CN115274298A - Lead zirconate nano composite dielectric film and preparation method thereof - Google Patents
Lead zirconate nano composite dielectric film and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title abstract description 9
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- 238000004146 energy storage Methods 0.000 claims abstract description 33
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
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- 238000001704 evaporation Methods 0.000 claims description 20
- 230000008020 evaporation Effects 0.000 claims description 20
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- 229910052681 coesite Inorganic materials 0.000 claims description 18
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- 239000000377 silicon dioxide Substances 0.000 claims description 18
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- XPGAWFIWCWKDDL-UHFFFAOYSA-N propan-1-olate;zirconium(4+) Chemical compound [Zr+4].CCC[O-].CCC[O-].CCC[O-].CCC[O-] XPGAWFIWCWKDDL-UHFFFAOYSA-N 0.000 claims description 16
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/02—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by baking
- B05D3/0254—After-treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/14—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to metal, e.g. car bodies
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G4/00—Fixed capacitors; Processes of their manufacture
- H01G4/002—Details
- H01G4/018—Dielectrics
- H01G4/06—Solid dielectrics
- H01G4/08—Inorganic dielectrics
- H01G4/10—Metal-oxide dielectrics
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D2202/00—Metallic substrate
- B05D2202/20—Metallic substrate based on light metals
- B05D2202/25—Metallic substrate based on light metals based on Al
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Abstract
A lead zirconate nano-composite dielectric film and a preparation method thereof belong to the technical field of electronic materials, functional materials and intelligent materials, and Al: pbZrO 23The volume ratio is 0.5-2.0%:99.5 to 98.0 percent, the aluminum-rich nano particles are distributed on the lead zirconate substrate in a layered mode, and the breakdown electric field intensity and the energy storage density of the aluminum-rich nano particles are respectively improved by about 182 percent and 68 percent compared with those of a lead zirconate film. The material is prepared by vacuum evaporation and chemical solution deposition methods, has the advantages of simple process, low cost, large-area uniform film formation and the like, and has wide application in the field of pulse power devicesThe application is as follows.
Description
Technical Field
The invention belongs to the technical field of electronic materials, functional materials and intelligent materials, and particularly relates to a lead zirconate nano-composite dielectric film and a preparation method thereof.
Background
With the introduction of the concept of "carbon neutralization and carbon peaking", the importance of new energy sources is increasingly highlighted. In addition to the development of new energy sources such as solar energy, wind energy, tidal power generation and the like, the energy storage technology is increasingly paid attention to by people, and the key point of the energy storage technology is to develop energy storage materials meeting application requirements. The dielectric capacitor has the advantages of high dielectric constant, low dielectric loss, high power density, high charging/discharging speed, large working voltage/current, good reliability, good temperature stability and the like, and is already applied to the field of pulse power devices. With zirconium titanic acid (PbZrO)3) The typical antiferroelectric dielectric material has high energy storage density due to its unique electric field induced antiferroelectric-ferroelectric phase transition characteristics, and is considered to be one of the most promising dielectric materials. In general, the energy storage density of the antiferroelectric material is determined by parameters such as remanent polarization, maximum polarization, antiferroelectric-ferroelectric phase transition electric field strength, and breakdown electric field strength. Although the difference between the maximum polarization strength and the residual polarization strength of the zirconium titanic acid is large, the breakdown electric field strength is low, so that the energy storage density of the zirconium titanic acid still cannot meet the requirement of practical application.
Disclosure of Invention
The purpose of the invention is as follows: the breakdown electric field intensity of the zirconium titanic acid is low, and the energy storage density cannot meet the application requirement; thus providing a lead zirconate nano-composite dielectric film and a preparation method thereof.
The technical scheme is as follows:
a lead zirconate nano-composite dielectric film is characterized in that: the components of the film material meet the following requirements: al: pbZrO 23The volume ratio is 0.5-2.0%:99.5 to 98.0 percent; the microstructure of the film material is that the aluminum-rich nano particles are distributed in the lead zirconate matrix in a layered manner.
The preparation method of the lead zirconate nano composite dielectric film is characterized by comprising the following steps of:
(1) With acetic acid (CH)3COOH) as solvent, lead acetate (Pb (CH)3COO)2·3H2O) and zirconium n-propoxide (Zr (OCH)2CH2CH3)4) Preparing a lead zirconate precursor solution as a solute, weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1, adding the lead acetate and the zirconium n-propoxide into acetic acid according to the standard that the concentration of the lead zirconate is 0.3-0.5M, distilling at constant temperature of 120 ℃ for 90 minutes, and then cooling to room temperature; adding deionized water according to the proportion of 175ml/L, and magnetically stirring until the solution is clear and transparent; then, lactic acid (CH) was added at a ratio of 42g/L3CH (OH) COOH) and 25g/L ethylene glycol (CH) were added2OH)2Stirring for 30 minutes; finally, acetic acid is added again to supplement the loss of the solvent in the distillation process, so that the concentration of the solution reaches 0.3-0.5M, and a light yellow transparent solution is obtained; filtering the solution with a 0.45-micron filter, and aging for 20 hours;
(2) In Pt/Ti/SiO2Depositing a metal Al layer on the Si substrate by a vacuum thermal evaporation method; setting the working current and the working voltage of the evaporation equipment to be 90-110A and 1.0V respectively, and controlling the evaporation rate of the metal Al layer to be
Obtaining a metal Al layer with the thickness of 2.5-10 nm on the substrate by regulating and controlling the evaporation time;
(3) Al/Pt/Ti/SiO with the metal Al layer prepared in the step (2)2Putting the Si substrate on a spin coater, and dripping the lead zirconate precursor solution prepared in the step (1) on Al/Pt/Ti/SiO2Spin coating on a Si substrate at the rotating speed of 2500-3500 rpm for 30-50 seconds to obtain a raw material film of lead zirconate;
(4) Drying the raw material film prepared in the step (3) on a hot plate at the temperature of 110-150 ℃ for 10 minutes, then putting the raw material film into an electric furnace for thermal decomposition treatment, firstly heating the raw material film at the temperature of 300-400 ℃ for 10-15 minutes, and then heating the raw material film at the temperature of 550-600 ℃ for 10-15 minutes;
(5) Repeating the spin coating in the step (3) and the drying and thermal decomposition in the step (4) for 4 times to prepare a lead zirconate film with the thickness of 500 nm;
(6) Putting the lead zirconate film prepared in the step (5) into an electric furnace for annealing, wherein the heating temperature is 600-750 ℃, and the heating time is 20-40 minutes; in the annealing process, the lead zirconate film is completely crystallized to form a perovskite phase, and the metallic aluminum is diffused into the lead zirconate film to form a microstructure in which aluminum-rich nano particles are distributed on a lead zirconate substrate in a layered manner, so that the lead zirconate nano composite dielectric film is obtained.
Preferably, the evaporation rate of the metal Al in the step (2) is
The evaporation time is 125-500 s.
Preferably, the annealing heating temperature in the step (6) is 700 ℃ and the time is 30 minutes.
Preferably, the lead zirconate nano composite dielectric film obtained in the step (6) has antiferroelectricity, wherein the volume ratio of aluminum to lead zirconate is 1.0%; the maximum polarization and the residual polarization were 79.8. Mu.C/cm, respectively2、18.8μC/cm2The breakdown strength of the electric field and the energy storage density are 1858kV/cm and 25J/cm respectively3。
Compared with the prior art, the invention has the following advantages and effects:
the invention utilizes vacuum evaporation and chemical solution deposition to prepare the nano composite film, and can effectively improve the breakdown electric field intensity and the energy storage density of the lead zirconate dielectric film material by embedding the aluminum-rich nano particles which are distributed in a layered manner on the lead zirconate substrate. The breakdown electric field strength and the energy storage density of the material are respectively improved by about 182 percent and 68 percent compared with those of a lead zirconate film. The material has the advantages of simple preparation method, low cost, large-area uniform film formation and the like, and can be widely applied to the field of pulse power devices.
Drawings
FIG. 1 is a schematic view showing the microstructure change before and after annealing of the lead zirconate nanocomposite film of the invention;
FIG. 2 is a transmission electron micrograph of the microstructure of the cross section of the lead zirconate nanocomposite film prepared by the invention;
FIG. 3 shows Al: pbZrO 23Is a hysteresis loop of 1Vol percent of the lead zirconate nano composite film after annealing at the temperature of 600-750 ℃;
FIG. 4 shows Al: pbZrO 23The polarization intensity of the nanocomposite film was 1Vol% as a function of annealing temperature;
and (4):
drying the lead zirconate raw material film prepared in the step (3) on a hot plate at 120 ℃ for 10 minutes, then putting the film into an electric furnace for thermal decomposition treatment, and firstly, 300 DEG CoHeating for 10min at C, and heating again at 550 deg.CoC, heating for 10 minutes;
and (5):
and (5) repeating the spin coating in the step (3) and the drying and thermal decomposition in the step (4) for 4 times to prepare the lead zirconate film with the thickness of 500 nm.
FIG. 6 shows the maximum polarization, remanent polarization and the difference between the maximum polarization and the remanent polarization of the lead zirconate nanocomposite film prepared by the invention as a function of Al: pbZrO 23A graph of change in volume ratio;
FIG. 7 shows that the breakdown electric field strength and energy storage density of the lead zirconate nano-composite film prepared by the invention are calculated according to the following formula: pbZrO 23Graph of the change in volume ratio.
Detailed Description
A lead zirconate nano composite dielectric film comprises the following components in percentage by weight: pbZrO 23The volume ratio is 0.5-2.0%:99.5 to 98.0 percent.
The film material structure is that the aluminum-rich nano particles are distributed on the lead zirconate substrate in a layered manner.
The preparation method of the lead zirconate nano composite dielectric film comprises the following steps:
(1) With acetic acid (CH)3COOH) as solvent, lead acetate (Pb (CH)3COO)2·3H2O) and zirconium n-propoxide (Zr (OCH)2CH2CH3)4) And preparing a lead zirconate precursor solution for the solute. Weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1And then cooled to room temperature. Then, lactic acid (CH) was added at a ratio of 42g/L3CH (OH) COOH) and 25g/L ethylene glycol (CH) were added2OH)2The solution viscosity was adjusted and stirred for 30 minutes. Finally, adding acetic acid again to supplement the loss of the solvent in the distillation process, so that the concentration of the solution reaches 0.4M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45-micron filter, and aging for 20 hours;
(2) In Pt/Ti/SiO2Depositing an Al metal layer on the Si substrate by a vacuum thermal evaporation method; setting the working current and the working voltage of the evaporation equipment to be 90-110A and 1.0V respectively, and controlling the evaporation rate of the metal Al layer to be
Obtaining a metal Al layer with the thickness of 2.5-10 nm by regulating and controlling the evaporation time to be 125-500 s;
(3) Mixing Al/Pt/Ti/SiO prepared in the step (2)2Putting the/Si substrate on a spin coating instrument, and dripping the lead zirconate precursor solution prepared in the step (1) on the Al/Pt/Ti/SiO prepared in the step (2)2Coating the substrate/Si in a spin mode at the rotating speed of 2500-3500 rpm for 30-50 seconds to obtain a raw material film of lead zirconate;
(4) Drying the raw material film prepared in the step (3) on a hot plate at the temperature of 110-150 ℃ for 10 minutes, then putting the raw material film into an electric furnace for thermal decomposition treatment, firstly heating the raw material film at the temperature of 300-400 ℃ for 10-15 minutes, and then heating the raw material film at the temperature of 550-600 ℃ for 10-15 minutes;
(5) Repeating the spin coating in the step (3) and the drying and thermal decomposition treatment in the step (4) for 4 times to prepare a lead zirconate film with the thickness of 500 nm;
(6) And (3) putting the lead zirconate film prepared in the step (5) into an electric furnace for annealing, wherein the heating temperature is 600-750 ℃, and the time is 20-40 minutes. During the heating process, the lead zirconate crystallizes to become a perovskite phase, and simultaneously aluminum diffuses into the lead zirconate layer to form aluminum-rich nano particles, so that the lead zirconate nano composite dielectric film is obtained.
The invention will be described in further detail with reference to the following drawings and specific examples, which are given by way of illustration and not by way of limitation.
Example 1
Step (1):
with acetic acid (CH)3COOH) as solvent, lead acetate (Pb (CH)3COO)2·3H2O) and zirconium n-propoxide (Zr (OCH)2CH2CH3)4) And preparing a lead zirconate precursor solution for the solute. Weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1, adding the weighed lead acetate and zirconium n-propoxide into acetic acid according to the standard that the concentration of the lead zirconate is 0.4M, distilling the mixture at the constant temperature of 120 ℃ for 90 minutes, and then cooling the mixture to room temperature. Then, lactic acid (CH) was added at a ratio of 42g/L3CH (OH) COOH) and 25g/L ethylene glycol (CH) were added2OH)2The solution viscosity was adjusted and stirred for 30 minutes. Finally, adding acetic acid again to supplement the loss of the solvent in the distillation process, so that the concentration of the solution reaches 0.4M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45-micron filter, and aging for 20 hours;
step (2):
using Pt/Ti/SiO2a/Si (100) substrate. In Pt/Ti/SiO2And depositing an Al metal layer on the/Si substrate by a vacuum thermal evaporation method. Setting the working current and the working voltage of the evaporation equipment to be 106A and 1.0V respectively, and controlling the evaporation rate of the metal Al to be
The deposition time was 250 seconds, and an Al metal layer having a thickness of 5nm was obtained.
And (3):
mixing Al/Pt/Ti/SiO prepared in the step (2)2Putting the/Si substrate on a spin coating instrument, and dripping the lead zirconate precursor solution prepared in the step (1) to Al/Pt/Ti/SiO2On a/Si substrate, spin-coating at 3500 rpm for 30 seconds to obtain a film on Al/Pt/Ti/SiO2A raw material film of lead zirconate on a Si substrate.
And (4):
drying the lead zirconate raw material film prepared in the step (3) on a hot plate at 120 ℃ for 10 minutes, then performing thermal decomposition treatment, heating in a furnace at 300 ℃ for 10 minutes, and then heating in an electric furnace at 600 ℃ for 10 minutes;
and (5):
and (5) repeating the spin coating in the step (3) and the drying and thermal decomposition in the step (4) for 4 times to prepare the lead zirconate film with the thickness of 500 nm.
And (6):
PbZrO prepared in the step (5)3/Al/Pt/Ti/SiO2Putting the Si multilayer film into an electric furnace for annealing, wherein the heating temperature is 700 ℃, and the heating time is 30 minutes; in the annealing process, the lead zirconate film is completely crystallized to form a perovskite phase, and the metallic aluminum is diffused into the lead zirconate film to form a microstructure that aluminum-rich nano particles are diffused and distributed on a lead zirconate substrate in a layered discontinuous way, so that the lead zirconate nano composite dielectric film is obtained.
As shown in fig. 1, in the annealing process of the lead zirconate nanocomposite film prepared in example 1, the lead zirconate film is completely crystallized to form a perovskite phase, and the aluminum metal is diffused into the lead zirconate film, so that aluminum-rich nanoparticles are formed and distributed on a lead zirconate substrate in a layered manner. FIG. 2 is a transmission electron microscope photograph of the cross section of the composite film, showing the microstructure characteristics of the Al-rich nanoparticles distributed in layers on the lead zirconate matrix. The thickness of the Al metal layer for preparing the composite film is 5nm3The thickness of the film was 500nm, so that the Al: pbZrO 23The volume ratio is 1%. As shown in FIG. 3, the polarization and electric field hysteresis loop of the composite film has antiferroelectric characteristics, and when the electric field strength is zero, the residual polarization strength is obviously reduced, i.e. a double hysteresis loop appears. The maximum polarization and the residual polarization of the composite film are respectively 79.8 mu C/cm2、 18.8μC/cm2(see FIG. 4), the breakdown strength of the electric field and the energy storage density are 1858kV/cm and 25J/cm, respectively3(see FIG. 7).
Example 2
Step (1):
with acetic acid (CH)3COOH) as solvent, lead acetate (Pb (CH)3COO)2·3H2O) and zirconium n-propoxide (Zr (OCH)2CH2CH3)4) And preparing a lead zirconate precursor solution for the solute. Weighing lead acetate and n-Zr according to the atomic ratio of Pb to Zr of 1Zirconium propoxide, added to acetic acid at a concentration of 0.4M lead zirconate, distilled at 120 ℃ for 90 minutes at constant temperature and subsequently cooled to room temperature. Then, lactic acid (CH) was added at a ratio of 42g/L3CH (OH) COOH) and 25g/L ethylene glycol (CH) were added2OH)2The solution viscosity was adjusted and stirred for 30 minutes. Finally, adding acetic acid again to supplement the loss of the solvent in the distillation process, so that the concentration of the solution reaches 0.4M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45-micron filter, and aging for 20 hours;
step (2):
using Pt/Ti/SiO2a/Si (100) substrate. Vacuum thermal evaporation method for preparing Pt/Ti/SiO2Depositing an Al metal layer on the Si substrate. Setting the working current and the working voltage of the evaporation equipment to be 106A and 1.0V respectively, and controlling the evaporation rate of metal Al to be
The evaporation time was 250 seconds, and an Al metal layer having a thickness of 5nm was obtained.
And (3):
mixing Al/Pt/Ti/SiO prepared in the step (2)2Putting the/Si substrate on a spin coating instrument, and dripping the lead zirconate precursor solution prepared in the step (1) to Al/Pt/Ti/SiO2Coating on Si substrate at 3000 rpm for 40 s to obtain Al/Pt/Ti/SiO2A raw material film of lead zirconate on a Si substrate.
And (4):
drying the lead zirconate raw material film prepared in the step (3) on a hot plate at 120 ℃ for 10 minutes, then putting the lead zirconate raw material film into an electric furnace for thermal decomposition treatment, heating the lead zirconate raw material film at 300 ℃ for 10 minutes, and then heating the lead zirconate raw material film at 550 ℃ for 10 minutes;
and (5):
and (5) repeating the spin coating in the step (3) and the drying and thermal decomposition in the step (4) for 4 times to prepare the lead zirconate film with the thickness of 500 nm.
And (6):
putting the lead zirconate film prepared in the step (5) into an electric furnace for annealing, wherein the heating temperature is 600 ℃, 650 ℃, 700 ℃ and 750 ℃ respectively, and the heating time isFor 30 minutes. The thickness of the Al metal layer for preparing the composite film is 5nm3The thickness of the film was 500nm, so that the Al: pbZrO 23The volume ratio is 1%.
According to the above method, (a), (b), (c) and (d) in fig. 3 are hysteresis loops of composite films of annealing temperatures of 600 ℃, 650 ℃, 700 ℃ and 750 ℃ respectively, showing that these films all have antiferroelectric properties, but the maximum polarization and the remanent polarization are different. As shown in fig. 4, as the annealing temperature increases, the maximum polarization and the remnant polarization increase and then decrease, and peaks at 700 ℃. As shown in FIG. 1, the annealing temperature is low, pbZrO3Can not be completely crystallized to become a perovskite phase, and has poor polarization performance; and the annealing temperature is high, the aluminum-rich nano particles are enriched and grown, the distribution is uneven, and the polarization performance can be reduced. Therefore, the annealing temperature for preparing the composite film can be optimized to 700 ℃.
Example 3
Step (1):
with acetic acid (CH)3COOH) as solvent, lead acetate (Pb (CH)3COO)2·3H2O) and zirconium (Zr (OCH) n-propoxide2CH2CH3)4) And preparing a lead zirconate precursor solution for the solute. Weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1, adding the weighed lead acetate and zirconium n-propoxide into acetic acid according to the standard that the concentration of the lead zirconate is 0.4M, distilling the mixture at the constant temperature of 120 ℃ for 90 minutes, and then cooling the mixture to room temperature. Then, lactic acid (CH) was added at a ratio of 42g/L3CH (OH) COOH) and 25g/L ethylene glycol (CH) were added2OH)2The solution viscosity was adjusted and stirred for 30 minutes. Finally, adding acetic acid again to supplement the loss of the solvent in the distillation process, so that the concentration of the solution reaches 0.4M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45-micron filter, and aging for 20 hours;
step (2):
using Pt/Ti/SiO2a/Si (100) substrate. Vacuum thermal evaporation method is used for preparing Pt/Ti/SiO2Depositing an Al metal layer on the Si substrate. The working current and the working voltage of the evaporation equipment are respectively set to be 106A and 1.0V, and the evaporation of metal Al is controlledA plating rate of
The evaporation time was 125 seconds, 250 seconds, 375 seconds and 500 seconds, respectively, and Al metal layers having thicknesses of 2.5nm, 5nm, 7.5nm and 10nm, respectively, were obtained.
And (3):
Al/Pt/Ti/SiO of Al metal layers with different thicknesses prepared in the step (2)2Respectively placing the/Si substrates on a spin coater, and dripping the lead zirconate precursor solution prepared in the step (1) on Al/Pt/Ti/SiO2And spin-coating on the/Si substrate at 3000 rpm for 40 s to obtain the lead zirconate raw material film on the Al metal layers with different thicknesses.
And (4):
drying the lead zirconate raw material film prepared in the step (3) on a hot plate at 120 ℃ for 10 minutes, then respectively heating in electric furnaces at 300 ℃ and 600 ℃ for 10 minutes, and carrying out thermal decomposition treatment;
and (5):
and (4) repeating the spin coating of the step (3) and the drying and thermal decomposition of the step (4) for 4 times to prepare the lead zirconate film with the thickness of 500 nm.
And (6):
and (3) putting the lead zirconate film prepared in the step (5) into an electric furnace for annealing, wherein the heating temperature is 700 ℃, and the time is 30 minutes. During the heating process, the lead zirconate crystallizes to become a perovskite phase, and simultaneously aluminum diffuses into the lead zirconate layer to form aluminum-rich nano particles, so that the lead zirconate nano composite dielectric film is obtained. Al/PbZrO of lead zirconate nano composite film prepared by using Al metal layer with thickness of 2.5nm3The volume ratio was 0.5Vol%, and as shown in FIG. 5 (b), the polarization and electric field hysteresis loop had typical antiferroelectric characteristics, and the maximum polarization and remanent polarization were 69.3. Mu.C/cm, respectively2And 11.4. Mu.C/cm2(see FIG. 6), the breakdown strength of the electric field and the energy storage density are 1557 kV/cm and 16.0J/cm respectively3(see FIG. 7). Al/PbZrO of lead zirconate nano composite film prepared by using Al metal layer with thickness of 5nm3The volume ratio was 1.0Vol%. As shown in FIG. 3 (c), the composite film has antiferroelectric properties, and its maximum polarization and residual polarization are dividedRespectively 77.6 mu C/cm2、 24.8μC/cm2(see FIG. 6), the electric field breakdown strength and the energy storage density were 1980kV/cm and 19.4J/cm, respectively3(see FIG. 7). Al/PbZrO of lead zirconate nano composite film prepared by using Al metal layer with thickness of 7.5nm3The volume ratio was 1.5Vol%. As shown in FIG. 5 (C), the composite film still had antiferroelectric properties, and its maximum polarization and remanent polarization were 77.6. Mu.C/cm, respectively2、 24.8μC/cm2(see FIG. 6), the electric field breakdown strength and the energy storage density were 1980kV/cm and 19.4J/cm, respectively3(see FIG. 7). Al/PbZrO of lead zirconate nano composite dielectric film material prepared by using Al metal layer with thickness of 10nm3The volume ratio was 2.0Vol%. As shown in fig. 5 (d), the ferroelectric hysteresis loop of the composite thin film has a typical ferroelectric characteristic, and the residual polarization is not significantly reduced when the electric field strength is zero. The maximum polarization and the residual polarization of the sample are 53.4 mu C/cm2、 36.7μC/cm2(see FIG. 6), the electric field breakdown strength and the energy storage density were 2043kV/cm and 7.8J/cm, respectively3(see FIG. 7).
Comparative example 1
Step (1):
with acetic acid (CH)3COOH) as solvent, lead acetate (Pb (CH)3COO)2·3H2O) and zirconium (Zr (OCH) n-propoxide2CH2CH3)4) And preparing a lead zirconate precursor solution for the solute. Weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1, adding the weighed lead acetate and zirconium n-propoxide into acetic acid according to the standard that the concentration of the lead zirconate is 0.4M, distilling the mixture at the constant temperature of 120 ℃ for 90 minutes, and then cooling the mixture to room temperature. Then, lactic acid (CH) was added in a ratio of 42g/L3CH (OH) COOH) and 25g/L ethylene glycol (CH) were added2OH)2The solution viscosity was adjusted and stirred for 30 minutes. Finally, adding acetic acid again to supplement the loss of the solvent in the distillation process, so that the concentration of the solution reaches 0.4M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45-micron filter, and aging for 20 hours;
step (2):
using Pt/Ti/SiO2a/Si (100) substrate. Dripping the lead zirconate precursor solution prepared in the step (1) on a substrate for spin coating,rotating at 3000 rpm for 40 s to obtain lead zirconate film;
and (3):
drying the raw material film of the lead zirconate prepared in the step (2) on a hot plate at 120 ℃ for 10 minutes, and then heating the raw material film in muffle furnaces at 300 ℃ and 600 ℃ for 10 minutes respectively to carry out thermal decomposition treatment;
and (4):
and (3) repeating the spin coating and the drying and the thermal decomposition for 4 times to prepare the lead zirconate film with the thickness of 500 nm.
And (5):
and (3) putting the lead zirconate film prepared in the step (4) into an electric furnace for annealing, wherein the heating temperature is 700 ℃, the heating time is 30 minutes, and the lead zirconate film is completely crystallized to form a perovskite phase. As shown in fig. 5 (a), the polarization and electric field hysteresis loop of the thin film has a typical antiferroelectric characteristic, and when the electric field strength is zero, the remanent polarization becomes significantly smaller, i.e. a double hysteresis loop occurs. The remanent polarization of the film is only 2.5 mu C/cm2. However, the maximum polarization intensity and the electric field breakdown intensity were 63.3. Mu.C/cm, respectively2(FIG. 6) and 659kV/cm (FIG. 7), significantly less than Al: pbZrO 23The lead zirconate nano composite film with the volume ratio of 0.5 percent, 1.0 percent and 1.5 percent has the maximum polarization strength and the electric field breakdown strength, so the energy storage density is only 14.9J/cm3And also significantly lower than the energy storage density of the lead zirconate nanocomposite film (figure 7).
Compared with the lead zirconate thin film material of the comparative example, the lead zirconate nanocomposite thin film has the microstructure characteristic that aluminum-rich nanoparticles are distributed on a lead zirconate matrix in a layered manner (see fig. 1 and fig. 2). PbZrO layered in perovskite phase3The aluminum-rich nano particles in the matrix can generate a local electric field to improve the maximum polarization strength on one hand, and can break PbZrO on the other hand3The antiferroelectric has long-range order, and the breakdown electric field intensity of the film is increased, and the antiferroelectric are both beneficial to improving the energy storage density of the film. In addition, the polarization characteristics of the lead zirconate nanocomposite film can be determined from Al: pbZrO 23The volume ratio is regulated. As shown in FIG. 5, the hysteresis loop of the composite film follows Al/PbZrO3The volume ratio is increased and gradually made of pure PbZrO3The antiferroelectric characteristics of the thin film evolved into Al: pbZrO 23The volume ratio of the lead zirconate nano composite film is 2.0 percent. The breakdown field strength of the composite film is also dependent on Al: pbZrO 23The volume ratio increases gradually (see fig. 7), and the maximum polarization intensity increases with Al: pbZrO 23The volume ratio increases and then decreases, as Al: pbZrO 23The volume ratio was 1.0%, and the peak was observed (see FIG. 6). Therefore, the energy storage density of the composite thin film is also in the range of Al: pbZrO 23The volume ratio was 1.0%, and a peak appeared (see FIG. 7). In contrast to pure lead zirconate films, al: pbZrO 23The breakdown electric field intensity of the lead zirconate nano composite film with the volume ratio of 1.0 percent is improved by about 182 percent, and the energy storage density is also improved by about 68 percent. The lead zirconate nano composite film material prepared by the invention is expected to be widely applied to the fields of pulse power devices and the like as a dielectric material of a dielectric energy storage capacitor.
The experiment shows that: FIG. 2 shows Al/PbZrO3The section picture of the transmission electron microscope of the composite film with the volume ratio of 1.0 percent shows that the aluminum-rich nano particles are distributed in the lead zirconate matrix in a layered manner; FIG. 3 shows Al: pbZrO 23The volume ratio of the ferroelectric hysteresis loop of the nano composite film is 1.0%, which shows that the composite film has antiferroelectricity. FIG. 4 shows Al/PbZrO3The change of the polarization strength of the nanocomposite film with a volume ratio of 1.0% with the annealing temperature shows that the polarization property increases first and then decreases with the increase of the annealing temperature, and the peak appears at 700 ℃. FIG. 5 shows different Al/PbZrO3The volume ratio of the electric hysteresis loop of the nano composite film; wherein FIG. 5 (a) is: 0Vol%; FIG. 5 (b) shows: 0.5Vol%; FIG. 5 (c) shows: 1.5Vol%; FIG. 5 (d) is: 2Vol%, shows that with Al/PbZrO3The volume ratio is increased, and the electric hysteresis loop of polarization and electric field gradually changes from pure PbZrO3The antiferroelectric characteristics of the thin film evolved into Al/PbZrO3The lead zirconate nano composite film with the volume ratio of 2 percent has the ferroelectric characteristic. FIG. 6 is a graph showing maximum polarization, remanent polarization, and difference between maximum polarization and remanent polarization of a composite film according to Al/PbZrO3The change of the volume ratio shows Al/PbZrO3The composite film with the volume ratio of 1.0% has the maximum polarization performance; FIG. 7 shows the breakdown strength of electric field and the energy storage density of the composite film with Al/PbZrO3The change in volume ratio indicates Al/PbZrO3The composite film with the volume ratio of 1.0% has the maximum energy storage density.
The prior art shows that the breakdown electric field intensity and the energy storage density of the dielectric thin film material can be effectively improved through the compounding of the nano material. For example, au-PbZrO prepared by chemical solution deposition3The energy storage density and the energy storage efficiency of the antiferroelectric nano composite film are respectively 10.8J/cm under the electric field intensity of 600kV/cm3And 60%, which is improved by 42% and 25% compared with PZO film. Uniformly distributed in perovskite phase PbZrO3Au nano-particles in the matrix can generate a local electric field to improve the maximum polarization strength on one hand and can lead PbZrO on the other hand3The antiferroelectric-ferroelectric phase change process has the characteristic of dispersion phase change, and the energy storage efficiency is improved. alpha-Fe prepared by chemical solution deposition method2O3-PbZrO3The antiferroelectric nano composite film is distributed in a perovskite phase PbZrO due to lamellar distribution3alpha-Fe in matrix2O3The local electric field effect around the nanoparticles increased the maximum polarization and energy storage density by 69.6% and 65.7% respectively compared to the PZO films.
Different from the nanometer material compounding technology, the Al metal layer is deposited by vacuum evaporation method, and then amorphous PbZrO is deposited on the Al metal layer by chemical solution deposition method3Film of amorphous PbZrO during annealing3Transformation into perovskite phase with diffusion of Al metal layer to PbZrO3The aluminum-rich nano particles distributed in a layered manner are formed in the matrix of the perovskite phase, so that the lead zirconate nano composite dielectric film material containing the aluminum-rich nano particles is prepared. The breakdown electric field intensity and the energy storage density of the dielectric film material can be effectively improved by the nano material compounding method. Al/PbZrO of example 13The breakdown electric field intensity and the energy storage density of the lead zirconate composite film with the volume ratio of 1.0 percent are respectively improved by about 18 percent compared with the lead zirconate film of the comparative example2% and 68%. The material has the advantages of simple preparation method, low cost, large-area uniform film formation and the like, and can be widely applied to the field of pulse power devices.
Claims (5)
1. A lead zirconate nano-composite dielectric film is characterized in that: the components of the film material meet the following requirements: al: pbZrO 23The volume ratio is 0.5-2.0%:99.5 to 98.0 percent; the microstructure of the film material is that aluminum-rich nano particles are distributed in a lead zirconate matrix in a layered manner.
2. A method for preparing the lead zirconate nanocomposite dielectric thin film according to claim 1, comprising the steps of:
(1) With acetic acid (CH)3COOH) as solvent, lead acetate (Pb (CH)3COO)2·3H2O) and zirconium n-propoxide (Zr (OCH)2CH2CH3)4) Preparing a lead zirconate precursor solution as a solute, weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1, adding the lead acetate and the zirconium n-propoxide into acetic acid according to the standard that the concentration of the lead zirconate is 0.3-0.5M, distilling at constant temperature of 120 ℃ for 90 minutes, and then cooling to room temperature; adding deionized water at a ratio of 175ml/L, and magnetically stirring until the solution is clear and transparent; then, lactic acid (CH) was added at a ratio of 42g/L3CH (OH) COOH) and 25g/L ethylene glycol (CH) were added2OH)2Stirring for 30 minutes; finally, adding acetic acid again to supplement the loss of the solvent in the distillation process, so that the concentration of the solution reaches 0.3-0.5M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45-micron filter, and aging for 20 hours;
(2) In Pt/Ti/SiO2Depositing a metal Al layer on the Si substrate by a vacuum thermal evaporation method; setting the working current and the working voltage of the evaporation equipment to 90-110A and 1.0V respectively, and controlling the evaporation rate of the metal Al layer to be
By regulating and controlling the evaporation time, a metal Al layer with the thickness of 2.5-10 nm on the substrate is obtained;
(3) The Al/Pt/Ti/SiO with the metal Al layer prepared in the step (2)2Putting the/Si substrate on a spin coating instrument, and dripping the lead zirconate precursor solution prepared in the step (1) on Al/Pt/Ti/SiO2Spin coating on a Si substrate at the rotating speed of 2500-3500 rpm for 30-50 seconds to obtain a raw material film of lead zirconate;
(4) Drying the raw material film prepared in the step (3) on a hot plate at the temperature of 110-150 ℃ for 10 minutes, then putting the raw material film into an electric furnace for thermal decomposition treatment, firstly heating the raw material film at the temperature of 300-400 ℃ for 10-15 minutes, and then heating the raw material film at the temperature of 550-600 ℃ for 10-15 minutes;
(5) Repeating the spin coating in the step (3) and the drying and thermal decomposition in the step (4) for 4 times to prepare a lead zirconate film with the thickness of 500 nm;
(6) Putting the lead zirconate film prepared in the step (5) into an electric furnace for annealing, wherein the heating temperature is 600-750 ℃, and the heating time is 20-40 minutes; in the annealing process, the lead zirconate film is completely crystallized to form a perovskite phase, and the metallic aluminum is diffused into the lead zirconate film to form a microstructure in which aluminum-rich nano particles are distributed on a lead zirconate substrate in a layered manner, so that the lead zirconate nano composite dielectric film is obtained.
3. The method for preparing a lead zirconate nanocomposite dielectric film according to claim 2, characterized in that: the evaporation rate of the metal Al in the step (2) is
The vapor deposition time is 125 to 500 seconds.
4. The method of preparing a lead zirconate nanocomposite dielectric thin film according to claim 2, wherein: and (4) the annealing heating temperature in the step (6) is 700 ℃, and the time is 30 minutes.
5. The method for preparing a lead zirconate nanocomposite dielectric film according to claim 2, characterized in that: the lead zirconate nano composite dielectric film obtained in the step (6) has the volume ratio of aluminum to lead zirconate of 1.0 percent and has anti-ironElectrical property; the maximum polarization and the residual polarization were 79.8. Mu.C/cm, respectively2、18.8μC/cm2The electric field breakdown strength and the energy storage density are 1858kV/cm and 25J/cm respectively3。
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