PbZrO3 antiferroelectric capacitor and preparation method thereof

Abstract

The invention provides a PbZrO3 antiferroelectric capacitor and a preparation method thereof, and relates to the technical field of ferroelectric materials, the PbZrO3 antiferroelectric capacitor comprises a first electrode layer, a PbO layer, a solid solution ferroelectric antiferroelectric layer, a LaNiO3 layer and the like, and phases in the solid solution ferroelectric antiferroelectric layer comprise PbZrO3, a ferroelectric and an Ag-containing Au phase. The invention also provides a preparation method of the capacitor, and the method comprises the following steps: depositing a LaNiO3 precursor solution on a single crystal substrate, and carrying out the crystallization; mixing the PbZrO3 precursor solution with the ferroelectric precursor solution, and then adding Au nanoparticles containing Ag; the LaNiO3 layer is coated with the mixed solution, and crystallization is carried out; depositing the PbO precursor solution on the surface of the antiferroelectric layer of the solid solution ferroelectric, and crystallizing; and carrying out gold electrode deposition to obtain the PbZrO3 antiferroelectric capacitor. The capacitor is high in energy storage efficiency and high in dielectric constant.

Description

Technical Field

[0001] The invention relates to the technical field of ferroelectric materials, and in particular to a PbZrO3 antiferroelectric capacitor and a preparation method thereof. Background Art

[0002] Capacitors are an important electronic component used to store and release electric charge and are widely used in various circuits. Its basic structure consists of two conductors (electrodes) and an insulating material (dielectric) between them. The main function of a capacitor is to store electrical energy and release it when needed.

[0003] When the two ends of a capacitor are connected to a power supply, the power supply voltage causes charges to accumulate on the two electrodes of the capacitor. These charges form an electric field between the electrodes and the medium. The capacitance of a capacitor reflects its ability to store charge, that is, the amount of charge that can be stored at a given voltage. The larger the capacitance value, the more charge the capacitor can store. The capacitor can smooth voltage fluctuations in the power supply and reduce noise and interference; in the transmission process of AC signals, the capacitor can isolate the DC component and allow AC signals to pass; reduce the impact of power supply noise on the circuit and provide a stable power supply voltage; in some applications, capacitors can store electrical energy and release it when needed, such as in flashlights. In general, capacitors are indispensable components in electronic circuits, and they come in a variety of types and are suitable for different application scenarios.

[0004] As an important component in electronic circuits, capacitors mainly store and release electrical energy. The performance and application of capacitors are widely dependent on the properties of their dielectric materials. In recent years, ferroelectric materials have been widely studied and applied in capacitors due to their excellent energy storage characteristics and electrical properties. Among them, antiferroelectric materials, as a special ferroelectric material, have high energy storage density, but they also face the problem of low efficiency in practical applications.

[0005] Antiferroelectric materials have a high energy storage density, which is due to their ability to store more electrical energy in a relatively small volume under the action of an external electric field. This makes antiferroelectric materials have significant advantages in high energy density energy storage devices.

[0006] Antiferroelectric materials are of great interest in capacitors mainly because of their high energy storage density. Energy storage density refers to the amount of electrical energy that can be stored per unit volume or per unit mass of a material. The special polarization characteristics of antiferroelectric materials enable them to store more electrical energy in a smaller volume under the action of an electric field. Compared with traditional dielectric materials, antiferroelectric materials can significantly increase the energy storage density of capacitors. This makes them of great application value in high energy density energy storage systems.

[0007] Since antiferroelectric materials can store more electrical energy in a smaller volume, capacitors using such materials can be smaller and lighter, which is a significant advantage for applications where space and weight are limited, such as portable electronic devices and high-power density energy storage systems.

[0008] In applications that require high energy storage, such as electric vehicle power systems, aerospace equipment, and high-power laser systems, antiferroelectric materials can provide higher energy storage capabilities and improve the overall performance and efficiency of the system.

[0009] Antiferroelectric materials have high energy storage density but low efficiency. Currently, antiferroelectric materials often use relaxation to refine the hysteresis loop to improve energy storage efficiency, but this relaxation often leads to polarization loss, which weakens the antiferroelectricity and reduces the dielectric constant. The reduction of the dielectric constant will directly affect the electrical properties of the capacitor, resulting in a decrease in energy storage capacity. Summary of the invention

[0010] The invention provides a PbZrO3 antiferroelectric capacitor and a preparation method thereof, so as to solve the technical problem in the prior art that the antiferroelectric material has high energy storage efficiency but low dielectric constant.

[0011] In order to achieve the above-mentioned invention object, the technical solution provided by the present invention is as follows:

[0012] A PbZrO3 antiferroelectric capacitor comprises a first electrode layer, a PbO layer, an antiferroelectric layer of a solid solution ferroelectric, a LaNiO3 layer, a single crystal substrate and a second electrode layer which are arranged in sequence. The physical phases in the antiferroelectric layer of the solid solution ferroelectric include PbZrO3, ferroelectric and an Au phase containing Ag.

[0013] Preferably, the volume ratio of PbZrO3, ferroelectric and Ag-containing Au phase in the antiferroelectric layer of the solid solution ferroelectric is 100:6-12:2-3.3.

[0014] A method for preparing the PbZrO3 antiferroelectric capacitor as described above comprises the following steps:

[0015] S1, dissolving lanthanum nitrate and nickel acetate in a solvent to obtain a LaNiO3 precursor solution;

[0016] S2, dissolving lead acetate in a solvent, heating at 60-150° C. for 0.5-3 hours, adding zirconium n-propoxide after cooling, stirring and dissolving to obtain a PbZrO3 precursor solution;

[0017] S3, preparing a ferroelectric precursor solution, wherein the ferroelectric precursor solution is a BiScO3 precursor solution, Bi 0.5 Na 0.5 One of the TiO3 precursor solutions;

[0018] S4, dissolving lead acetate in a solvent to obtain a PbO precursor solution;

[0019] S5, spin coating the LaNiO3 precursor solution onto the single crystal substrate, performing the first spin coating deposition, and repeating this process multiple times after drying and crystallization to achieve the desired film thickness, thereby obtaining a LaNiO3 layer coated on the single crystal substrate;

[0020] S6, after mixing the PbZrO3 precursor solution with the ferroelectric precursor solution, adding Au nanoparticles containing Ag to obtain a mixed solution; spin coating the mixed solution onto the LaNiO3 layer, performing a second spin coating deposition, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness (100 to 1000 nm), thereby obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer;

[0021] S7, depositing the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, performing a third spin coating deposition, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness, thereby obtaining a capacitor film;

[0022] S8. Depositing gold electrodes on both sides of the capacitor film through a stainless steel mask to construct a first electrode layer and a second electrode layer with a diameter of about 50 to 500 μm and a thickness of about 10 to 200 nm to obtain a PbZrO3 antiferroelectric capacitor.

[0023] Preferably, the solvent is one or more of 2-methoxyethanol, propionic acid, ethylene glycol, and acetic acid.

[0024] Preferably, the concentrations of the LaNiO3 precursor solution, the PbZrO3 precursor solution, the ferroelectric precursor solution and the PbO precursor solution are 0.1-0.4M.

[0025] Preferably, the drying and crystallization are: baking at 100-300°C for 0.5-5 minutes, then pyrolyzing at 350-500°C for 0.5-5 minutes, and crystallizing at 550-800°C for 3-30 minutes.

[0026] Preferably, the single crystal substrate in S5 is one of a LaAlO3 substrate, a SrTiO3 substrate, a Pt / Si substrate, and a DyScO3 substrate.

[0027] Preferably, the rotation speed of the first spin coating deposition is 3000-6000 rpm.

[0028] Preferably, the second spin coating deposition and the third spin coating deposition have the same rotation speed.

[0029] Preferably, the particle size of the Ag-containing Au nanoparticles is 40-50 nm.

[0030] It should be explained that the preparation method of the Ag-containing Au nanoparticles in the present invention can refer to the relevant preparation process in the prior art, and can be prepared by the Link method. The mass of Ag in the Ag-containing Au nanoparticles used in the present invention accounts for 30% of the total mass.

[0031] The structure of the capacitor in the present invention is a first electrode layer, a PbO layer, an antiferroelectric layer of a solid solution ferroelectric, a LaNiO3 layer, a single crystal substrate and a second electrode layer, wherein the antiferroelectric layer of the solid solution ferroelectric is arranged on the LaNiO3 layer. After the LNO interface layer is introduced, the quality of the antiferroelectric layer film of the solid solution ferroelectric is improved, the breakdown performance is enhanced, and the energy storage density will be improved.

[0032] The phases in the antiferroelectric layer of the solid solution ferroelectric of the present invention include PbZrO3, ferroelectric and Au phase containing Ag, wherein the ferroelectric is BiScO3 ferroelectric or Bi 0.5 Na 0.5 TiO3 ferroelectrics, in which Au and Ag are transition metal elements, their ions can replace some Pb or Zr atomic sites in the PbZrO3 crystal structure, this substitution may affect the local stress of the lattice, and then affect the overall structure and performance of the film. The mixture of Au and Ag can optimize the conductivity and reduce the resistance in the film. This improved conductivity makes the electric field more evenly distributed in the film, thereby improving the dielectric response; the good conductivity of Au-Ag can reduce the interface resistance between the electrode and the PbZrO3 film, and the optimized interface contact can reduce the interface charge accumulation and interface resistance, improve the injection and extraction efficiency of the charge, and thus improve the dielectric constant and energy storage performance of the film; in addition, the surface plasmon resonance effect of Au-Ag can enhance the local electromagnetic field at a specific wavelength. This effect can increase the local intensity of the electric field in the film, enhance the polarization ability, and thus improve the dielectric constant and energy storage capacity; the addition of Au will reduce the grain size of the film, increase the stress within the matrix grain boundary, cause field-induced phase transition, and gradually enhance the dispersion, making the hysteresis loop become slender and tilted, which is conducive to improving the energy storage performance of the film. In addition, the atomic radius of Ag is different from that of Au, which may cause changes in the nature of lattice distortion. Au nanoparticles containing Ag may cause different degrees of lattice stress and optimize the dielectric stability of the film.

[0033] BiScO3 or Bi 0.5 Na 0.5 As a high dielectric constant material, the introduction of TiO3 ferroelectric can significantly increase the dielectric constant of PbZrO3 film. 0.5 Na 0.5TiO3 can provide a higher charge polarization strength. This strong polarization ability can enhance the polarization response of the film when an electric field is applied, thereby increasing the dielectric constant.

[0034] Au-Ag improves the interface contact between the electrode and PbZrO3 film and reduces the interface impedance. 0.5 Na 0.5 The introduction of TiO3 not only provides a higher dielectric constant, but also improves the polarization behavior. The combined effect of the two can make the electric field more uniformly distributed in the PbZrO3 film, thereby improving the dielectric constant. 0.5 Na 0.5 The strong polarization ability of TiO3 and the optimized conductivity of Au-Ag work together to create a stronger local electric field in the film, thereby increasing the energy storage density. This combined effect can significantly improve the energy storage capacity of the film.

[0035] Compared with the prior art, the technical solution of the present invention has at least the following beneficial effects:

[0036] The structure of the constructed capacitor is a first electrode layer, a PbO layer, an antiferroelectric layer of a solid solution ferroelectric, a LaNiO3 layer, a single crystal substrate and a second electrode layer. The electron transfer ability between the layers is strong and the interface impedance is low. The capacitor has a high energy storage density and a high dielectric constant.

[0037] By dissolving ferroelectrics in antiferroelectric materials, the long-range antiferroelectric order is broken, allowing the system to relax and improve the energy storage efficiency. At the same time, the large polarization of the ferroelectric maintains the large polarization of the system and improves the dielectric constant.

[0038] Building Au(Ag)-BiScO3 or Bi into capacitor structures 0.5 Na 0.5 The TiO3-PbZrO3 thin film system improves the electron transfer ability of the film and the local intensity of the electric field in the film, enhances the polarization ability, and thus improves the dielectric constant and energy storage capacity.

[0039] The invention also provides a method for preparing a PbZrO3 antiferroelectric capacitor, which constructs different conductive layers by batch spin coating, has a simple method and a high yield. BRIEF DESCRIPTION OF THE DRAWINGS

[0040] Figure 1 This is a schematic structural diagram of a PbZrO3 antiferroelectric capacitor provided in Example 1 of the present invention.

[0041] Among them; 1-first electrode layer, 2-PbO layer, 3-antiferroelectric layer of solid solution ferroelectric, 4-LaNiO3 layer, 5-single crystal substrate, 6-second electrode layer. DETAILED DESCRIPTION

[0042] In order to make the purpose, technical solution and advantages of the embodiment of the present invention clearer, the technical solution of the embodiment of the present invention will be clearly and completely described below in conjunction with the drawings of the embodiment of the present invention. Obviously, the described embodiment is a part of the embodiment of the present invention, not all of the embodiments. Based on the described embodiment of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0043] Example 1

[0044] like Figure 1 As shown, a PbZrO3 antiferroelectric capacitor comprises a first electrode layer 1, a PbO layer 2, an antiferroelectric layer 3 of a solid solution ferroelectric, a LaNiO3 layer 4, a single crystal substrate 5 and a second electrode layer 6 which are arranged in sequence, wherein the physical phases in the antiferroelectric layer 3 of the solid solution ferroelectric include PbZrO3, ferroelectric and an Au phase containing Ag.

[0045] The volume ratio of PbZrO3, ferroelectric and Au phase containing Ag in the antiferroelectric layer 3 of the solid solution ferroelectric is 100:6:2.

[0046] A method for preparing the PbZrO3 antiferroelectric capacitor described in this embodiment comprises the following steps:

[0047] S1, dissolving lanthanum nitrate and nickel acetate in a solvent to obtain a LaNiO3 precursor solution;

[0048] S2, dissolving lead acetate in a solvent, heating at 60° C. for 0.5 hour, adding zirconium n-propoxide after cooling, stirring and dissolving to obtain a PbZrO3 precursor solution;

[0049] S3, preparing a ferroelectric precursor solution, wherein the ferroelectric precursor solution is a BiScO3 precursor solution;

[0050] S4, dissolving lead acetate in a solvent to obtain a PbO precursor solution;

[0051] S5, spin coating the LaNiO3 precursor solution onto the LaAlO3 substrate, performing the first spin coating deposition at a rotation speed of 3000 rpm, and repeating this process multiple times after drying and crystallization to achieve the desired film thickness, thereby obtaining a LaNiO3 layer coated on the single crystal substrate;

[0052] S6, after mixing the PbZrO3 precursor solution with the ferroelectric precursor solution, adding Ag-containing Au nanoparticles with a particle size of 40 nm to obtain a mixed solution; spin coating the mixed solution onto the LaNiO3 layer, performing a second spin coating deposition at a speed of 3000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness, thereby obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer;

[0053] S7, depositing the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, performing a third spin coating deposition at a rotation speed of 3000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness to obtain a capacitor film;

[0054] S8. Depositing gold electrodes on both sides of the capacitor film through a stainless steel mask to construct a first electrode layer and a second electrode layer to obtain a PbZrO3 antiferroelectric capacitor.

[0055] In this embodiment, the solvent is 2-methoxyethanol. The concentration of the LaNiO3 precursor solution, the PbZrO3 precursor solution, the ferroelectric precursor solution and the PbO precursor solution is 0.1M.

[0056] The drying and crystallization are as follows: baking at 100° C. for 0.5 minutes, then pyrolyzing at 350° C. for 0.5 minutes, and crystallizing at 550° C. for 3 minutes.

[0057] Example 2

[0058] like Figure 1 As shown, a PbZrO3 antiferroelectric capacitor comprises a first electrode layer 1, a PbO layer 2, an antiferroelectric layer 3 of a solid solution ferroelectric, a LaNiO3 layer 4, a single crystal substrate 5 and a second electrode layer 6 which are arranged in sequence, wherein the physical phases in the antiferroelectric layer 3 of the solid solution ferroelectric include PbZrO3, ferroelectric and an Au phase containing Ag.

[0059] The volume ratio of PbZrO3, ferroelectric and Au phase containing Ag in the antiferroelectric layer 3 of the solid solution ferroelectric is 100:12:3.3.

[0060] A method for preparing the PbZrO3 antiferroelectric capacitor described in this embodiment comprises the following steps:

[0061] S1, dissolving lanthanum nitrate and nickel acetate in a solvent to obtain a LaNiO3 precursor solution;

[0062] S2, dissolving lead acetate in a solvent, heating at 150° C. for 3 hours, adding n-propyl zirconium after cooling, stirring and dissolving to obtain a PbZrO3 precursor solution;

[0063] S3, prepare a ferroelectric precursor solution, wherein the ferroelectric precursor solution is Bi 0.5 Na 0.5 TiO3 precursor solution;

[0064] S4, dissolving lead acetate in a solvent to obtain a PbO precursor solution;

[0065] S5, spin coating the LaNiO3 precursor solution onto the SrTiO3 substrate, performing the first spin coating deposition at a rotation speed of 6000 rpm, and repeating this process multiple times after drying and crystallization to achieve the desired film thickness, thereby obtaining a LaNiO3 layer coated on the single crystal substrate;

[0066] S6, after mixing the PbZrO3 precursor solution with the ferroelectric precursor solution, adding Au nanoparticles containing Ag with a particle size of 50 nm to obtain a mixed solution; spin coating the mixed solution onto the LaNiO3 layer, and performing a second spin coating deposition at a speed of 6000 rpm. After drying and crystallization, this process can be repeated multiple times to achieve a desired film thickness, thereby obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer;

[0067] S7, depositing the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, performing a third spin coating deposition at a rotation speed of 6000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness to obtain a capacitor film;

[0068] S8. Depositing gold electrodes on both sides of the capacitor film through a stainless steel mask to construct a first electrode layer and a second electrode layer to obtain a PbZrO3 antiferroelectric capacitor.

[0069] In this embodiment, the solvent is propionic acid. The concentration of the LaNiO3 precursor solution, the PbZrO3 precursor solution, the ferroelectric precursor solution and the PbO precursor solution is 0.4M.

[0070] The drying and crystallization are as follows: baking at 300°C for 5 minutes, then pyrolyzing at 500°C for 5 minutes, and crystallizing at 800°C for 30 minutes.

[0071] Example 3

[0072] like Figure 1 As shown, a PbZrO3 antiferroelectric capacitor comprises a first electrode layer 1, a PbO layer 2, an antiferroelectric layer 3 of a solid solution ferroelectric, a LaNiO3 layer 4, a single crystal substrate 5 and a second electrode layer 6 which are arranged in sequence, wherein the physical phases in the antiferroelectric layer 3 of the solid solution ferroelectric include PbZrO3, ferroelectric and an Au phase containing Ag.

[0073] The volume ratio of PbZrO3, ferroelectric and Au phase containing Ag in the antiferroelectric layer 3 of the solid solution ferroelectric is 100:10:2.5.

[0074] A method for preparing the PbZrO3 antiferroelectric capacitor described in this embodiment comprises the following steps:

[0075] S1, dissolving lanthanum nitrate and nickel acetate in a solvent to obtain a LaNiO3 precursor solution;

[0076] S2, dissolving lead acetate in a solvent, heating at 120° C. for 2 hours, adding zirconium n-propoxide after cooling, stirring and dissolving to obtain a PbZrO3 precursor solution;

[0077] S3, prepare a ferroelectric precursor solution, wherein the ferroelectric precursor solution is Bi 0.5 Na 0.5 TiO3 precursor solution;

[0078] S4, dissolving lead acetate in a solvent to obtain a PbO precursor solution;

[0079] S5, spin coating the LaNiO3 precursor solution onto a Pt / Si substrate, performing the first spin coating deposition at a rotation speed of 5000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness, thereby obtaining a LaNiO3 layer coated on the single crystal substrate;

[0080] S6, after mixing the PbZrO3 precursor solution with the ferroelectric precursor solution, adding Ag-containing Au nanoparticles with a particle size of 45 nm to obtain a mixed solution; spin coating the mixed solution onto the LaNiO3 layer, and performing a second spin coating deposition at a speed of 5000 rpm. After drying and crystallization, this process can be repeated multiple times to achieve a desired film thickness, thereby obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer;

[0081] S7, depositing the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, performing a third spin coating deposition at a rotation speed of 5000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness to obtain a capacitor film;

[0082] S8. Depositing gold electrodes on both sides of the capacitor film through a stainless steel mask to construct a first electrode layer and a second electrode layer to obtain a PbZrO3 antiferroelectric capacitor.

[0083] In this embodiment, the solvent is ethylene glycol. The concentration of the LaNiO3 precursor solution, the PbZrO3 precursor solution, the ferroelectric precursor solution and the PbO precursor solution is 0.2M.

[0084] The drying and crystallization are as follows: baking at 200°C for 2 minutes, then pyrolyzing at 400°C for 3 minutes, and crystallizing at 700°C for 10 minutes.

[0085] The solvent in this example is replaced by acetic acid, and the substrate is replaced by a DyScO3 substrate. The performance of the obtained product is similar to that of the product in this example.

[0086] Example 4

[0087] like Figure 1 As shown, a PbZrO3 antiferroelectric capacitor comprises a first electrode layer 1, a PbO layer 2, an antiferroelectric layer 3 of a solid solution ferroelectric, a LaNiO3 layer 4, a single crystal substrate 5 and a second electrode layer 6 which are arranged in sequence, wherein the physical phases in the antiferroelectric layer 3 of the solid solution ferroelectric include PbZrO3, ferroelectric and an Au phase containing Ag.

[0088] The volume ratio of PbZrO3, ferroelectric and Au phase containing Ag in the antiferroelectric layer 3 of the solid solution ferroelectric is 100:8:3.

[0089] A method for preparing the PbZrO3 antiferroelectric capacitor described in this embodiment comprises the following steps:

[0090] S1, dissolving lanthanum nitrate and nickel acetate in a solvent to obtain a LaNiO3 precursor solution;

[0091] S2, dissolving lead acetate in a solvent, heating at 100° C. for 1 hour, adding zirconium n-propoxide after cooling, stirring and dissolving to obtain a PbZrO3 precursor solution;

[0092] S3, prepare a ferroelectric precursor solution, wherein the ferroelectric precursor solution is Bi 0.5 Na 0.5 TiO3 precursor solution;

[0093] S4, dissolving lead acetate in a solvent to obtain a PbO precursor solution;

[0094] S5, spin coating the LaNiO3 precursor solution onto the DyScO3 substrate, performing the first spin coating deposition at a rotation speed of 5000 rpm, and repeating this process multiple times after drying and crystallization to achieve the desired film thickness, thereby obtaining a LaNiO3 layer coated on the single crystal substrate;

[0095] S6, after mixing the PbZrO3 precursor solution with the ferroelectric precursor solution, adding Ag-containing Au nanoparticles with a particle size of 45 nm to obtain a mixed solution; spin coating the mixed solution onto the LaNiO3 layer, and performing a second spin coating deposition at a speed of 5000 rpm. After drying and crystallization, this process can be repeated multiple times to achieve a desired film thickness, thereby obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer;

[0096] S7, depositing the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, performing a third spin coating deposition at a rotation speed of 5000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness to obtain a capacitor film;

[0097] S8. Depositing gold electrodes on both sides of the capacitor film through a stainless steel mask to construct a first electrode layer and a second electrode layer to obtain a PbZrO3 antiferroelectric capacitor.

[0098] In this embodiment, the solvent is acetic acid. The concentration of the LaNiO3 precursor solution, the PbZrO3 precursor solution, the ferroelectric precursor solution and the PbO precursor solution is 0.2M.

[0099] The drying and crystallization are as follows: baking at 250°C for 1.5 minutes, then pyrolyzing at 450°C for 2 minutes, and crystallizing at 750°C for 15 minutes.

[0100] Example 5

[0101] like Figure 1 As shown, a PbZrO3 antiferroelectric capacitor comprises a first electrode layer 1, a PbO layer 2, an antiferroelectric layer 3 of a solid solution ferroelectric, a LaNiO3 layer 4, a single crystal substrate 5 and a second electrode layer 6 which are arranged in sequence, wherein the physical phases in the antiferroelectric layer 3 of the solid solution ferroelectric include PbZrO3, ferroelectric and an Au phase containing Ag.

[0102] The volume ratio of PbZrO3, ferroelectric and Au phase containing Ag in the antiferroelectric layer 3 of the solid solution ferroelectric is 100:12:2.

[0103] A method for preparing the PbZrO3 antiferroelectric capacitor described in this embodiment comprises the following steps:

[0104] S1, dissolving lanthanum nitrate and nickel acetate in a solvent to obtain a LaNiO3 precursor solution;

[0105] S2, dissolving lead acetate in a solvent, heating at 100° C. for 3 hours, adding zirconium n-propoxide after cooling, stirring and dissolving to obtain a PbZrO3 precursor solution;

[0106] S3, prepare a ferroelectric precursor solution, wherein the ferroelectric precursor solution is Bi 0.5 Na 0.5 TiO3 precursor solution;

[0107] S4, dissolving lead acetate in a solvent to obtain a PbO precursor solution;

[0108] S5, spin coating the LaNiO3 precursor solution onto a Pt / Si substrate, performing the first spin coating deposition at a rotation speed of 5000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness, thereby obtaining a LaNiO3 layer coated on the single crystal substrate;

[0109] S6, after mixing the PbZrO3 precursor solution with the ferroelectric precursor solution, adding Ag-containing Au nanoparticles with a particle size of 45 nm to obtain a mixed solution; spin coating the mixed solution onto the LaNiO3 layer, and performing a second spin coating deposition at a speed of 5000 rpm. After drying and crystallization, this process can be repeated multiple times to achieve a desired film thickness, thereby obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer;

[0110] S7, depositing the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, performing a third spin coating deposition at a rotation speed of 5000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness to obtain a capacitor film;

[0111] S8. Depositing gold electrodes on both sides of the capacitor film through a stainless steel mask to construct a first electrode layer and a second electrode layer to obtain a PbZrO3 antiferroelectric capacitor.

[0112] In this embodiment, the solvent is ethylene glycol. The concentration of the LaNiO3 precursor solution, the PbZrO3 precursor solution, the ferroelectric precursor solution and the PbO precursor solution is 0.2M.

[0113] The drying and crystallization are as follows: baking at 250°C for 2 minutes, then pyrolyzing at 500°C for 3 minutes, and crystallizing at 800°C for 10 minutes.

[0114] Example 6

[0115] like Figure 1 As shown, a PbZrO3 antiferroelectric capacitor comprises a first electrode layer 1, a PbO layer 2, an antiferroelectric layer 3 of a solid solution ferroelectric, a LaNiO3 layer 4, a single crystal substrate 5 and a second electrode layer 6 which are arranged in sequence, wherein the physical phases in the antiferroelectric layer 3 of the solid solution ferroelectric include PbZrO3, ferroelectric and an Au phase containing Ag.

[0116] The volume ratio of PbZrO3, ferroelectric and Au phase containing Ag in the antiferroelectric layer 3 of the solid solution ferroelectric is 100:11:2.5.

[0117] A method for preparing the PbZrO3 antiferroelectric capacitor described in this embodiment comprises the following steps:

[0118] S1, dissolving lanthanum nitrate and nickel acetate in a solvent to obtain a LaNiO3 precursor solution;

[0119] S2, dissolving lead acetate in a solvent, heating at 80° C. for 3 hours, adding zirconium n-propoxide after cooling, stirring and dissolving to obtain a PbZrO3 precursor solution;

[0120] S3, prepare a ferroelectric precursor solution, wherein the ferroelectric precursor solution is Bi 0.5 Na 0.5 TiO3 precursor solution;

[0121] S4, dissolving lead acetate in a solvent to obtain a PbO precursor solution;

[0122] S5, spin coating the LaNiO3 precursor solution onto a Pt / Si substrate, performing the first spin coating deposition at a rotation speed of 5000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness, thereby obtaining a LaNiO3 layer coated on the single crystal substrate;

[0123] S6, after mixing the PbZrO3 precursor solution with the ferroelectric precursor solution, adding Au nanoparticles containing Ag with a particle size of 48 nm to obtain a mixed solution; spin coating the mixed solution onto the LaNiO3 layer, and performing a second spin coating deposition at a speed of 5000 rpm. After drying and crystallization, this process can be repeated multiple times to achieve a desired film thickness, thereby obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer;

[0124] S7, depositing the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, performing a third spin coating deposition at a rotation speed of 5000 rpm, and repeating this process multiple times after drying and crystallization to achieve a desired film thickness to obtain a capacitor film;

[0125] S8. Depositing gold electrodes on both sides of the capacitor film through a stainless steel mask to construct a first electrode layer and a second electrode layer to obtain a PbZrO3 antiferroelectric capacitor.

[0126] In this embodiment, the solvent is ethylene glycol. The concentration of the LaNiO3 precursor solution, the PbZrO3 precursor solution, the ferroelectric precursor solution and the PbO precursor solution is 0.2M.

[0127] The drying and crystallization are as follows: baking at 250°C for 4 minutes, then pyrolyzing at 450°C for 5 minutes, and crystallizing at 800°C for 12 minutes.

[0128] Comparative Example 1

[0129] This comparative example is similar to Example 1, except that in this comparative example, no Bi0.5Na0.5TiO3 precursor solution is added to S6.

[0130] Comparative Example 2

[0131] This comparative example is similar to Example 1, except that in this comparative example, no Ag-containing Au nanoparticles are added to S6.

[0132] Comparative Example 3

[0133] This comparative example is similar to Example 1, except that in this comparative example, Au nanoparticles without Ag are added to S6.

[0134] The capacitors in Examples 1-6 and Comparative Examples 1-3 were tested for performance, each sample was tested 5 times, and the average value was taken. The test results of energy storage density are shown in Table 1;

[0135] Table 1 Energy storage density test results

[0136]

[0137] The test results of dielectric constant are shown in Table 2.

[0138] Table 2 Test results of dielectric constant

[0139]

[0140] The above are only specific embodiments of the present invention, but the protection scope of the present invention is not limited thereto. The protection scope of the present invention shall be based on the protection scope of the claims.

Claims

1. A PbZrO3 antiferroelectric capacitor, characterized in that: It comprises a first electrode layer, a PbO layer, an antiferroelectric layer of a solid solution ferroelectric, a LaNiO3 layer, a single crystal substrate and a second electrode layer which are arranged in sequence. The physical phases in the antiferroelectric layer of the solid solution ferroelectric include PbZrO3, ferroelectric and an Au phase containing Ag.

2. The PbZrO3 antiferroelectric capacitor according to claim 1, characterized in that: The volume ratio of PbZrO3, ferroelectric and Au phase containing Ag in the antiferroelectric layer of the solid solution ferroelectric is 100:6-12:2-3.

3.

3. A method for preparing a PbZrO3 antiferroelectric capacitor as claimed in claim 1 or 2, characterized in that: The following steps are involved: S1, dissolving lanthanum nitrate and nickel acetate in a solvent to obtain a LaNiO3 precursor solution; S2, dissolving lead acetate in a solvent, heating at 60-150° C. for 0.5-3 hours, adding zirconium n-propoxide after cooling, stirring and dissolving to obtain a PbZrO3 precursor solution; S3, preparing a ferroelectric precursor solution, wherein the ferroelectric precursor solution is a BiScO3 precursor solution, Bi 0.5 Na 0.5 One of the TiO3 precursor solutions; S4, dissolving lead acetate in a solvent to obtain a PbO precursor solution; S5, spin coating the LaNiO3 precursor solution onto a single crystal substrate, performing a first spin coating deposition, and obtaining a LaNiO3 layer coated on the single crystal substrate after drying and crystallization; S6, mixing the PbZrO3 precursor solution with the ferroelectric precursor solution, and then adding Au nanoparticles containing Ag to obtain a mixed solution; spin coating the mixed solution onto the LaNiO3 layer, performing a second spin coating deposition, and obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer after drying and crystallization; S7, depositing the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, performing a third spin coating deposition, and obtaining a capacitor film after drying and crystallization; S8. Depositing gold electrodes on both sides of the capacitor film through a stainless steel mask to construct a first electrode layer and a second electrode layer to obtain a PbZrO3 antiferroelectric capacitor.

4. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 3, characterized in that: The solvent is one or more of 2-methoxyethanol, propionic acid, ethylene glycol and acetic acid.

5. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 3, characterized in that: The concentrations of the LaNiO3 precursor solution, the PbZrO3 precursor solution, the ferroelectric precursor solution and the PbO precursor solution are 0.1-0.4M.

6. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 3, characterized in that: The drying and crystallization are as follows: baking at 100-300°C for 0.5-5 minutes, then pyrolyzing at 350-500°C for 0.5-5 minutes, and crystallizing at 550-800°C for 3-30 minutes.

7. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 3, characterized in that: The single crystal substrate in S5 is one of a LaAlO3 substrate, a SrTiO3 substrate, a Pt / Si substrate, and a DyScO3 substrate.

8. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 3, characterized in that: The rotation speed of the first spin coating deposition is 3000-6000 rpm.

9. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 8, characterized in that: The second spin coating deposition and the third spin coating deposition have the same rotation speed.

10. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 3, characterized in that: The particle size of the Ag-containing Au nanoparticles is 40-50 nm.

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