLT-based composite liquid) of Bi-Ti-La. To the above BLT-based composite liquid, 0.33 000 moles of hydrazine was added; the acetylated acetic acid of the condensing agent was heated and stirred, and then 0.2000 mol of water was added thereto, followed by stirring at room temperature. Further, propylene glycol, which is an additive of 0·1000 molar stabilizer, was added thereto, and then stirred at room temperature to obtain a coating liquid for forming a barium titanate (B LT-based) film. -26· (23) 1286996 Synthesis Example 3

[The above formula (〇: n = K0250, χ = 〇 · 6829, y = = 〇, z = Ο · 5, α 2 0.1 5 00 coating solution (Bi : ( Ti + A ) = i 13 · J (Morbi))] In 1, methoxy-2-propanol, add 0·〇4〇0 mole acetic acid steel, 0.3 000 mol of tetrabutoxy titanium, and then put it into the eggplant In the flask, heat it under the heat of C. C• C. Add 〇· 3 4 〇〇 耳 三 丁 丁 秘 、 、, 0.03 00 摩尔 三 triisopropoxy 鐯, and then heat it under 6 〇 Stirring to synthesize four kinds of complex alkoxylates (BLT-based composite liquid) of Bi-Ti-La-Pr. Add 0.2000 mol of water to the BLT-based composite solution, and then stir at room temperature. Further, adding 0·3 000 mole of stabilizer to 2-ethylhexanoic acid, stirring at room temperature, and heating and concentrating it under 6 Torr to obtain 1-methoxy-2-propanol 1,2 · Dimethoxypropane-substituted barium titanate® bismuth (BLT-based) film-forming coating liquid. Synthesis Example 4 [In the above formula (I), η==0·9762, x=〇. 6829, y = Ο · 1 4 2 9 , z = 1, α = - Ο · 1 4 2 9 Coating solution (bi : (Ti + A) 2·〇8 : 1 (Morbi))] In the methoxy-2-propanol, 0. 0667 moles of yttrium acetate, 0.2 8 5 7 moles of titanium tetrabutoxide, After 〇·〇 M3 mol tetrabutoxy oxime, put it into an eggplant flask and heat and stir at 8 ° C. Add -27- (24) 1286996 κ · 0.3 23 8 Molar Butyloxy ruthenium is further heated and stirred at 60 ° C to synthesize four kinds of complex alkoxy metal (BLT-based composite liquid) of Bi-Ti-La-Ge. 0.2000 moles is added to the above BLT-based composite liquid. The water is stirred at a temperature of 0. The addition of 0.3000 mol of the stabilizer to the base of the hexanoic acid is stirred at room temperature, and concentrated by heating at 60 ° C to obtain methoxy-2-propanol. A coating liquid for forming a thin film of barium titanate (BLT type) substituted with 1,2-dimethoxy-propane. Synthesis Example 5 [In the above formula (I), n = 0.9 881, x = 〇.7〇 8〇, v=ry 0 · 1 4 2 9 , z = 0 · 943 5, α = - ο · ο 7 1 4 The coating liquid (Bi : (Ti + A) = 1·08 : 1 ( Moerby))] In 1-methoxy-2-propanol, 0. 0 6 6 0 moles of cerium acetate, 0.0040 moles of methoxytrimethoxypropionate, 0.2 After 857 moles of tetrabutoxyxine and 0·0 1 4 3 moles of tetrabutoxy oxime, they were placed in a nodal flask and heated and stirred at 8 ° C. 0.323 8 moles of tributoxy fluorene was added thereto, and then heated to disturb at 60 C to synthesize five kinds of compound oxymetals (B L T complex liquid) of Bi-Ti-La-Ce-Ge. To the above BLT-based composite liquid, 〇·2〇〇〇 Mo ear ice was added, and the mixture was stirred at room temperature. After adding 0.3000 mol of the stabilizer to the 2-ethylhexanoic acid, it was stirred at room temperature, and concentrated by heating at 60 t to obtain a methoxy-propanol from 1,2-dimethyl A coating liquid for forming a thin film of barium titanate (bLT) which is substituted with an oxy-propane. -28- (25) 1286996 [Coating liquid for forming a normal dielectric film of lanthanum] λ Synthesis Example 6 [In the above formula (1), n = 〇.83〇, x = 0.6747, y = 0, z = = ' 1, a = - 1.020 coating solution (Bi : ( Ti + A ) = 0.92 : 1 (mr ratio))] - in 1-methoxy-2-propanol, add 0.0560 After the ear acetic acid ruthenium, Φ 0.3 000 mol tetrabutoxytitanium, it was placed in an eggplant type flask and heated and stirred at 80 °C. 0.2760 mol of tributoxy fluorene was added thereto, and the mixture was heated and stirred at 6 ° C to synthesize three kinds of composite alkoxy metal (BLT-based composite liquid) of Bi-Ti-La. To the above B L T-based composite liquid, 〇·2000 water was added and stirred at room temperature. After adding 0.3000 mol of the stabilizer to the diethyl hexanoic acid, the mixture was stirred at room temperature, and concentrated by heating at 60 ° C to obtain 1,1 methoxy·2-propanol. 2-Dimethoxy-propane-substituted barium titanate• (BLT-based) film forming solution. Synthesis Example 7 [In the above formula (I), a coating liquid (Bi ·· ( Ti + A) shown by η = 〇 · 9338, x = 0.6747, y = 〇, ζ = 1, α = · 0·3 975 ) = 1.04 :] (Morby))] In the methoxy-2-propanol, after adding 〇〇63〇mol acetic acid 〇, 〇·3 000 mol tetrabutoxy titanium, Place in an eggplant flask at μ. (: heating and stirring. Add 0.3 1 05 moles of Η 铋 铋, -29- (26) (26) 1286996 4 &lt; and then stir at 6 (TC) to synthesize Bi_Ti-La a composite oxygen-burning metal (BLT-based composite liquid). Add 〇·2〇〇〇 Moer water to the BLT-based composite liquid, and stir at room temperature. Add 0·3 0..0 0 Mo After the 2's ethylhexanoic acid stabilizer was stirred at room temperature, it was heated and concentrated under 601 to obtain 1-methoxy-2-propanol substituted by U2-dimethoxy-propane. Titanate fiber = (BLT system) coating liquid for film formation. Synthesis Example 8 [In the above formula (I), η = 1·03 75, χ = 1·3 3 9 8 , y = 〇, 0·4029, a = 0.225 0 coating solution (Bi : ( Ti + A ) ~ 〇 · 92 : 1 (mole ratio))] in methoxy-2-propanol, adding 〇·〇56〇莫耳After the acetic acid steel is 0.3 000 mol of titanium tetrabutoxide, it is placed in an eggplant type flask and heated and stirred at ^ ° C. The ruthenium 2 260 mM tributoxy group 0.083 0 Mo is added thereto. The ear is triisopropoxy oxime, and then heated and stirred under 6 Torr, to form a composite alkoxy metal of Bi-Ti-La-Pr. Lt system composite liquid). Add 0.2000 mol water to the above BLT-based composite liquid, and stir at a temperature. Add 卩.〇·3 0 0 Moer's stabilizer to 2 _ hexanoic acid After stirring at room temperature, it was concentrated by heating at 60 ° C to obtain a titanic acid (BLT) in which 1-methoxy-2-propanol was substituted with 1,2-dimethoxy-propane. Coating liquid for film formation -30- (27) 1286996 Synthesis Example 9 [In the above formula (I), a coating liquid represented by n = 0.8893, χ = οπό 0.1429, z = 1, a = -0.6645 ( (Ti + A) = 0.99 ··:[(Morbi))] In 1-methoxy-2-propanol, add 0.0600 moles of 0.2 8 75 moles of tetrabutoxytitanium, 0.0143 moles The tetrabutoxy oxime was placed in a sputum flask and heated and stirred at 80 ° C. The butyl methoxy hydrazine was added to the mixture and heated at 60 ° C to form Bi. - Ti-La-Ge four kinds of complex alkoxy metal (BLT system liquid). Add 0.2000 moles of water to the above BLT-based composite solution: stir at a temperature, and add 0 · 3 0 0 0 Stabilizing agent 2 hexanoic acid, stirring at room temperature, and heating and concentrating at 60 ° C, Forming a moon liquid with a 1,2-dimethoxy-propane barium titanate (BLT) film. Synthesis Example 1 0 ► [In the above formula (I), n = 0.9881, χ = 〇 · 8210 • 0·1 429, z = 0.7622, α = -0.0714 The coating solution ((Ti + A) = ι·05 : 1 (mole ratio))] in 1-methoxy-2-propanol After adding 0.0633 moles of 0.2875 moles of tetrabutoxytitanium and 0.0143 moles of tetrabutoxybutane, they were placed in an eggplant flask at 80. (: under heating and stirring. Among them, 0.3 121 moles of tributoxy fluorene, 0.0198 moles of isopropyloxy bait, ' y = Bi : only 镧, and added to combine with chamber-ethyl [ Substituting 丨 coating y = Bi : 镧, adding it and heating and stirring at -31- (28) 1286996 6〇 °C to synthesize five kinds of compound oxide metal of Bi-Ti-La-Er-Ge ( BLT-based composite liquid). Add 〇·2〇〇0 mol water to the BLT-based composite solution, and stir at room temperature. After adding 0.3 000 mol of stabilizer to ethyl hexanoic acid, Stir at room temperature, heat at 60 t, and concentrate to obtain a film of barium titanate (BLT) substituted with 1,2-dimethoxy-propanol. Synthesis Example 1 [In the above formula (I), η = 0.988, x = 〇. 8 2i 〇, y = = 0·1 429, z = 〇 · 7622, α = · 〇 ·07]6 Coating solution ((1): (Ti + A ) = 1 ·〇5 : 1 (Morbi))]

In the case of b-methoxy-2-propanol, 0.063 3 moles of acetic acid steel, 0.28 75 moles of tetrabutoxytitanium, and 0.0143 moles of tetrabutoxy oxime are added, and then placed in the oxime type. In the flask, at 80. (: heating and stirring underneath. Add 0.3 121 moles of tributoxy hydrazine, hydrazine 〇 198 molar trimethoxy propionate cerium, and then stir and stir at 60 ° C to synthesize 5 kinds of composite alkane of Bi_Ti_LaKe Oxygen metal (BLT-based composite liquid). Add 〇·2〇〇〇 Moer water to the BLT-based composite solution, and stir at room temperature. Add 3 000 mol of stabilizer to the mixture. Ethylhexanoic acid is stirred at room temperature', and its μ 6 (concentrated by heating under rc to obtain !-methoxy-2 -cohol) is replaced by U2-dimethoxy-propylamine. (BLT system) Coating liquid for film formation. -32- (29) 1286996 Synthesis Example 1 2 [In the above formula (I), n = 1.0128, x = 0.918 0, 0·1429, ζ = 〇 · 6812, α = 0.0768 coating solution ((Ti + A) = 1·〇4 : 1 (mole ratio))] In 1-methoxy-2-propanol, add 0.0633 mol acetic acid 0.2 8 75 After the ear was tetrabutoxytitanium, 〇〇1 43 mol tetrabutoxy oxime, placed in an eggplant flask and heated and stirred at 80 t, in which 0.3121 mol of tributoxy fluorene, 0.0296 mol Di-isopropoxy lock is heated and stirred at 60C to synthesize Bi-Ti - 5 kinds of alkoxylates of La-Ba-Ge (BLT-based composite liquid). Add 〇· 2 〇〇〇 Moer water to the BLT-based composite solution, and stir at a temperature. Add 〇·3〇 to it. After the hexanoic acid stabilizer is stirred at room temperature, it is heated and concentrated under 6 〇t:, and 1-methoxy-2-propanol is used as l52-dimethoxy- A propane-substituted titanic acid (BLT) film-forming coating liquid. Synthesis Example 1 3 [In the above formula (I), η=1·0128, χ=〇·9180, 0·1 429, ζ = 〇·6812 , coating solution of (α + 0·0768) ((Ti + A) = L04 ·· i (mole ratio))] In 1-methoxy-2-propanol, 0.0633 mol acetic acid was added. After 2875 獒 四 tetrabutoxy titanium, 〇·〇 143 mol tetrabutoxy oxime, placed in a crucible flask and heated and stirred at 80 ° C. The tributoxy group of 0·3 121 獒 ear铋, 〇.〇296 Mo Er Diisopropoxy 缌 y = Bi : 镧, add it 're-combined with room ethyl to make 镧 · y = Bi : 镧, add it, then -33- (30 (30)1286996 t 9 is heated and stirred at 60 ° C to synthesize Bi-Ti-La-Sr-Ge s chain a compound burning Oxygen metal (BLT-based composite liquid) 0.2000 mol of ice was added to the above BLT-based composite liquid, and stirred at room temperature. After adding 0. 3 000 mole of stabilizer to h ethylhexanoic acid, it is stirred at room temperature, and concentrated by heating at 60 ° C to obtain 1-methoxy and 2-propanol. A coating liquid for forming a thin film of barium titanate (BLT) which is substituted with 2-dimethoxy-propane. Example 1 The coating liquid for forming a lanthanoid-based ferroelectric thin film produced in Synthesis Examples 1 and 2 was used, and the coatability and density were evaluated by the following methods. [Coating property] A Pt lower electrode of 60 ηηι was formed by sputtering on a 6-inch wafer on which a thermal oxide film SiO 2 having a thickness of 10 nm was formed. The coating liquid for forming a lanthanoid-based dielectric thin film formed in Synthesis Examples 1 and 2 was applied to the substrate at 500 rpm for 1 second, and then at a temperature of 2 OOO rpm for 30 seconds. The surface state of the coating film was visually observed. Thereafter, heat treatment was carried out at 7 ° C for 30 minutes, and the surface state of the film was observed in the same visual manner. The results are shown in Table 1. (The state of the coating film before the heat treatment after coating) ◎: Uniform coating (film state after heat treatment) ◎: Formation of a uniform film _34- (31) (31) 1286996 [density] The 3 〇〇nm thermal oxide film SiO 2 obtained on the coating liquid for forming a lanthanum-based ferroelectric thin film produced in Examples 1 and 2 was subjected to a condition of 50 rpm and 1 second, and then The coating was applied by rotary coating at 2000 rpm for 30 seconds, followed by heat treatment at 7 ° C for 30 minutes to obtain a film. Thereafter, an elliptical symmetry was used to determine the film thickness and refractive index, and the density was measured. When the film thicknesses are equal, the higher the refractive index, the higher the density, and the lower the refractive index, the lower the density. The results are shown in Table 1. In the spin coating stage, the surface state of the coating film was visually observed. Thereafter, heat treatment was carried out at 700 ° C for 30 minutes, and the surface state of the film was observed in the same visual manner. The results are shown in Table 1. Table 1 Coating of a coating film for forming a strong dielectric film, film thickness (nm) after firing at a density coating Example 1 ◎ ◎ 47.8 2.414 Synthesis Example 2 ◎ ◎ 47.0 2.404 Coating as shown in Table 1 As a result of the cloth properties, the coating liquid of Synthesis Example 1 did not crack, and the film after the culturing did not form a mist. It is speculated that this result should be an effect that the added alkanolamine can effectively improve the coatability. In Synthesis Example 2, a uniform film was formed without any problem. It is speculated that it should be the effect of hydrolysis. Further, as a result of the density shown in Table 1, the film obtained from the coating liquids of Synthesis Examples 1 and 2 had a high refractive index and a high density. -35- (32) 1286996 Example 2 [The relationship between the heating temperature and the crystallization of the film was evaluated using the coating liquids prepared in Synthesis Examples 1 and 2] m Using the coating liquids prepared in Synthesis Examples 1 and 2, The film was heat-treated at a heating temperature of 650 ° C ' or 700 ° C to evaluate the relationship between the heating temperature and the crystallization of the film. • That is, a 60 nm Pt lower electrode was first formed by sputtering on a 6-inch wafer on which a thermal oxide film Si〇2 having a thickness of 10 nm was formed. Using the coating liquid prepared in Synthesis Examples 1 and 2 on the substrate having the lower electrode, the coating was performed at 500 rpm for 1 second using a spin coater, and then rotated at 200 rpm for 30 seconds. And then dry at &quot; 250 ° C for 5 minutes. The coating-drying step is repeated four times in total, and finally, in an oxygen atmosphere, heat treatment is performed at 65 ° C, 60 minutes, or 70 ° C, 60 minutes (first heat treatment), A BLT dielectric thin film having a film thickness of 150 nm was formed. The film was subjected to X-ray diffraction (XRD) measurement to obtain an XRD curve. The XRD curve of the film obtained in Synthesis Example 1 is shown in Fig. 1, and the XRD curve of the film obtained in Synthesis Example 2 is shown in Fig. 2. As is apparent from the results of Figs. 1 and 2, regardless of the coating liquids of Synthesis Examples 1 and 2, the film can form the target barium titanate under the conditions of low temperature sintering at 65 ° C and 700 ° C. Crystal structure of (BLT). Example 3 -36- (33) 12869.96 [Magnetic hysteresis characteristics of the dielectric member obtained by using the dielectric thin film formed in Example 2] The respective films formed in Example 2 were passed through a metal mask. Rf magnetron sputtering method to form a Pt upper electrode with a film thickness of 300 nm. Next, in the oxygen atmosphere, at the same temperature as that treated in Example 2, 6 5 〇 ° c, 30 minutes, or 700 ° (:, 30 minutes of annealing annealing treatment (second heat treatment) A dielectric element is formed, and the hysteresis curve of the dielectric element is as shown in Figure 3-1 and Figure 3-2. It is known from Figures 3-1 and 3-2 that the coatings of Synthesis Examples 1 and 2 are obtained. In the film prepared by the cloth liquid, a BLT-based ferroelectric thin film having a large polarization (Pr) can be formed under the conditions of low temperature sintering at 65 ° C and 700 ° C. Example 4 [Use Hysteresis characteristics of the dielectric element formed by the coating liquid obtained in Synthesis Example 3] The coating liquid prepared in Synthesis Example 3 was subjected to the conditions of 500 rpm and 1 second in the same manner as in Example 2, and After 2 rpm and 3 〇 seconds, the coating was repeated and then dried for 5 minutes at 2 5 01. This coating-drying step was repeated 4 times in total, and finally 65 ° in an oxygen atmosphere. C, 30 minutes of heat treatment (the second heat treatment), followed by 70 ° C, 60 minutes of heat treatment (second heat treatment) to form a BLT with a film thickness of 150 nm Dielectric film Next, the pt upper electrode was formed in the same manner as in Example 3, followed by a recovery annealing treatment (3rd heat treatment) of 700 ° C to form a member of the element 37-(34) 1286996. The hysteresis curve is shown in Fig. 4. It can be seen from Fig. 4 that a blT-based ferroelectric thin film having a large polarization pr (Pr) can be formed even under a low temperature sintering condition of 7 〇. Example 5 [Magnetic hysteresis characteristics and leakage characteristics of a dielectric member formed using the coating liquid obtained in Synthesis Example 4] Φ The coating liquid prepared in accordance with Synthesis Example 4 was treated in the same manner as in Example 2 The condition was 50 〇 TPm, 1 second, followed by 2 rpm, 3 〇 second, and then 25,000. (: 5 minutes of drying. Repeat 5 times After the coating-drying step, heat treatment is performed in an oxygen atmosphere for 650 Torr for 30 minutes (first heat treatment), and then heat treatment at 700 ° C for 60 minutes (second heat treatment) is performed to form A BLT dielectric thin film having a film thickness of 190 nm. Next, a Pt upper electrode was formed in the same manner as in Example 3, and then subjected to 700 ° C. The dielectric annealing element is formed by a recovery annealing treatment (third heating treatment). The hysteresis curve of the dielectric element is as shown in Fig. 5, and the shallow leakage characteristic is shown in Fig. 6. It is understood from Fig. 5 that even 7〇(The low-temperature sintering condition of TC can also form a BLT-based ferroelectric thin film with a large polarization (Pr). Further, as shown in Fig. 6, the element has excellent leakage characteristics. -38-(35) 1286996 using a dielectric member formed from the coating liquid obtained in Synthesis Example 5.

Preparation I Hysteresis characteristics and leakage characteristics] The coating liquid prepared in Synthesis Example 5 was subjected to spin coating at 2000 rpm for 30 seconds in the same manner as in Example 2, followed by 500 rpm and then for 2 seconds. Then, it was dried at 25 ° C for 5 minutes. After repeating this coating-drying step four times, heat treatment was carried out in an oxygen atmosphere at 650 ° C for 30 minutes (first heat treatment), and then heat treatment was performed at 700 ° C for 60 minutes ( The second heat treatment) was performed to form a BLT dielectric thin film having a film thickness of 150 nm. Next, a pt upper electrode was formed in the same manner as in Example 3, followed by a recovery annealing treatment (third heat treatment) at 700 ° C to form a dielectric member. The hysteresis curve of this dielectric element is shown in Figure 7, and the leakage characteristics are shown in Figure 8. As is apparent from Fig. 7, a BLT-based ferroelectric thin film having a large polarization (Pr) can be formed even under a low-temperature sintering condition at 700 °C. Further, as seen from Fig. 8, the element has extremely excellent leakage characteristics. Example 7 Using the same coating liquid as the coating liquid capable of forming a ferroelectric thin film, the dielectric properties were formed under changing film forming conditions (heating conditions); the film method was as follows. The coating liquid obtained in Synthesis Example 2 was prepared. Further, the film obtained by using the coating liquid was a BLT crystalline film portion having a strong dielectric property, which was confirmed by Examples 2 and 3. That is, firstly formed with a thickness of OOnm thermal oxide film Si〇2 6-39- (36) 1286996

On the n I 吋矽 wafer, a 60 nm Pt lower electrode was formed by sputtering. On the substrate having the lower electrode, the coating liquid prepared in Synthesis Example 2 was spin-coated at 500 rpm for 1 second and then at 2000 rpm for 30 seconds using a spin coater. In an oxygen atmosphere, heat treatment is performed at 600 ° C, 60 minutes, or 65 ° C for 60 minutes (the first heat treatment). After repeating the coating and heat treatment steps four times, heat treatment was carried out in an oxygen atmosphere at 65 ° C for 60 minutes (second heat treatment) to form a BLT dielectric film having a film thickness of 150 nm. . The film was subjected to X-ray diffraction (XRD) measurement to obtain an XRD curve, and the results are shown in Fig. 9. 9 and the coating liquid of Synthesis Example 2 in which the target barium titanate crystal structure was formed in Examples 2 and 3, and the lower crystal of barium titanate was shown in Example 7. It is known that it has a relatively high amorphous state. Example 8 [Hysteresis characteristics and leakage characteristics of a dielectric member formed using the dielectric film obtained in Example 7] The film formed in Example 7 was passed through a metal mask to an RF magnetron A Pt upper electrode having a diameter of 200//m and a film thickness of 300 nm was formed by sputtering. Next, in the oxygen atmosphere, a recovery annealing treatment at 650 °C (third heat treatment) was carried out. The hysteresis curve after the recovery and annealing of the dielectric element is as shown in Fig. 1 . -40- (37) (37) 1286996 It is known from Fig. 10 that the coating liquid of Synthesis Example 2 of the dielectric thin film showing the dielectric properties of Examples 2 and 3 was changed by heating (roasting). After the method, a dielectric film having a dielectric property can be formed even under a low temperature sintering condition of 65 ° C. Further, as shown in FIG. 11, the dielectric element obtained by using the film has Excellent leak characteristics. [Example 9] [Example of metal composition having a dielectric constant] On a 6-inch wafer on which a thermal oxide film SiO 2 having a thickness of 10 nm was formed, a Pt lower electrode of 60 nm was formed by sputtering. On the substrate having the lower electrode, the coating liquid prepared in Synthesis Examples 6 to 13 was rotated at 2 OO rpm and 30 seconds using a spin coater at 500 rpm, for 2 seconds. After coating, it was dried at 25 ° C for 5 minutes. After repeating the coating and drying steps four times, the heat treatment was carried out in an oxygen atmosphere at 65 ° C for 30 minutes (the first heat treatment), and then the heat treatment was carried out at 65 ° C for 60 minutes. 2 heat treatment) to form a BLT dielectric thin film having a film thickness of 140 nm. The film was subjected to X-ray diffraction (XRD) measurement to obtain an XRD curve, and the results are shown in Fig. 12. It is understood from the hidden 1 2 that even when the coating liquid of any of Synthesis Examples 6 to 13 is used, it is confirmed that the crystallinity of barium titanate in the film is lowered under the low-temperature burning condition at 650 °C. The situation in which the amorphous state increases. EXAMPLES 〇-41- (38) (38) 1286996 [Magnetic hysteresis characteristics and leakage characteristics of a dielectric element formed using the dielectric thin film obtained in Example 9] The film formed in Example 9 was used. The dielectric film formed by the coating liquids prepared in Synthesis Examples 9 to 11 was formed by a metal photomask by RF magnetron sputtering to form a Pt upper portion having a diameter of 200 // m and a film thickness of 300 nm. electrode. Next, in this oxygen atmosphere, recovery annealing treatment (third heating treatment) was carried out at 650 ° C which was the same temperature as that of the treatment of Example 9. The hysteresis curve and leakage characteristics of each dielectric film after the recovery and annealing are as shown in the following figures. Further, the dielectric constants of the coating liquids of Synthesis Examples 9 to 11 are shown in Table 2. Fig. 13 is a hysteresis graph of a dielectric member formed by the coating liquid of Synthesis Example 9. Fig. 14 is a graph showing the leakage characteristics of a dielectric member formed by the coating liquid of Synthesis Example 9. Fig. 15 is a graph showing the hysteresis of a dielectric member formed by the coating liquid of Synthesis Example 1. Fig. 16: A graph showing the leakage characteristics of a dielectric member formed by the coating liquid of Synthesis Example 10. Fig. I 7 is a hysteresis graph of a dielectric member formed by the coating liquid of Synthesis Example 1. Fig. 18 is a graph showing the leakage characteristics of a dielectric member formed by the coating liquid of Synthesis Example 1. -42- (39) 1286996 Table 2 Dielectric Rate (ε) of Coating Liquid for Dielectric Film Formation Synthesis Example 9 490 Synthesis Example 1 〇 380 Synthesis Example 1 1 360 It is known from Figs. 13 to 18 at 65 0° (Under the low-temperature burning condition, a dielectric film having a dielectric property can also be formed. Further, it is known that the B LT dielectric film has excellent leakage characteristics and has a high dielectric constant. In addition to the coating liquids of Synthesis Examples 6 to 8, 12 to 13, when the dielectric element was produced, it was found that the BLT dielectric film also had a dielectric property, excellent leakage characteristics, and high dielectric properties. As shown above, a conventional dielectric material having a good high dielectric constant (low bleed current, high dielectric constant) can be obtained by using a coating liquid obtained by using a specific alkoxide metal raw material. In the case of a complex alkoxy metal, a coating having good coating properties, a dense film can be formed, a stable metal composition ratio, a change in the ratio of metal composition in the film can be suppressed, and excellent handleability (not easily affected) can be obtained. Coating solution that is affected by environmental conditions such as humidity) and stability (storability). The coating liquid of a specific composite alkoxy metal raw material can be formed at a low temperature (below 700 ° C) to have a good high dielectric property (lower discharge: flow, high dielectric constant), and strong dielectric property ( a strong dielectric film having a large residual enthalpy, etc., and which is a metal coating composition having good coating properties, capable of forming a dense film, and stabilizing, and suppressing a metal composition ratio in the film -43- ( 40) 1286996 A phenomenon in which the change occurs, and a coating liquid having excellent workability (not susceptible to humidity and the like) and stability (storability). Further, when a hydrolyzate is used, a stable metal composition ratio can be obtained. Further, it is possible to suppress a change in the ratio of the metal composition in the film. Further, when the alkanolamine is added, the coatability can be further increased. The present invention provides a metal composition ratio which can be stabilized and can be suppressed. A coating liquid for forming a lanthanide dielectric film in a phenomenon in which a ratio of a metal composition in a film is changed. Further, the present invention provides a lanthanide dielectric body having a low dielectric constant and a high dielectric constant to form a dielectric constant. Coating liquid of the film. When the coating liquid of the present invention is controlled to control the metal composition ratio of the coating liquid, or when the conditions for forming the film are controlled, the normal dielectric forming material and the ferroelectric body can be formed. Therefore, the coating liquid of the present invention is extremely suitable for use as, for example, a DRAM as a normal dielectric material, or a nonvolatile memory as a ferroelectric material, and is widely applicable to semiconductor devices. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an XRI3 graph of a dielectric thin film formed using the coating liquid of Synthesis Example 1. Fig. 2 is a dielectric thin film formed by using the coating liquid of Synthesis Example 2. XRD graph Fig. 3-1 is a hysteresis graph of a dielectric member formed using the coating liquid of Synthesis Example 1. • 44-(41) (41) 1286996 Fig. 3-2 is a hysteresis graph of a dielectric member formed using the coating liquid of Synthesis Example 2. Fig. 4 is a hysteresis graph of a dielectric member formed using the coating liquid of Synthesis Example 3. Fig. 5 is a hysteresis graph of a dielectric member formed using the coating liquid of Synthesis Example 4. Fig. 6 is a graph showing the leakage characteristics of a dielectric member formed by using the coating liquid of Synthesis Example 4. Fig. 7 is a graph showing the hysteresis of a dielectric element formed by the coating liquid of the synthesis example 5. Fig. 8 is a graph showing the leakage characteristics of a dielectric member formed using the coating liquid of Synthesis Example 5. Fig. 9 is an XRD chart of a dielectric thin film (normal dielectric property) formed using the coating liquid of Synthesis Example 2. Fig. 1 is a hysteresis graph of a dielectric member (normal dielectric property) formed using the coating liquid of Synthesis Example 2. Fig. 11 is a graph showing the leakage characteristics of a dielectric member (normal dielectric property) formed by using the coating liquid of Synthesis Example 2. Fig. 12 is an XRD graph of a dielectric film formed by using the coating liquid of Synthesis Example 6 "3. Fig. 13 is a hysteresis curve of a dielectric member formed using the coating liquid of Synthesis Example 9. Fig. 14 is a graph showing the leakage characteristics of a dielectric member formed using the coating liquid of Synthesis Example 9. -45- (42) 1286996 Fig. 15 is a dielectric formed using the coating liquid of Synthesis Example 1 The hysteresis graph of the bulk component. Fig. 16 is a graph showing the leakage characteristics of the dielectric component formed by using the coating liquid of Synthesis Example 1. Fig. 17 is a medium formed by using the coating liquid of Synthesis Example 1. The hysteresis curve of the electric component Fig. 18 is a leakage characteristic diagram of the dielectric member formed using the coating liquid of Synthesis Example 11. -46-

Claims (1)

1286996 t year f month repair (healing) original ten, patent application scope 94 107016 patent application Chinese patent application scope amendments, the Republic of China, August 31, 1995 amendments 1 · a coating liquid, which is formed to contain the following A coating liquid of a ferroelectric lanthanide dielectric thin film of a composite metal oxide represented by the formula (I), which is characterized in that it contains a complex alkane oxygen formed by at least two kinds of alkoxymetals of Bi and Ti. Metal-reuse water, or water-catalyst-hydrolyzed-partially condensed gel-sol solution, {Bi4_x, (Laz, Bh) x "(Ti3_y, Ay) 012" (I) (wherein A It is at least one metal element selected from V, Cr, Mn, Si, Ge, Zr, Nb, Ru, Sn, Ta, and W, and B is a rare earth element containing no antimony, Ca, Sr, and Ba. At least one selected gold element, x, y, and z are each 0$x&lt;4,0SyS0.3, 00&lt;zSl, η is 0·7 to 1-4, α is According to the metal composition ratio, the price is determined by φ). 2. The coating liquid according to claim 1, wherein the coating liquid is further added with an alkanolamine. 3. The coating liquid according to claim 1, wherein in the above formula (I), 'X is 0 &lt; χ < 4 is the number of Tpc. 4. The coating liquid according to claim 1, wherein in the above formula (I), z is a number represented by 0 &lt; ζ &lt; 5. The coating liquid according to claim 1, wherein in the above formula (I), y is a number represented by 0 &lt; yS 0·3. 12.86996 6. The coating liquid according to claim 1, wherein in the above formula (I), the metal element A is Ge and y = 0.05 to 0.20. 7. The ratio of the coating liquid of claim 1, wherein Bi, Ti and A metal elements (which also contain no A metal element) are Bi : ( Ti + A ) = 1.07 To 1.15: 1 (Morbi) ratio. A coating liquid for forming a normal dielectric lanthanide dielectric film containing a composite φ metal oxide represented by the following formula (I), characterized in that it contains at least Bi a composite alkoxy metal formed by two kinds of alkoxides of Ti or a mixed alkoxy metal obtained by mixing at least a mixture of alkoxide and alkoxide, and then subjected to hydrolysis-partial condensation treatment using water or water and a catalyst. The resulting gel-sol solution, {Bi4-x, (Laz, Bbz) x}n(Ti3-y, Ay) 〇ΐ2+α (I) (where A is V, Cr, Μη, Si, Ge , at least one metal element selected from Zr, Nb, Ru, Sn, Ta, and W, and b is at least one metal element selected from the group consisting of rare earth elements not containing φ, Ca, Sr and Ba , X, y, and z are each 0$x&lt;4,0SyS0.3, 〇&lt;ζ$ΐ, η is a number from 0.7 to 1.4, and α is a valence determined by the metal composition ratio). . 9. The coating liquid according to claim 8, wherein the coating liquid is further added with an alkanolamine. 10. The coating liquid according to claim 8, wherein 'X' in the above formula (I) is a number represented by 0 &lt; x &lt; In the above formula -2- 1286996 (I), z is a number represented by 0 &lt; ζ &lt;1. 1 2 The coating liquid according to item 8 of the patent application, wherein in the above formula (I), 丫 is a number represented by 0 &lt; yS 0.3. 13. The ratio of the coating liquid of claim 8 in which the Bi, Ti and A metal elements (which also have no a metal element) are Bi: (Ti + A ) = 〇 · The ratio of 90 to 1·〇6: 1 (Morbi). Φ 1 4 · a method for forming a dielectric film of a dielectric ray-based dielectric film, characterized in that the coating liquid of the eighth application of the patent application is applied to a substrate without being subjected to heat drying treatment The heat treatment (first heat treatment) at 500 to 700 ° C is performed to form a coating film, and the above-described application to the heat treatment (first heat treatment) may be repeated several times to form a layer of the coating film. Further, the mixture is further subjected to heat treatment at 600 to 700 ° C (second heat treatment). 15. A normally φ dielectric lanthanide dielectric film containing a composite metal oxide represented by the following formula (I), which is applied to a substrate provided on the substrate of the eighth application of the patent application. On the electrode, and baked, { B i 4 - X ( Laz, Bi_z) x}n ( Ti3-y, Ay) 〇ΐ 2 + α ( I) (where A is V, Cr, At least one metal element selected from the group consisting of Μη, Si, Ge, Zr, Nb, Ru, Sn, Ta, and W, and B is at least 1 selected from rare earth elements not containing cerium, Ca, Sr, and Ba The metal elements, x, y, and z are each 0Sx&lt;4,0$yS0.3, 00&lt;zSl, η is a number from 0.7 to 1.4, and α is a valence determined by the metal composition ratio). -3- 1286996 16. The film of claim 15 wherein the ratio of Bi, Ti and A metal elements (which also contains no A metal elements) is Bi : ( Ti + A ) = 0.90 to 1.06 : 1 (Mo Erbi) ratio.