A PbZrO3 antiferroelectric capacitor and its preparation method

Abstract

The present invention provides a PbZrO3 antiferroelectric capacitor and a preparation method thereof, relating to the technical field of ferroelectric materials. A PbZrO3 antiferroelectric capacitor includes a first electrode layer, a PbO layer, an antiferroelectric layer with a solid-solution ferroelectric body, a LaNiO3 layer, etc. The phases in the antiferroelectric layer with a solid-solution ferroelectric body include PbZrO3, a ferroelectric body, and an Au phase containing Ag. The present invention also provides a preparation method of the capacitor, including the following steps: depositing a LaNiO3 precursor solution onto a single-crystal substrate and crystallizing; mixing a PbZrO3 precursor solution with a ferroelectric precursor solution and adding Au nanoparticles containing Ag; coating the mixture onto the LaNiO3 layer and crystallizing; depositing a PbO precursor solution onto the surface of the antiferroelectric layer with a solid-solution ferroelectric body and crystallizing; performing gold electrode deposition to obtain a PbZrO3 antiferroelectric capacitor. The capacitor in the present invention has a high energy storage efficiency and a high dielectric constant.

Description

Technical Field

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

[0002] A capacitor is an important electronic component used for storing and releasing electric charges and is widely applied in various circuits. Its basic structure includes 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 source, the power source voltage causes charges to accumulate on the two electrodes of the capacitor. These charges form an electric field between the electrodes and the dielectric. The capacitance value of a capacitor reflects its ability to store charges, that is, the amount of electric charges that can be stored under a given voltage. The larger the capacitance value, the more charges the capacitor can store. The capacitor can smooth the voltage fluctuations in the power source, reduce noise and interference; during the transmission of an AC signal, the capacitor can isolate the DC component and allow the AC signal to pass through; reduce the influence of power source noise on the circuit and provide a stable power source voltage; in some applications, the capacitor can store electrical energy and release it when needed, such as in a flash. Generally speaking, a capacitor is an indispensable component in an electronic circuit, and there are various types of capacitors suitable for different application scenarios.

[0004] As an important component in an electronic circuit, the main function of a capacitor is to store and release electrical energy. The performance and applications of a capacitor widely depend on the properties of its dielectric material. 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 type of ferroelectric materials, have a high energy storage density, but also face the problem of low efficiency in practical applications.

[0005] Antiferroelectric materials have a high energy storage density because they can 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 mainly concerned in capacitors due to their high energy storage density. The energy storage density refers to the amount of electrical energy that can be stored per unit volume or per unit mass of the 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 improve the energy storage density of capacitors. This makes them have important application values 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 achieve a smaller volume and lighter weight. This has significant advantages 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 the power systems of electric vehicles, aerospace equipment, and high-power laser systems, antiferroelectric materials can provide higher energy storage capabilities, improving the overall performance and efficiency of the system.

[0009] Antiferroelectric materials have a high energy storage density but low efficiency. Currently, antiferroelectric materials often refine the ferroelectric hysteresis loop through relaxation to improve the energy storage efficiency. However, this relaxation often leads to a loss of polarization, weakening the antiferroelectricity and decreasing the dielectric constant. The decrease in the dielectric constant will directly affect the electrical properties of the capacitor, resulting in a decline in the energy storage capacity. Summary of the Invention

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

[0011] To achieve the above invention object, the technical solutions provided by the present invention are as follows:

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

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

[0014] A preparation method of the PbZrO3 antiferroelectric capacitor described above includes the following steps:

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

[0016] S2. Dissolve lead acetate in a solvent, heat it at 60 - 150 °C for 0.5 - 3 hours, add zirconium n-propoxide after cooling, and stir to dissolve to obtain a PbZrO3 precursor solution;

[0017] S3. Prepare a ferroelectric precursor solution, and the ferroelectric precursor solution is one of a BiScO3 precursor solution, a Bi 0.5 Na 0.5 TiO3 precursor solution;

[0018] S4. Dissolve lead acetate in a solvent to obtain a PbO precursor solution;

[0019] S5. Spin-coat and deposit the LaNiO3 precursor solution onto a single-crystal substrate for the first spin-coating deposition. This process can be repeated multiple times after drying and crystallization to achieve the desired film thickness, and a LaNiO3 layer coated on the single-crystal substrate is obtained;

[0020] S6. Mix the PbZrO3 precursor solution with the ferroelectric precursor solution and then add Au nanoparticles containing Ag to obtain a mixture; Spin-coat the mixture onto the LaNiO3 layer for the second spin-coating deposition. This process can be repeated multiple times after drying and crystallization to achieve the desired film thickness (100 - 1000 nm), and an antiferroelectric layer of solid-solution ferroelectric is obtained coated on the LaNiO3 layer;

[0021] S7. Deposit the PbO precursor solution onto the surface of the antiferroelectric layer of the solid-solution ferroelectric for the third spin-coating deposition. This process can be repeated multiple times after drying and crystallization to achieve the desired film thickness, and a capacitor film is obtained;

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

[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, PbZrO3 precursor solution, ferroelectric precursor solution, and PbO precursor solution are 0.1 - 0.4 M.

[0025] Preferably, the drying and crystallization are as follows: Bake at 100 - 300 °C for 0.5 - 5 minutes, then pyrolyze at 350 - 500 °C for 0.5 - 5 minutes, and crystallize at a temperature of 550 - 800 °C for 3 - 30 minutes.

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

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

[0028] Preferably, the rotation speeds of the second spin-coating deposition and the third spin-coating deposition are the same.

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

[0030] It should be noted that the preparation method of the Ag-containing Au nanoparticles in the present invention can refer to the relevant preparation processes 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. Among them, the antiferroelectric layer of the solid-solution ferroelectric is arranged above the LaNiO3 layer. After introducing the LNO interface layer, the film quality of the antiferroelectric layer of the solid-solution ferroelectric is improved, and the breakdown performance is enhanced, which will increase the energy storage density.

[0032] The phases in the antiferroelectric layer of the solid-solution ferroelectric in the present invention include PbZrO3, a ferroelectric, and an Ag-containing Au phase. The ferroelectric is a BiScO3 ferroelectric or a Bi 0.5 Na 0.5 TiO3 ferroelectric. Among them, both Au and Ag are transition metal elements, and their ions can replace some Pb or Zr atomic sites in the crystal structure of PbZrO3. This substitution may affect the local stress of the lattice, and then affect the overall structure and properties of the film. The mixing of Au and Ag can optimize the conductivity and reduce the resistance in the film. This improved conductivity makes the distribution of the electric field in the film more uniform, thereby improving the dielectric response; the good conductivity of Au-Ag can reduce the interface resistance between the electrode and the PbZrO3 film. The optimized interface contact can reduce the interface charge accumulation and interface resistance, improve the charge injection and extraction efficiency, and then enhance 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 then improve the dielectric constant and energy storage ability; the addition of Au will reduce the grain size of the film, increase the internal stress of the matrix grain boundary, cause field-induced phase transformation, and the diffusivity gradually increases, making the hysteresis loop become slender and inclined, which is beneficial to improving the energy storage performance of the film. In addition, the atomic radius of Ag is different from that of Au, which may lead to a change in the nature of lattice distortion. The Ag-containing Au nanoparticles 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 the BiScO3 or Bi 0.5 Na 0.5TiO3 can provide a relatively high charge polarization intensity. This strong polarization ability can enhance the polarization response of the thin film when an electric field is applied, thereby increasing the dielectric constant.

[0034] Au - Ag improves the interfacial contact between the electrode and the PbZrO3 thin film, reducing the interfacial impedance. BiScO3 or Bi 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 distribution of the electric field in the PbZrO3 thin film more uniform, thus increasing the dielectric constant. Additionally, BiScO3 or Bi 0.5 Na 0.5 The strong polarization ability of TiO3 and the optimized conductivity of Au - Ag act together to create a stronger local electric field in the thin film, thereby enhancing the energy storage density. This composite effect can significantly improve the energy storage capacity of the thin film.

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

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

[0037] By solid - solution of ferroelectrics in antiferroelectric materials, the long - range antiferroelectric order is broken, making the system relax and improving the energy storage efficiency. Also, due to the large polarization characteristics of ferroelectrics, the large polarization of the system is maintained, enhancing the dielectric constant.

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

[0039] The present invention also provides a preparation method of a PbZrO3 antiferroelectric capacitor. Different conductive layers are constructed by spin - coating in batches, and the method is simple with a high yield. Description of the Drawings

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

[0041] Wherein: 1 - the first electrode layer, 2 - PbO layer, 3 - antiferroelectric layer of solid - solution ferroelectrics, 4 - LaNiO3 layer, 5 - single - crystal substrate, 6 - the second electrode layer. Detailed Embodiments

[0042] To make the objectives, technical solutions, and advantages of the embodiments of the present invention clearer, the technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the accompanying drawings of the embodiments of the present invention. Obviously, the described embodiments are some, but not all, of the embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the described embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

[0043] Embodiment 1

[0044] As Figure 1 shown, a PbZrO3 antiferroelectric capacitor includes 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 arranged in sequence. The phases in the antiferroelectric layer 3 of the solid-solution ferroelectric include PbZrO3, a ferroelectric, and an Au phase containing Ag.

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

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

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

[0048] S2. Dissolve lead acetate in a solvent, heat it at 60 °C for 0.5 hours, add zirconium n-propoxide after cooling, and stir to dissolve to obtain a PbZrO3 precursor solution;

[0049] S3. Prepare a ferroelectric precursor solution, and the ferroelectric precursor solution is a BiScO3 precursor solution;

[0050] S4. Dissolve lead acetate in a solvent to obtain a PbO precursor solution;

[0051] S5. Spin-coat and deposit the LaNiO3 precursor solution onto a LaAlO3 substrate, perform the first spin-coat deposition at a speed of 3000 revolutions per minute, and this process can be repeated multiple times after drying and crystallization to achieve the required film thickness, obtaining a LaNiO3 layer coated on the single-crystal substrate;

[0052] S6. Mix the PbZrO3 precursor solution with the ferroelectric precursor solution, and then add Au nanoparticles containing Ag with a particle size of 40 nm to obtain a mixed solution. Spin-coat the mixed solution onto the LaNiO3 layer, and perform the second spin-coating deposition at a speed of 3000 revolutions per minute. This process can be repeated multiple times after drying and crystallization to achieve the desired film thickness, and an antiferroelectric layer of solid-solution ferroelectric is obtained, which is coated on the LaNiO3 layer.

[0053] S7. Deposit the PbO precursor solution onto the surface of the antiferroelectric layer of the solid-solution ferroelectric, and perform the third spin-coating deposition at a speed of 3000 revolutions per minute. This process can be repeated multiple times after drying and crystallization to achieve the desired film thickness, and a capacitor film is obtained.

[0054] S8. Deposit gold electrodes on both sides of the capacitor film through a stainless-steel mask plate to construct a first electrode layer and a second electrode layer, and a PbZrO3 antiferroelectric capacitor is obtained.

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

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

[0057] Example 2

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

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

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

[0061] S1. Dissolve lanthanum nitrate and nickel acetate in a solvent to obtain a LaNiO3 precursor solution.

[0062] S2. Dissolve lead acetate in a solvent, heat it at 150 °C for 3 hours, add n-propyl zirconium after cooling, and stir to dissolve to obtain a PbZrO3 precursor solution.

[0063] S3. Configure a ferroelectric precursor solution, which is a Bi 0.5 Na 0.5 TiO3 precursor solution;

[0064] S4. Dissolve lead acetate in a solvent to obtain a PbO precursor solution;

[0065] S5. Spin-coat and deposit the LaNiO3 precursor solution onto the SrTiO3 substrate, perform the first spin-coat deposition at a speed of 6000 revolutions per minute, and after drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, obtaining a LaNiO3 layer coated on the single-crystal substrate;

[0066] S6. Mix the PbZrO3 precursor solution with the ferroelectric precursor solution and add Ag-containing Au nanoparticles with a particle size of 50 nm to obtain a mixture; spin-coat the mixture onto the LaNiO3 layer, perform the second spin-coat deposition at a speed of 6000 revolutions per minute, and after drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, obtaining an antiferroelectric layer of a solid-solution ferroelectric coated on the LaNiO3 layer;

[0067] S7. Deposit the PbO precursor solution onto the surface of the antiferroelectric layer of the solid-solution ferroelectric, perform the third spin-coat deposition at a speed of 6000 revolutions per minute, and after drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, obtaining a capacitor film;

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

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

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

[0071] Example 3

[0072] As Figure 1 shown, a PbZrO3 antiferroelectric capacitor includes 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 arranged in sequence. The phases in the antiferroelectric layer 3 of the solid-solution ferroelectric include PbZrO3, ferroelectric, and Ag-containing Au phase.

[0073] In the antiferroelectric layer 3 of the solid solution ferroelectric, the volume ratios of PbZrO3, ferroelectric, and Ag-containing Au phase are 100:10:2.5.

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

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

[0076] S2. Dissolve lead acetate in a solvent, heat it at 120 °C for 2 hours, add zirconium propoxide after cooling, and stir to dissolve to obtain a PbZrO3 precursor solution;

[0077] S3. Prepare a ferroelectric precursor solution, and the ferroelectric precursor solution is a Bi 0.5 Na 0.5 TiO3 precursor solution;

[0078] S4. Dissolve lead acetate in a solvent to obtain a PbO precursor solution;

[0079] S5. Spin-coat and deposit the LaNiO3 precursor solution onto the Pt / Si substrate, perform the first spin-coat deposition at a speed of 5000 revolutions per minute, and repeat this process multiple times after drying and crystallization to achieve the desired film thickness, obtaining a LaNiO3 layer coated on the single-crystal substrate;

[0080] S6. Mix the PbZrO3 precursor solution and the ferroelectric precursor solution, add Ag-containing Au nanoparticles with a particle size of 45 nm to obtain a mixture; spin-coat the mixture onto the LaNiO3 layer, perform the second spin-coat deposition at a speed of 5000 revolutions per minute, and repeat this process multiple times after drying and crystallization to achieve the desired film thickness, obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer;

[0081] S7. Deposit the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, perform the third spin-coat deposition at a speed of 5000 revolutions per minute, and repeat this process multiple times after drying and crystallization to achieve the desired film thickness, obtaining a capacitor film;

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

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

[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] Replacing the solvent in this example with acetic acid and the substrate with a DyScO3 substrate, the performance of the obtained product is similar to that of the product in this example.

[0086] Example 4

[0087] As Figure 1 shown, a PbZrO3 antiferroelectric capacitor includes 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 arranged in sequence. The phases in the antiferroelectric layer 3 of the solid-solution ferroelectric include PbZrO3, a ferroelectric, and an Au phase containing Ag.

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

[0089] A preparation method of the PbZrO3 antiferroelectric capacitor described in this example includes the following steps:

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

[0091] S2. Dissolve lead acetate in a solvent, heat at 100 °C for 1 hour, add zirconium n-propoxide after cooling, and stir to dissolve to obtain a PbZrO3 precursor solution;

[0092] S3. Prepare a ferroelectric precursor solution, and the ferroelectric precursor solution is a Bi 0.5 Na 0.5 TiO3 precursor solution;

[0093] S4. Dissolve lead acetate in a solvent to obtain a PbO precursor solution;

[0094] S5. Spin-coat and deposit the LaNiO3 precursor solution onto a DyScO3 substrate, perform the first spin-coat deposition at a speed of 5000 revolutions per minute, and repeat this process multiple times after drying and crystallization to achieve the required film thickness, obtaining a LaNiO3 layer coated on the single-crystal substrate;

[0095] S6. Mix the PbZrO3 precursor solution with the ferroelectric precursor solution, and then add Au nanoparticles containing Ag with a particle size of 45 nm to obtain a mixed solution. Spin-coat the mixed solution onto the LaNiO3 layer, and perform the second spin-coating deposition at a speed of 5000 revolutions per minute. After drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, and an antiferroelectric layer of solid-solution ferroelectric is obtained on the LaNiO3 layer.

[0096] S7. Deposit the PbO precursor solution onto the surface of the antiferroelectric layer of the solid-solution ferroelectric, and perform the third spin-coating deposition at a speed of 5000 revolutions per minute. After drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, and a capacitor film is obtained.

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

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

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

[0100] Example 5

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

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

[0103] A preparation method of the PbZrO3 antiferroelectric capacitor described in this embodiment includes the following steps:

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

[0105] S2. Dissolve lead acetate in a solvent, heat at 100 °C for 3 hours, add zirconium n-propoxide after cooling, and stir to dissolve to obtain a PbZrO3 precursor solution;

[0106] S3. Configure a ferroelectric precursor solution, which is a Bi 0.5 Na 0.5 TiO3 precursor solution;

[0107] S4. Dissolve lead acetate in a solvent to obtain a PbO precursor solution;

[0108] S5. Spin-coat and deposit the LaNiO3 precursor solution onto a Pt / Si substrate, perform the first spin-coat deposition at a speed of 5000 revolutions per minute. After drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, obtaining a LaNiO3 layer coated on the single-crystal substrate;

[0109] S6. Mix the PbZrO3 precursor solution with the ferroelectric precursor solution and add Ag-containing Au nanoparticles with a particle size of 45 nm to obtain a mixture; spin-coat the mixture onto the LaNiO3 layer, perform the second spin-coat deposition at a speed of 5000 revolutions per minute. After drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, obtaining an antiferroelectric layer of a solid-solution ferroelectric coated on the LaNiO3 layer;

[0110] S7. Deposit the PbO precursor solution onto the surface of the antiferroelectric layer of the solid-solution ferroelectric, perform the third spin-coat deposition at a speed of 5000 revolutions per minute. After drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, obtaining a capacitor film;

[0111] S8. Deposit 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, obtaining a PbZrO3 antiferroelectric capacitor.

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

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

[0114] Example 6

[0115] As Figure 1 shown, a PbZrO3 antiferroelectric capacitor includes 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 arranged in sequence. The phases in the antiferroelectric layer 3 of the solid-solution ferroelectric include PbZrO3, a ferroelectric, and an Ag-containing Au phase.

[0116] In the antiferroelectric layer 3 of the solid solution ferroelectric, the volume ratios of PbZrO3, ferroelectric, and Ag-containing Au phase are 100:11:2.5.

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

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

[0119] S2. Dissolve lead acetate in a solvent, heat it at 80 °C for 3 hours, add zirconium propoxide after cooling, and stir to dissolve to obtain a PbZrO3 precursor solution;

[0120] S3. Prepare a ferroelectric precursor solution, and the ferroelectric precursor solution is a Bi 0.5 Na 0.5 TiO3 precursor solution;

[0121] S4. Dissolve lead acetate in a solvent to obtain a PbO precursor solution;

[0122] S5. Spin-coat and deposit the LaNiO3 precursor solution onto a Pt / Si substrate, perform the first spin-coat deposition at a speed of 5000 revolutions per minute, and after drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, obtaining a LaNiO3 layer coated on the single crystal substrate;

[0123] S6. Mix the PbZrO3 precursor solution with the ferroelectric precursor solution, add Ag-containing Au nanoparticles with a particle size of 48 nm to obtain a mixture; spin-coat the mixture onto the LaNiO3 layer, perform the second spin-coat deposition at a speed of 5000 revolutions per minute, and after drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, obtaining an antiferroelectric layer of a solid solution ferroelectric coated on the LaNiO3 layer;

[0124] S7. Deposit the PbO precursor solution onto the surface of the antiferroelectric layer of the solid solution ferroelectric, perform the third spin-coat deposition at a speed of 5000 revolutions per minute, and after drying and crystallization, this process can be repeated multiple times to achieve the desired film thickness, obtaining a capacitor film;

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

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

[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, the Bi0.5Na0.5TiO3 precursor solution is not added in S6.

[0130] Comparative Example 2

[0131] This comparative example is similar to Example 1, except that in this comparative example, the Ag-containing Au nanoparticles are not added in S6.

[0132] Comparative Example 3

[0133] This comparative example is similar to Example 1, except that in this comparative example, the Ag-free Au nanoparticles are added in S6.

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

[0135] Table 1 Test Results of Energy Storage Density

[0136]

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

[0138] Table 2 Test Results of Dielectric Constant

[0139]

[0140] The above is only the specific implementation manner 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 subject to the protection scope of the claims.

Claims

1. A PbZrO3 antiferroelectric capacitor, characterized in that: The invention 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, wherein the antiferroelectric layer of the solid solution ferroelectric comprises PbZrO3, a ferroelectric and an Au phase containing Ag, and the ferroelectric is BiScO3 or Bi 0.5 Na 0.5 TiO3, 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.

2. A method for preparing a PbZrO3 antiferroelectric capacitor as claimed in claim 1, 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.

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

4. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 2, 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.

5. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 2, 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.

6. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 2, 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.

7. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 2, characterized in that: The rotation speed of the first spin coating deposition is 3000-6000 rpm.

8. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 7, characterized in that: The second spin coating deposition and the third spin coating deposition have the same rotation speed.

9. The method for preparing a PbZrO3 antiferroelectric capacitor according to claim 2, characterized in that: The particle size of the Ag-containing Au nanoparticles is 40-50 nm.

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