JPS60236404A - Method of producing thin film ferrodielectric material - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a dielectric material, particularly lead titanate (hereinafter referred to as "machi").
, lead titanium zirconate (hereinafter referred to as 1-PZT), composition formula: Pb (M'l/3-M"2)
/3)03 (Here, M' is bivalent My, Co,
Lead titanium zirconate (hereinafter referred to as three-component system PZT j) in which a third component represented by Fe, Crs, Zn, Mn, Ni or Cd is added and dissolved as a solid solution. ) or lanthanum-containing lead titanium zirconate (hereinafter referred to as PLZTJ) on a metal substrate.

Since the thin film ferroelectric material formed by the method of the present invention has a high dielectric constant and excellent ferroelectric properties, it can be used as a thin film capacitor, piezoelectric material, pyroelectric material, etc.

[Prior art]

Conventionally, many methods have been proposed for manufacturing pb-based dielectric thin films (Thin Film Handbook, 243-571).
(See page, Ohmsha, December 1981). In particular, thin films manufactured by RF sputtering exhibit ferroelectric properties and are expected to be applied to devices using piezoelectricity and pyroelectricity. It is difficult to control, and the manufacturing equipment is multi-spindle and expensive.

On the other hand, a method for manufacturing dielectric thin films using C■ has also been proposed (Jpn, J, ApptPhys, Part
2198121 (10)655-6). However, the electrical properties of the dielectric thin film obtained by this method are
This is significantly inferior to thin films obtained by sputtering.

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 then left in air at room temperature for 30 minutes, and then for 1 hour.
A method for manufacturing a dielectric thin film is to dry it in a constant temperature bath at 10°C for 30 minutes to complete the hydrolysis reaction, and then to sinter it at a temperature of 800°C while forcing steam into an electric furnace. Proposed. However, the solution of the organometallic compound exemplified in this method is extremely unstable;
It absorbs moisture from laughing gas and is easily hydrolyzed, making it difficult to obtain a homogeneous coating. Furthermore, the thin film obtained by this method tends to cause electrical conduction and cannot be used as a practical thin film ferroelectric material.

[Problem to be solved]

SUMMARY OF THE INVENTION An object of the present invention is to provide a method for manufacturing a thin film ferroelectric material in which a thin film of a pb-based dielectric material having ferroelectric properties without conduction is formed on a metal substrate by a solution method.

[Means for solving problems]

The present invention uses lead titanate (PT), lead titanium zirconate (PZT), lead titanium zirconate with a third component added (ternary component PZT), and lanthanum-containing lead titanium zirconate (PZT).
One type selected from the group PLZT') (7"l-1
[wI*-/I'rRei Shita Kyou 1H Kouran Kei Man °Ikg-IGa Maru 1fi-mA-Diketones, ketonic acids, ketoesters, oxyacids, oxyacid esters, and oxyketones. A dielectric-forming precursor solution prepared by dissolving in an organic solvent containing at least one selected from the group as a main component is applied to a metal substrate and dried to form a coating film of the dielectric-forming precursor. Calcination is performed at a temperature above the decomposition temperature of the organic matter in the film and below the crystallization temperature of the dielectric, and the application, drying, and calcination of the dielectric forming precursor solution are repeated, and then the temperature above the crystallization temperature of the dielectric is repeated. Lead titanate is formed on the metal substrate by firing at a high temperature, or by repeatedly applying the dielectric forming precursor solution to the metal substrate, drying, and firing at a temperature higher than the crystallization temperature of the dielectric. (PT)
Forming two or more layers of one type of thin film selected from the group consisting of lead titanium zirconate (PZT), lead titanium zirconate with a third component (ternary component PZT), and lead titanium zirconate containing ditanium (PLZT). This is a method for manufacturing a thin film ferroelectric material.

In the present invention, the thin film ferroelectric material is formed on a metal substrate by general formula (1) and compositional formula (1) shown in (a) to d) below.
A thin film of one type of pb-based dielectric material selected from the group consisting of PT, PZT, three-component PZT, and PLZT represented by 2) or 4) is formed.

(a) General formula (1) Lead titanate (PT) expressed by % formula % (1) (b) Composition formula (2) % formula % (2) y can be 0.7 to 0.45. , and xyy=i. ) Lead titanium zirconate (PZT), for example, Ti/Zr is 0.3-0.55 / 0.1-0.45
17) PZT.

(c) Composition formula (3) % formula % (3) M" represents Nbt or Ta, X is 0.3 to 0.55, y is 0.7 to 0.45, and x + y = 1 t s + t = 1 and rare≦0.6).
lead titanium zirconate (three-component PZT)
) For example, if M' is Mari and M'' is Nb, then PZT -PM
N, M' are Ni, M"d (Nb "t'al PZT
- Three-component system PZT such as PNN.

(d) Composition formula (4) % Formula % (4) (Here, M represents Ti and Zr, and 2≦0.2.) Lanthanum-containing lead titanium zirconate (PLZT
) The following (a) to d) are used as precursors for forming these Pb-based dielectrics.

(a) A mixture of an organic titanium compound and a lead compound or a reaction product thereof (PT) (b) A mixture of an organic titanium compound, an organic zirconium compound and a lead compound or a reaction product thereof (PZT) {(C) Magnesium compound , cobalt compounds, iron compounds, one selected from the group consisting of chromium compounds, zinc compounds, manganese compounds, nickel compounds and cadmium compounds, tantalum compounds or niobium compounds, organic titanium compounds, organic zirconium compounds and mixtures of lead compounds. or a reaction product thereof (ternary PZT) (d) a mixture of a lanthanum compound, an organic titanium compound, an organic zirconium compound, and a lead compound, or a reaction product thereof (PLZT) In the present invention, the metal substrate is gold, platinum It is a plate or foil made of heat-resistant metal such as nickel, nickel-chromium alloy, etc., coated with a thin film of silver, copper, nickel, nickel-chromium alloy, etc., or platinum group metal. As a result of intensive research into a method for forming a non-conducting Pb-based dielectric thin film on a metal substrate by a solution method, they dissolved the dielectric forming precursor described above in a polar solvent such as acetylacetone and made S. /a The lightning-shaped skin precursor solution is extremely stable against hydrolysis, has excellent coating properties on substrates, especially metal substrates, and easily forms a homogeneous coating film of the dielectric forming precursor. What can be obtained - After repeating the coating film formation and temporary stitching to laminate an amorphous thin film of dielectric material □
Or, by repeating coating film formation and firing, a dielectric crystallized thin film is laminated, and the resulting thin film has no conduction and has excellent dielectric and ferroelectric properties. Through line diffraction, it was discovered that preferential orientation of specific crystal planes was observed in the thin film, and the present invention was completed.

In the present invention, the selection of the dielectric-forming precursor and its solvent affects the film-forming properties of the dielectric-forming precursor. The organic titanium compound and organic zirconium compound used in the dielectric forming precursor described above may be organic solvent-soluble compounds, for example, the following general formula (5) % formula % (5) R is a monovalent hydrocarbon group represents the same species of the same species. ) The following general formula (6) % formula % (6) (herein, M and R have the same meanings as above) is repeated. Polymers with a degree of polymerization of 2 to 20,
Examples include compounds in which part or all of the alkoxy groups of an alkoxide or a polymer thereof are substituted with the residue of a chelating agent having two functional groups. Specific examples of organic titanium compounds include tetramethoxytitanium, tetrabutoxytitanium, tetraisopropoxytitanium, tetrabutoxytitanium, dimethoxydiimpropoxytitanium, jetoxydiisopropoxytitanium, jetoxydibutoxytitanium, etc. titanium alkoxides having a substituent, polymers produced by hydrolysis of titanium alkoxide, a part or all of the alkoxy groups of these alkoxides or polymers, acetylacetone, benzoylacetone, etc. β of
- diketones, ketonic acids such as acetoacetic acid, glopionylbutyric acid, benzoylformic acid, methyl and ethyl ketonic acids,
Lower alkyl esters such as propyl and butyl, lactic acid,
Oxyacids such as glycolic acid, α-oxybutyric acid, and salicylic acid, lower alkyl esters of oxyacids, oxyketones such as diacetone alcohol and acetoin, α-amino acids such as glycine and alanine, and amino alcohols such as amine ethyl alcohol. Examples include compounds substituted with the residue of a chelating agent having two functional groups, such as.

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 group of the oyohizirconium alkoxide or the polymer thereof may be substituted with the above-mentioned two. Examples include compounds obtained by t-substitution with a 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, and a part of the alkoxy group of the alkoxide, or residues of chelating agents having two functional groups as described above, are used. Use compounds substituted with . In addition, magnesium compounds,
As 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, acetates, Carboxylate salts such as propionate and butyrate, and alkoxides are used.

A mixture of the metal compounds described above can be used as the dielectric body forming precursor, but in consideration of coating film forming properties, it is preferable to use a reaction product between these metal compounds, and more preferably PT, PZT, 3 For each of the component systems PZT and PLZT, the present applicant previously published JP-A No. 5
Monomers or multimers having a repeating number of 1 to 50 structural units shown in the following compositional formulas (7) to 9) are used, as disclosed in No. 8-41725 and JP-A No. 59-42392.

PbTi0; (OR)j (OCOR')k...
・・・・・・・・・・・・・・・(7) (Here, R and R' represent different and similar monovalent hydrocarbon groups, and j+ = 2.) PZT : Th j and three-component system PZT K, Pb
Ms'(M' 1/3 M"2/3) t Ox
(OR month (0COR') k・・・・・・・・・・・
・・・・・・・・・(8) (Here, MFiTi and Zr M′ are divalent balls, Co, Fe, Cr, Zn, I
vln, Ni or Cd M" is Nb or Ta R and R' represent different and similar monovalent hydrocarbon groups, s+ When t=1 and t≦0.6, t=0, PZT, t
'When Fo(7), the three-component system PZTj + k = 2. ) For PLZT, Pbi-zLazMl-z/402(OR)j (OC
OR')k・・・・・・・・・・・・・・・(9)(2
> (y y k〒4 trigram k 1g7.vR and R'
represents different and similar monovalent hydrocarbon groups, and 2≦0.2 j+=2. ) Lower alcohols such as methanol, ethanol, isopropanol, butanol, β-alcohols such as acetylacetone, benzoylacetone, etc. can be used as a solvent for the dielectric forming precursor consisting of a mixture of the metal compounds or their reaction products.
- diketones, ketonic acids such as acetoacetic acid, propionylbutyric acid, benzoylformic acid, methyl and ethyl ketonic acids,
Lower alkyl nisdels such as propyl and butyl, lactic acid,
1m of a single solvent or a mixed solvent of two or more selected from the group consisting of oxyacids such as glycolic acid, α-oxybutyric acid, and salicylic acid, lower alkyl esters of oxyacids, and oxyketones such as diacetone alcohol and acetoin. An organic solvent containing as the main component is used. Considering the stability of the dielectric forming precursor solution and the applicability to metal substrates, it is preferable to use β-diketones, and more preferably, the dielectric forming precursor has excellent coating film forming properties and is available at low cost. Use easy acetylacetone. These organic solvents are used for purposes such as adjusting the viscosity of the dielectric forming precursor solution.
As a target, an alcohol solvent or an aromatic hydrocarbon solvent can be added. In addition, when the metal compound is a chelate, methanol, ethanol,
A similar effect can be obtained by using a solvent whose main component is a lower alcohol such as Impropatol or butanol.

In the present invention, the dielectric-forming precursor solution is prepared by dissolving the dielectric-forming precursor in the organic solvent, but if the concentration of the dielectric-forming precursor is too low, one application, drying and This is undesirable because the dielectric thin film formed by firing is too thin, and the coating, drying, and firing steps must be repeated too many times to obtain a thin film dielectric having the desired i thickness. On the other hand, if the concentration is too high, the coating film formed by one application will be too thick, and thin film defects such as pinholes and cracks will easily occur during baking, which is not preferable.

The preferred concentration range of the dielectric forming precursor solution varies depending on the coating method employed, but is 5 to 20% by weight in terms of the metal complex oxide contained in the precursor solution.

In the present invention, the dielectric-forming precursor solution is applied to a metal substrate, particularly a metal substrate used as an electrode, and dried to form a coating film of the dielectric-forming precursor. The dielectric is heated and maintained at a temperature above the decomposition temperature of the organic matter and below the crystallization temperature of the dielectric and calcined, and then the dielectric forming precursor solution is applied, dried, and calcined repeatedly to form the dielectric. After forming multiple layers of amorphous thin films, the method involves heating and firing to a temperature higher than the crystallization temperature of the dielectric, or repeating the formation of a coating film of a dielectric forming precursor and firing at a temperature higher than the crystallization temperature. Accordingly, a crystallized dielectric thin film having a desired thickness, no conductivity, and exhibiting ferroelectricity is formed on a metal substrate, and the purpose and repeated operations of coating film formation and baking are - It acts on the formation of a thin film without any manipulation. The dielectric forming precursor solution can be applied to the substrate by any method that provides a coating film of uniform thickness, such as dipping method, spray method, spinner method, roll coating method, brush coating method, etc. can. Especially 1. The dipping method is preferably employed because it is easy to obtain a coating film with a uniform thickness with simple operations and it is easy to process in large quantities. More preferably, the precursor solution is 40 to 9
A hot dipping method is used in which the substrate is heated to a temperature of 5°C and dipped. The calcination temperature varies depending on the dielectric forming precursor and the type of organic solvent used, but is usually in the range of 200 to 500°C, and the firing temperature is usually 450°C, although it varies depending on the dielectric composition. That's all. For example, when using an acetylacetone solution of the dielectric forming precursor represented by the above-mentioned compositional formula (7) to 9), the calcination temperature is 200 to 450°C, preferably 350 to 450°C.
, firing temperature 450°C or higher, preferably 450-700°C
, PZT te has a calcination temperature of 2oo~5oooC, fresh→I
, / 糾J (11N--B l'l oY' Yuc
, e aJ #C: A
0 to 500°C, preferably 400 to 500°C, firing temperature 600°C or higher, preferably 600 to 800°C, and P
For LZT, the calcination temperature is 200 to 500°C, preferably 40°C.
0 to 500℃, firing temperature 600℃ or higher, preferably 600℃
~800°C. The coating film formation and calcination of the dielectric material forming precursor, or the coating film formation and firing operations need to be repeated at least once in order to repair thin film defects such as pinholes and cracks, and are preferably repeated. ,2
Repeat ~30 times.

In the present invention, by employing the above structure, PT, PZT, 3 represented by the general formula (1) and compositional formulas (2) to (4) described above can be formed on a metal substrate, particularly a metal electrode.
Component system PZT or 1. PLZT, (D 0.1~50
It is possible to form a thin film with ferroelectricity (fimf) conductivity (D), and to manufacture the desired thin film ferroelectric material.

In addition, instead of a metal substrate, a glass substrate, a ceramic substrate, a conductive film such as a tin-doped indium oxide film C
A thin film ferroelectric material can be manufactured using a glass substrate or a ceramic substrate on which a gold vapor-deposited film (ITO film) or a gold vapor-deposited film is formed in the same manner as in the case of a metal substrate.

〔Example〕

Hereinafter, the present invention will be explained in more detail with reference to examples showing one aspect thereof. However, the scope of the present invention is not limited in any way by the following examples.

[Example 1] Production of PTT film ferroelectric material Lead acetate with a purity of 99.0%: 8.9 t (40 mmo
t), 99.0% purity tetrabutoxytitanium: 13
．． 6F (40mmot) and acetylacetate 7:15
The mixture was charged into a 0 ml reaction vessel, heated and kept under reflux for 2 hours, and then distilled off with acetylacetone and methanol: 1
00mft and PbTi0. Converting to 11.3
A PT spindle-forming precursor solution with a wt concentration was prepared.

Using one spinner for the solution, 2QOOOrpmX40
It was coated on a platinum foil with a thickness of 10 μm under the conditions of
After heating and firing to 570°C at a temperature increase rate of 0°C/m1n, the product was cooled. Repeat this operation 4 times, 9 times, 11 times and 2 times.
By repeating the process five times, a PT thin film ferroelectric material having the film thickness shown in Table 1 was manufactured.

A 0.10-gold thin film was formed on the surface of the obtained PTT film by sputtering, and Ag paste was applied thereon to form an electrode, and the dielectric properties, ferroelectric properties, and pyroelectric properties were measured.

Table 1 shows dielectric properties (relative permittivity: ε and dielectric loss:
ferroelectric properties (remanent polarization: Pr and coercive electric field: E), applied voltage: 440 KV/50 Hz
c) and the pyroelectric properties (pyroelectric coefficient Pr: Teitei/αT) of Pr after polarization for 10 minutes at 300 KV/air at room temperature, measured by temperature change.

The ferroelectric characteristic curve of the PTT film ferroelectric obtained by repeating the thin film formation 25 times is shown in FIG. 1, and the X-ray diffraction pattern is shown in FIG.

Table 1 rr [Example 2] Production purity of PZT thin film ferroelectric material: 99.
096 lead oxide: 8.9 t (40 mmot), purity 99.01 tetrabutoxy titanium: 6.6 F (19
Pb (TiO,48・ZrO,52) was charged with 85t of tetrabutoxydil (mmot), purity 86.6%, into a reaction vessel, heated and reacted under reflux.
A PZT dielectric forming precursor solution having a concentration of 12.5 wt % in terms of 0.03 was prepared.

A nickel foil with a thickness of 5 μm was immersed in the solution maintained at a temperature of 50 to 60° C., pulled up and dried at a rate of 47 cm/min, and a coating film of the PZT dielectric precursor was formed. Then, 3
It was held for 0 minutes and fired. Repeating coating film formation and firing,
A transparent PZT thin film dielectric was fabricated.

In Table 2, the number of repetitions of thin film formation, film thickness, 0.1KH
Dielectric properties measured in alternating current electric field of z, applied voltage: 250K
The ferroelectric properties measured in an alternating current electric field of V, 50 Hz and the pyroelectric properties after polarization treatment for 10 minutes at 250 KV/air at room temperature are shown in Table 2.

[Example 3] Production of ternary PZT thin film ferroelectric
COO) 216.4 f (50 mmot), purity 86
．． 6wt tetrabutoxyzirconium: Zr (
0C4H11) 43,3 f (7,5 mmot),
Tetrabuto-T ciquititay with purity 99w1%:h(QC4He)46. Of (17
,5mmot), purity 9 & 2wt96(Dacetic acid dichloride: Ni (CH3COO)23.Of (16,7m
mot), pentabutoxyniobium with a purity of 99.99 wt%: Nb (0C4Ho )s 15.2 f (3
3,3 mmot ) and xylene 309 were charged, and the temperature was raised while stirring under a nitrogen atmosphere. Reaction temperature approx. 130
Butanol and butyl acetate began to distill out from ℃, and the reaction solution changed from its original white turbid state to a yellow-brown homogeneous and transparent solution. Approximately 150P of acetylacetone is added to the reaction solution.
was added and heated to reflux, Q, 15PbZr03...0.
35 PbTiO3-0,500Pb(Nil/3Nb
2/3) Three-component system P with a concentration of 10 wt% converted to 03
A ZT dielectric forming precursor solution was prepared.

A platinum substrate of 30wn x 50mm x O12 tone was heated to 60°C and immersed in the above-prepared three-component dielectric forming precursor solution maintained at 60 to 70°C, and pulled up at a rate of 47 min/min to remove the precursor. A film was formed. Then, 5
Temporary firing was carried out by holding the sample in an electric furnace heated to a temperature of 00° C. for 30 minutes. After repeating dipping in the precursor solution and calcining, it was placed in an electric furnace heated to 700°C.
The main firing was held for 0 minutes, and the formed thin film was crystallized.

As a result of X-ray diffraction of the obtained thin film, 0.15 PbZrO
It was confirmed that the film was a thin film of three-component PZT having composition No. 3. The film thickness obtained by repeating the thin film formation 13 times is 1,
Dielectric constant: ε is 408, dielectric loss: t
anδ was 6elb. Applied voltage 250KV/an
The nine ferroelectric properties measured with remanent polarization: I'r = 22.5
μc/cri= and coercive electric field: Ec = 75 KV
/cm.

[Example 4] Production purity of PLZT thin film ferroelectric material: 99.1
wt% lead acetate: 15.2 f (46,5 mmot
), lanthanum acetate with purity 95.6wt: 1.169
(3.5 mmot), tetrabutoxyzirconium with a purity of 86.6 wt%: 14. ．． 1 t, purity 99.1
wt% tetrabutoxytitanium: 5.9 t (17
, 2 mmot) Butanol and butyl acetate began to distill out from 30° C., and the reaction solution changed from its initial cloudy state to a yellowish-brown homogeneous transparent solution.

Under reduced pressure, xylene: 25f was distilled off, and then reacted under reflux to form PbO,93LaO,07(ZrO,65
Concentration converted to Ti0.350.9830i is 10wt
% amber-colored PLZT dielectric forming precursor solution was prepared.

60~70C: 30 rrrm x 50 th
A platinum substrate of em X 0.2 van was heated to 60°C, immersed, pulled up at a speed of 47 m/min to form a film of the precursor, and then heated to 500°C.

It was held in an electric furnace for 30 minutes to perform temporary firing. After repeating dipping in the precursor solution and calcining, an additional 75
The resulting thin film was crystallized by main firing by holding it in an electric furnace heated to 0° C. for 30 minutes.

As a result of X-ray diffraction of the obtained thin film, it was confirmed that it was a PLZT thin film.

Table 3 shows the number of repetitions of thin film formation, film thickness, o, IKH.
Dielectric properties measured in an alternating electric field of z and applied voltage 120
KN'/d, measured in an alternating current electric field of 50 KHz and exhibits nine ferroelectric properties.

) [Reference Example 1] Pyrex coated with Sn-doped indium oxide transparent conductive film (ITO film) in which the PLOT dielectric forming precursor solution prepared in Example 4 was kept at a temperature of 60 to 70°C. Board (30m x 50m x IWII
ll) and then treated in the same manner as in Example 4 to form a transparent PL film 13 times and with a film thickness of 1.7 μm.
A ZT thin film was formed. The direct transmittance of light with a wavelength of 600 nm is 481, ε = 540, tan δ = 5.2%, Pr = 10.2 μc/a/l, measured with an applied voltage of 12 KV/i and an AC electric field of 50 Hz. Ec==3K
It was V4n.

〔Effect of the invention〕

In the present invention, as shown in the above embodiments, gold can be used to produce the desired thin film ferroelectric material having excellent dielectric properties and ferroelectric properties.

As shown in FIG. 1 and each example, the ferroelectric properties of the produced thin film formed body are obtained as a synergistic effect of the selection of the dielectric forming precursor and its solvent, and the adoption of the multilayer thin film forming method. . In particular, - the adhesion of the thin film to the metal substrate is
Much depends on the choice of solvent.

In the present invention, a method for forming a Pb-based dielectric thin film on a metal substrate is specified, but as shown in Reference Example 1, the same type of thin film can also be formed on a transparent substrate coated with a transparent conductive film, such as a glass substrate. In particular, in the case of PLZT, the thin film ferroelectric material is manufactured using a solution method, which makes it easy to control the stoic geometry, making it desirable. In other words, the present invention has the advantage of being able to produce a thin film ferroelectric having the desired performance, and also has the advantage of low production costs because the production equipment is simple and the operation is simple.

The thin film ferroelectric material produced by the method of the present invention can be expected to be applied to thin film capacitors, piezoelectric materials, pyroelectric materials, etc. by utilizing its excellent dielectric properties, ferroelectric properties, and/or pyroelectric properties. .

The present invention provides a method for manufacturing Pb-based thin film ferroelectric materials, which have been considered difficult to manufacture due to difficult stoichiometry control and easy conduction, using a simple method called a solution method. However, its industrial significance is extremely large.

[Brief explanation of the drawing]

Fig. 1 Hysteresis curve of the PT thin film ferroelectric obtained in Example 1-4 X-ray diffraction diagram of the electric thin film Patent applicant Nippon Soda Co., Ltd. Agent (6286) Haruyuki Ito (7125) Yoshimi Yokoyama No. 1 figure

Claims (1)

[Claims] 1. Lead titanate (FT), lead titanium zirconate (FA)
T), third component added titanium lead zirconate (three component system PZ
T) and lanthanum-containing titanium lead zirconate (PLZT)
) a dielectric forming precursor selected from the group consisting of lower alcohols, β-diketones, ketonic acids, ketoesters, oxyacids, oxyacid esters and oxyketones; A dielectric formation precursor solution prepared by dissolving in an organic solvent containing at least one selected one as a main component is applied to a metal substrate and dried to form a coating film of the dielectric formation precursor. Calcination is performed at a temperature above the decomposition temperature of the organic matter in the film and below the crystallization temperature of the dielectric, and the application, drying, and calcination of the dielectric forming precursor solution are repeated, and then the temperature above the crystallization temperature of the dielectric is repeated. Baking at temperature or
Alternatively, lead titanate (PT) can be formed on a metal substrate by repeatedly applying the dielectric formation precursor solution on a metal substrate, drying it, and firing it at a temperature higher than the crystallization temperature of the dielectric.
), forming two or more 1s thin films selected from the group consisting of lead titanium zirconate (PZT), third component-added lead titanium zirconate (ternary component PZT), and lanthanum-containing lead titanium zirconate (PLZT). ◇ 2. The dielectric formation precursor is one of the following (a), (b), (c)
) and (d) (a) A mixture of an organic titanium compound and a lead compound or a reaction product thereof. (b) A mixture of an organic titanium compound, an organic zirconium compound and a lead compound or a reaction product thereof. (C) one compound selected from the group consisting of magnesium compounds, cobalt compounds, iron compounds, iron compounds, zinc compounds, manganese metal compounds, nickel compounds, and cadmium compounds, tantalum compounds or niobium compounds, organic titanium compounds, Mixtures of organic dihydroxide compounds and lead compounds or their reaction products. (d) A mixture of a lanthanum compound, an organic titanium compound, an organic zirconium compound, and a lead compound or a reaction product thereof. Claim 1 which is one type selected from the group
A method for producing a thin film ferroelectric material as described in 2.