JP2007005161A - Ferroelectric substance, its manufacturing method and ferroelectric device using the method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a ferroelectric substance having a high dielectric constant, manufacturable by a simple method, and capable of preventing toxic heavy metals from being included therein. <P>SOLUTION: This ferroelectric substance contains organic cation-containing polyanions comprising organic cations, and at least one kind of polyanions selected from a group comprising polytitanic acid anions, polyniobic acid anions and polytantalic acid anions. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a ferroelectric used for a ferroelectric device such as a nonvolatile memory device, a capacitor, a piezoelectric device, a pyroelectric infrared sensor device, a manufacturing method thereof, and a ferroelectric device using the same.

  Ferroelectrics have functions such as spontaneous polarization, high dielectric constant, pyroelectric effect, piezoelectric effect, and electro-optic effect. Conventionally, capacitors, infrared sensors, ultrasonic oscillators, pressure sensors, frequency filters, optical switches, etc. It has been applied to many device developments. In recent years, development of a nonvolatile memory using spontaneous polarization and a gate insulating film of an FET using a high dielectric constant has been carried out.

  By the way, barium titanate is a ferroelectric substance having a perovskite structure that has been known for a long time, and is used in capacitors and the like.

Non-Patent Document 1 describes that most ferroelectrics exhibiting large spontaneous polarization have a perovskite structure or a structure similar thereto. As a specific example thereof, lead titanate (PbTiO 3) having a perovskite structure is described. ₃ ), lead zirconate titanium (Pb (Ti, Zr) O ₃ ), Bi ₄ Ti ₃ O _{12 having} a layered perovskite structure, and the like. However, these ferroelectrics contain toxic heavy metals such as lead and bismuth, and a vacuum process such as sputtering or a heat treatment at a high temperature of 1000 ° C. or more is required for production.

Patent Document 1, a simple perovskite structure (Ba, Sr, Sn) ferroelectric does not contain lead consisting of TiO _3, and, the simple perovskite structure (Ba, Sr, Sn) TiO 3 and other conventional perovskite A ferroelectric with a low lead content, which is a solid solution with a structured ferroelectric, is disclosed. However, since these ferroelectrics are manufactured by a pulse laser deposition method on a substrate heated to 600 ° C. or higher, heat treatment at a high temperature is required.
Supervised by Tadashi Shiogama “Development and Application of Ferroelectric Materials”, CMC Publishing, published December 2001, pages 14-15 JP 2003-146660 A

  An object of the present application is to provide a ferroelectric having a high dielectric constant or a large remanent polarization that can be manufactured by a simple method and that can avoid the inclusion of toxic heavy metals, and a method for manufacturing the same, and It is to provide a ferroelectric device using the above.

  The present invention for achieving the above object is a ferroelectric including an organic cation and an organic cation-containing polyanion comprising at least one polyanion selected from the group consisting of a polytitanate anion, a polyniobate anion and a polytantalate anion. .

  Here, the ferroelectric material is a dielectric material in which the relationship between an applied electrode and polarization is not linear but exhibits hysteresis.

  The ferroelectric of the present invention can be produced by a very simple method such as drying the dispersion, and does not require a vacuum process such as sputtering or a heat treatment at a high temperature. In addition, even if lead or bismuth is not included, since it exhibits a high dielectric constant or a large remanent polarization, the inclusion of toxic heavy metals can be avoided.

  Hereinafter, embodiments of the present invention will be described in detail.

(Ferroelectric and ferroelectric device using the same)
The ferroelectric of the present invention includes an organic cation-containing polyanion comprising an organic cation and at least one polyanion selected from the group consisting of a polytitanate anion, a polyniobate anion and a polytantalate anion. That is, this ferroelectric is configured to include at least one of an organic cation-containing polytitanate anion, an organic cation-containing polyniobate anion, and an organic cation-containing polytantalate anion.

  Here, as the organic cation, for example, quaternary ammonium cation such as tetramethylammonium cation, tetraethylammonium cation, tetrapropylammonium cation, tetrabutylammonium cation, benzyltrimethylammonium cation, tetramethylphosphonium cation, tetraethylphosphonium cation, Quaternary phosphonium cations such as tetrapropylphosphonium cation and tetrabutylphosphonium cation, methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine, tributylamine, Pentylamine, dipentylamine, tripentylamine , One or more selected from cations derived from primary to tertiary amines such as hexylamine, dihexylamine, trihexylamine, dimethylhexylamine, dimethylbenzylamine, and dimethyloctylamine. It is done. Of these, quaternary ammonium cations and quaternary phosphonium cations are particularly preferred.

The polytitanate anion means an anion formed by dissociating a part of its proton from that represented by TiO ₂ .xH ₂ O condensed with titanium hydroxide. Specifically, examples of the polytitanate anion include 2 titanate anion, 3 titanate anion, 4 titanate anion, and 5 titanate anion. Similarly, Poriniobu anions, from what niobium hydroxide is represented by fused _{Ti 2 O 5 · xH 2 O} , means that part of the protons becomes dissociated anions, specifically Examples include 2-niobate anion. Similarly, Poritantaru anions, from what tantalum hydroxide is represented by fused _{Ta 2 O 5 · xH 2 O} , means that part of the protons becomes dissociated anions, specifically Examples include 2-tantalate anion.

  Note that the ferroelectric of the present invention may contain a plurality of types of organic cations, and even if two types of polytitanate anion, polyniobate anion and polytantalate anion are contained, three types are included. All may be included.

  The ferroelectric of the present invention may contain an organic acid as an optional component. However, the content of the organic acid is preferably not more than an organic cation neutralization equivalent.

  The ferroelectric of the present invention preferably has a laminated structure formed by nanosheet layers composed of polyanions. Among the laminated structures, a polytitanate anion having a lipidocrosite type structure is more preferable. For example, in an organic cation-containing polyanion ferroelectric composed of a tetramethylammonium cation and a polytitanate anion, the basic unit expands in a planar shape with an octahedral structure in which eight oxygens are coordinated centering on titanium. The polytitanate anion nanosheet layer formed in this manner has a laminated structure laminated at an interval of about 1 nm, and a tetramethylammonium cation layer is formed between the polytitanate anion nanosheet layers. And an alternate laminated structure is configured. Whether or not it has a laminated structure of a polyanion layer can be confirmed by whether or not there are two or more diffraction peaks whose plane spacing is an integer ratio in X-ray diffraction.

The ferroelectric of the present invention has a very excellent dielectric performance without performing a heat treatment at a high temperature, and the remanent polarization is 1 μC / cm ² or more at room temperature or the relative dielectric constant is 40 or more. It is. As described above, the ferroelectric of the present invention exhibits a high dielectric constant or a large remanent polarization even if it does not contain lead, bismuth or the like, so that it is possible to avoid the inclusion of toxic heavy metals.

  And the ferroelectric substance of this invention can comprise ferroelectric devices, such as a non-volatile memory device, a capacitor | condenser, a piezoelectric device, a pyroelectric infrared sensor device, by providing between a pair of electrodes.

(Ferroelectric manufacturing method)
Hereinafter, a method for manufacturing a ferroelectric according to the present invention will be described.

<Dispersion preparation step>
First, an organic cation and at least one hydroxide selected from the group consisting of titanium hydroxide, niobium hydroxide and tantalum hydroxide are contained in water so that the organic cation dissolves and from the hydroxide. A dispersion in which the produced polyanion is dispersed is prepared.

  As a method for preparing the dispersion, (1) an organic cation and at least one hydroxide selected from the group consisting of titanium hydroxide, niobium hydroxide and tantalum hydroxide are mixed in advance, (2) A method in which an aqueous solution of an organic cation contains at least one hydroxide selected from the group consisting of titanium hydroxide, niobium hydroxide and tantalum hydroxide, and (3) an organic cation. And at least one compound selected from the group consisting of a compound that hydrolyzes to produce titanium hydroxide, a compound that hydrolyzes to produce niobium hydroxide, and a compound that hydrolyzes to produce tantalum hydroxide, And (4) at least selected from the group consisting of layered titanic acid, layered niobic acid and layered tantalate having an alkali metal as a counter ion Processing the seed with an acid, after washing away the alkali metal ions ion-exchanged, and a method of treating with a cation or an amine.

  Examples of the organic cation include quaternary ammonium salts such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium hydroxide, and benzyltrimethylammonium hydroxide, which are quaternary ammonium cation sources. A quaternary phosphonium cation, a quaternary phosphonium salt such as tetramethylphosphonium hydroxide, tetraethylphosphonium hydroxide, tetrapropylphosphonium hydroxide, tetrabutylphosphonium hydroxide or the like, a cation derived from a primary to tertiary amine Sources of methylamine, dimethylamine, trimethylamine, ethylamine, diethylamine, triethylamine, propylamine, dipropylamine, tripropylamine, butylamine, dibutylamine Emissions, tributylamine, pentylamine, dipentylamine, tripentylamine, hexylamine, dihexylamine, trihexylamine, dimethyl hexylamine, dimethyl benzylamine, amine compounds such as dimethyl octyl amine, and the like. And what is necessary is just to use 1 type chosen from these compounds, or 2 or more types.

  Examples of the compound that generates titanium hydroxide, niobium hydroxide, or tantalum hydroxide by hydrolysis include metal alkoxides such as titanium tetraisopropoxide, titanium tetrabutoxide, niobium pentaethoxide, tantalum pentaethoxide, titanium chloride, Examples thereof include halides such as titanium fluoride, niobium chloride and tantalum chloride, nitrates such as titanium nitrate, niobium nitrate and tantalum nitrate, sulfates such as titanium sulfate, niobium sulfate and tantalum sulfate, titanyl nitrate and titanyl sulfate. And what is necessary is just to use 1 type chosen from these compounds, or 2 or more types.

  In addition, in order to improve the solubility of an organic cation, you may add a water-soluble organic solvent, for example, C1-C4 alcohol, to water.

  The dispersion may further contain, as optional components, an organic acid for adjusting pH and a polyol for improving dispersibility.

  The dispersion to be prepared preferably has an organic cation concentration of 0.01 to 30% by mass, and more preferably 0.1 to 15% by mass. And the amount of the hydroxide or the compound that hydrolyzes to produce a hydroxide, that is, the polyanion content is determined by the molar ratio of metal (titanium, niobium, tantalum) to organic cation (metal / organic cation). The amount is preferably 0.5 to 5, and more preferably 0.8 to 3. Quantitatively, the polyanion concentration is preferably 0.01 to 30% by mass, and more preferably 0.1 to 15% by mass.

  Further, the dispersion to be prepared preferably has a pH of 10 or more, more preferably a strong alkalinity of 12 or more. Therefore, as the organic cation, a quaternary ammonium cation and a quaternary phosphonium cation are particularly suitable. Alternatively, the dispersion may be prepared in a strongly alkaline state, and the pH may be lowered by adding an organic acid within a range that does not impair the dispersibility of the polyanion after the preparation of the dispersion.

  Further, the dispersion is preferably prepared by adjusting the temperature to 2 to 200 ° C., more preferably 10 to 150 ° C., and further preferably 20 to 100 ° C. from the viewpoint of product stability.

  Further, the stirring of the dispersion, that is, the reaction time is preferably 0.1 to 20 hours, and more preferably 1 to 10 hours.

<Solidification step>
Following the dispersion preparation step, the organic cation and polyanion contained in the prepared dispersion are solidified.

  Here, as a method of solidifying the organic cation-containing polyanion, for example, a method of removing water by drying the dispersion, a method of removing moisture by heating the dispersion, and placing the dispersion under reduced pressure And a method for removing moisture.

  In addition, if a solvent having a lower solubility in organic cation-containing polyanions than water is added to the dispersion, excess organic cations are extracted into the added solvent, so that a higher-purity organic cation-containing polyanion can be obtained. In this case, the solvent may be removed after the organic cation-containing polyanion is precipitated, but it is preferable to perform drying after washing the precipitate with a solvent having low solubility thereto. By doing in this way, content of an excess organic cation can be suppressed further low. Such a solvent includes isopropyl alcohol when the organic cation is a tetramethylammonium cation.

  The temperature at which the organic cation-containing polyanion is solidified needs to be a temperature that does not reach the temperature at which the organic cation decomposes or volatilizes. For example, when the organic cation is a tetramethylammonium cation, the temperature may be 200 ° C. or lower.

  As described above, the organic cation-containing polyanion ferroelectric of the present invention can be produced by a very simple method such as drying the dispersion. In addition, although vacuum processes, such as sputtering, and the heat processing at high temperature are not required, those processes and processes can also be added.

  The obtained solidified product, which is a ferroelectric substance of an organic cation-containing polyanion, is generally in the form of powder, but it can be put into practical use by forming the powdered solidified product into a predetermined shape such as a film or plate. (Molding step). Specifically, for example, a method in which a predetermined amount of powdered solidified material is filled in a mold, heated and pressurized, and press-molded can be used. At this time, in order to improve moldability, a binder may be mixed into the powdered solidified product.

  Further, the organic cation-containing polyanion may be solidified on a flat substrate and formed into a film for practical use. Specifically, the dispersion liquid may be attached to the surface of a flat substrate, and moisture may be removed on the substrate.

  Here, examples of the substrate include a metal substrate, a semiconductor substrate, a transparent conductive oxide film such as ITO, a conductive polymer substrate, and a polymer substrate on which a conductive layer such as metal is formed on the surface. If it is a board | substrate which has electroconductivity, it can be used as an electrode.

  Examples of the method for attaching the dispersion to the substrate include an immersion method in which the substrate is immersed in the dispersion, a spray method in which the dispersion is sprayed on the substrate, a spin coating method, a brush coating method, and the like.

  An organic cation-containing polyanion ferroelectric such as a film is provided between a pair of electrodes to constitute a ferroelectric device.

  Here, the electrode can be constituted by the substrate itself as described above, or can be constituted by formation of a conductive layer by vapor deposition or sputtering, application of a conductive paste, or in contact with a ferroelectric substance of an organic cation-containing polyanion. It can also be made of metal or the like.

(Test evaluation 1)
<Test evaluation sample>
Example 1
10 g of water was mixed with 1.823 g (tetramethylammonium hydroxide: 5 mmol) of 25 mass% tetramethylammonium hydroxide aqueous solution (manufactured by Wako Pure Chemical Industries, Ltd.).

  Next, while stirring this at room temperature, 2.8422 g (10 mmol) of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise little by little. At this time, immediately after the dropwise addition of titanium tetraisopropoxide, it hydrolyzed and became cloudy, but when stirring was continued, it became a colorless and transparent dispersion. This dispersion has a tetramethylammonium cation concentration of 3 mass%, a polytitanate anion concentration of 6 mass%, and a molar ratio of titanium to organic cation of 2. The pH of the dispersion was 12.

  Then, this dispersion is diluted with water so that the concentration of polytitanate anion is 0.5% by mass, applied onto a titanium substrate, and dried by scattering water to produce polytitanium ammonium cation-containing polytitanium. A thin film of acid anion was designated as Example 1.

-Example 2-
Instead of the tetramethylammonium hydroxide aqueous solution, 40% by mass of a tetrabutylphosphonium hydroxide aqueous solution (made by Wako Pure Chemical Industries, Ltd.) 3.456 g (tetrabutylphosphonium hydroxide: 5 mmol) was used. Was a dispersion having a polytitanate anion concentration of 5 mass% and a molar ratio of titanium to organic cation of 2. The pH of the dispersion was 12.

  Then, this dispersion is diluted with water so that the concentration of polytitanate anion is 0.5% by mass, applied onto a titanium substrate, and dried by dispersing the water to produce tetrabutylphosphonium cation-containing polytitanium. An acid anion thin film was designated as Example 2.

-Example 3-
The amount of 25 mass% tetramethylammonium hydroxide aqueous solution was 3.646 g (tetramethylammonium hydroxide: 10 mmol), and niobium pentaethoxide (manufactured by Wako Pure Chemical Industries, Ltd.) 3.182 g instead of titanium tetraisopropoxide. (10 mmol) was used to prepare a dispersion having a tetramethylammonium cation concentration of 4 mass%, a polyniobate anion concentration of 8 mass%, and a molar ratio of niobium to organic cation of 1. The pH of the dispersion was 12.

  Then, this dispersion is diluted with water so that the concentration of polyniobate anion becomes 0.5% by mass, applied onto a titanium substrate, and dried by scattering water to produce polyniobium cation-containing polyniobium. Example 3 was a thin film of acid anion.

Example 4
The amount of 25 mass% tetramethylammonium hydroxide aqueous solution was 3.646 g (tetramethylammonium hydroxide: 10 mmol), and tantalum pentaethoxide (manufactured by Wako Pure Chemical Industries, Ltd.) 4.063 g instead of titanium tetraisopropoxide. (10 mmol) was used to prepare a dispersion having a tetramethylammonium cation concentration of 4 mass%, a polytantalate anion concentration of 12 mass%, and a molar ratio of tantalum to an organic cation of 1. The pH of the dispersion was 12.

  Then, this dispersion is diluted with water so that the concentration of the polytantalate anion is 0.5% by mass, applied onto a titanium substrate, and dried by scattering the water to produce tetramethylammonium cation-containing polytantalum. An acid anion thin film was designated as Example 4.

-Comparative Example 1-
A dispersion was prepared by dispersing 0.1 g (0.43 mmol) of commercially available barium titanate (manufactured by Kyoritsu Ceramic Co., Ltd.) in 19.9 g of water.

  A thin film of barium titanate prepared by applying this dispersion on a titanium substrate and drying the moisture was used as Comparative Example 1.

  The prepared dispersion has a barium titanate concentration of 0.5% by mass.

<Test evaluation method>
-X-ray diffraction analysis-
For each of Examples 1 to 4 and Comparative Example 1, X-ray diffraction analysis was performed to obtain an X-ray diffraction pattern.

-Residual polarization measurement-
For each of Examples 1 to 4 and Comparative Example 1, residual polarization was determined by performing hysteresis measurement.

  The hysteresis measurement was performed based on the description on pages 272 to 275 of Non-Patent Document 1 in order to eliminate the influence of leakage current due to water remaining in the sample. Specifically, a pair of electrodes is attached to each sample, a triangular wave pulse sequence as shown in FIG. 1 is performed, and the difference in current value between when the pulse polarity is inverted and when it is not inverted is determined by the current due to spontaneous polarization. The remanent polarization was read from the hysteresis curve obtained by integrating the current due to the spontaneous polarization as the spontaneous polarization charge. Note that the upper and lower peak voltages of the triangular wave pulse were +5 V and -5 V, the pulse width was 2 seconds, and the pulse interval was 1 second. The measurement was performed at room temperature.

<Test evaluation results>
-X-ray diffraction analysis-
As a result of X-ray diffraction analysis, in Examples 1 to 4, an X-ray diffraction pattern showing a layered structure with polytitanate anions was obtained, whereas in Comparative Example 1, an X-ray diffraction pattern showing such a layered structure was obtained. Was not obtained.

  FIG. 2 shows the X-ray diffraction pattern of Example 2.

  According to FIG. 2, a first peak (main peak) is observed near 1.70 nm (2θ = 5.2 °) in terms of d value, and then around 0.89 nm (2θ = 9.9 °) in terms of d value. The second peak is observed in the vicinity of the second peak, and the third peak is observed near the d value of 0.60 nm (2θ = 14.7 °). Since the d value of the second peak is 1/2 and the d value of the third peak is 1/3, respectively, with respect to the d value of the first peak, Example 2 is polytitanate. It is thought that it has a layered structure formed by layers composed of anions. In addition, the peak after 40 degreeC vicinity is a peak derived from the titanium metal used for the board | substrate.

-Remanent polarization-
Table 1 shows the remanent polarization of each of Examples 1 to 4 and Comparative Example 1.

According to Table 1, it can be said that all of Examples 1 to 4 and Comparative Example 1 are ferroelectrics, but in Examples 1 to 4, all show very high remanent polarization of 10 μC / cm ² or more. On the other hand, in Comparative Example 1, it is 0.2 μC / cm ² . If the thin film of barium titanate of Comparative Example 1 is also formed into a single crystal by performing a high temperature heat treatment, a high residual polarization can be obtained. However, in Examples 1 to 4, a very high remanent polarization is obtained without the need for such high-temperature heat treatment.

(Test evaluation 2)
<Test evaluation sample>
-Example 5
100 g of isopropyl alcohol was added to 14.6 g of the same dispersion prepared in the production of Example 1. At this time, a white precipitate of tetramethylammonium cation-containing polytitanate anion was generated.

  Next, the precipitate obtained by filtering this was thoroughly washed with isopropyl alcohol and then dried for 12 hours in a vacuum drier set at 60 ° C. to be a ferroelectric substance containing tetramethylammonium cation-containing polytitanate anions. A white powder was produced.

  And, this tetramethylammonium cation-containing polytitanate anion white powder was molded into a disk-shaped pellet having a diameter of 16 mm, a thickness of 0.59 mm and a weight of 0.2 g by applying a pressure of 98 MPa by a press molding machine, This was designated as Example 5.

-Comparative Example 2-
Ferroelectric barium titanate (manufactured by Kyoritsu Ceramic Co., Ltd.) is formed into a disk-shaped pellet having a diameter of 16 mm, a thickness of 0.76 mm, and a main weight of 0.6 g by applying a pressure of 490 MPa by a press molding machine. This was designated as Comparative Example 2.

<Test evaluation method>
For each of Example 5 and Comparative Example 2, electrodes were brought into contact with both surfaces of the disk-shaped pellet, and the relative dielectric constant at a frequency of 1 kHz was measured using an impedance meter (HP4284A manufactured by Hewlett-Packard Company).

<Test evaluation results>
Table 2 shows the relative dielectric constants of Example 5 and Comparative Example 2.

  According to Table 2, it can be seen that Example 5 has a relative dielectric constant 60 times larger than that of Comparative Example 2. If the barium titanate of Comparative Example 2 is also formed into a single crystal by performing a high-temperature heat treatment, a high dielectric constant can be obtained. However, in Example 5, a very high relative dielectric constant was obtained without the need for such high-temperature heat treatment during production.

(Test evaluation 3)
<Test evaluation sample>
-Example 6
After dissolving 7.3 g of diethylamine (manufactured by Wako Pure Chemical Industries, Ltd.) in 160 g of water, 28.4 g of titanium tetraisopropoxide (manufactured by Wako Pure Chemical Industries, Ltd.) was added dropwise little by little.

  Next, it was stirred at room temperature for 1 day to prepare a transparent dispersion, which was dried in a vacuum dryer set at 60 ° C. for 12 hours, and then cation-containing polytitanate anion derived from diethylamine as a ferroelectric substance. A white powder was produced.

  Subsequently, the white powder of the tetramethylammonium cation-containing polytitanate anion was molded into a plate-shaped pellet ferroelectric by applying pressure with a press molding machine.

  Then, as shown in FIG. 3, an aluminum foil electrode 13 is bonded to each of both surfaces of a plate-like pellet ferroelectric 11 via a conductive nickel paste 12 to form a ferroelectric device 10. Was taken as Example 6.

<Test evaluation method>
After applying the voltage of + 5V to the other electrode 13 for 2 seconds with the ferroelectric device 10 of Example 6 as a reference, the device is positively polarized, and then the peak voltage + 5V is read in order to read the polarization state. Then, a triangular wave voltage having a pulse width of 2 seconds was applied, and the amount of charge flowing from the current value was determined. Similarly, a voltage of −5 V is applied to the ferroelectric device 10 with reference to one electrode 13 for 2 seconds to negatively polarize the device, and then the peak voltage +5 V is read in order to read the polarization state. Then, a triangular wave voltage having a pulse width of 2 seconds was applied, and the amount of charge flowing from the current value was determined.

<Test evaluation results>
The amount of charge that flowed when the state of the device that was positively polarized by applying +5 V to the other electrode 13 was read out with a +5 V triangular wave was 1.2 μC, whereas −5 V was applied to the other electrode 13. The amount of charge that flowed when the state of the device that was negatively polarized by application was read out with a +5 V triangular wave was 1.8 μC, and the direction of polarization could be known from the amount of charge. Therefore, it can be seen that the ferroelectric device 10 of Example 6 operates as a memory that stores different information depending on the positive and negative directions of polarization.

  INDUSTRIAL APPLICATION This invention is useful about a ferroelectric, its manufacturing method, and a ferroelectric device using the same.

It is a figure which shows the voltage waveform applied to the sample in the case of the test evaluation 1 at the time of a residual polarization measurement. 6 is a diagram showing an X-ray diffraction pattern of Example 2. FIG. It is a perspective view which shows a ferroelectric device.

Explanation of symbols

10 Ferroelectric Device 11 Ferroelectric 13 Electrode

Claims (7)

An organic cation,
At least one polyanion selected from the group consisting of a polytitanate anion, a polyniobate anion and a polytantalate anion;
A ferroelectric material comprising an organic cation-containing polyanion.   The ferroelectric substance according to claim 1, wherein the ferroelectric substance has a laminated structure formed by layers composed of the polyanion. An organic cation and at least one hydroxide selected from the group consisting of titanium hydroxide, niobium hydroxide and tantalum hydroxide are contained in water so that the organic cation dissolves and is generated from the hydroxide. A dispersion preparation step for preparing a dispersion in which the polyanion is dispersed;
A solidification step for solidifying the organic cation and polyanion contained in the dispersion prepared in the dispersion preparation step;
A method for manufacturing a ferroelectric comprising:   In the dispersion preparation step, instead of hydroxide, from a compound that hydrolyzes to produce titanium hydroxide, a compound that hydrolyzes to produce niobium hydroxide, and a compound that hydrolyzes to produce tantalum hydroxide The method for producing a ferroelectric according to claim 3, wherein water contains at least one compound selected from the group consisting of:   4. The method for manufacturing a ferroelectric according to claim 3, wherein in the solidification step, the organic cation and the polyanion are solidified on a flat substrate.   The method for manufacturing a ferroelectric according to claim 3, further comprising a forming step of forming the solidified product obtained in the solidifying step into a predetermined shape. A ferroelectric device in which a ferroelectric is provided between a pair of electrodes,
The ferroelectric material is
An organic cation,
At least one polyanion selected from the group consisting of a polytitanate anion, a polyniobate anion and a polytantalate anion;
A ferroelectric device comprising an organic cation-containing polyanion.

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