CN115274298B - 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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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 230000005684 electric field Effects 0.000 claims abstract description 32
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 29
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000004146 energy storage Methods 0.000 claims abstract description 26
- 230000015556 catabolic process Effects 0.000 claims abstract description 23
- 239000000956 alloy Substances 0.000 claims abstract description 20
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 20
- 239000002105 nanoparticle Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000011159 matrix material Substances 0.000 claims abstract description 12
- 230000008569 process Effects 0.000 claims abstract description 5
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 63
- 230000010287 polarization Effects 0.000 claims description 48
- 229910052751 metal Inorganic materials 0.000 claims description 34
- 239000002184 metal Substances 0.000 claims description 34
- 239000000758 substrate Substances 0.000 claims description 31
- 238000010438 heat treatment Methods 0.000 claims description 26
- 239000002994 raw material Substances 0.000 claims description 26
- 238000000137 annealing Methods 0.000 claims description 24
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 238000001704 evaporation Methods 0.000 claims description 21
- 230000008020 evaporation Effects 0.000 claims description 21
- 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 21
- 229940046892 lead acetate Drugs 0.000 claims description 20
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 16
- 238000005979 thermal decomposition reaction Methods 0.000 claims description 16
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 15
- 125000000896 monocarboxylic acid group Chemical group 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- 239000002904 solvent Substances 0.000 claims description 13
- 238000004528 spin coating Methods 0.000 claims description 13
- 230000032683 aging Effects 0.000 claims description 7
- 238000001816 cooling Methods 0.000 claims description 7
- 238000004821 distillation Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 239000013589 supplement Substances 0.000 claims description 7
- 238000005303 weighing Methods 0.000 claims description 7
- 239000004310 lactic acid Substances 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- 238000002207 thermal evaporation Methods 0.000 claims description 6
- 230000001276 controlling effect Effects 0.000 claims description 5
- 238000000151 deposition Methods 0.000 claims description 4
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 2
- 238000007740 vapor deposition Methods 0.000 claims 1
- 238000000224 chemical solution deposition Methods 0.000 abstract description 4
- 238000007738 vacuum evaporation Methods 0.000 abstract description 3
- 239000012776 electronic material Substances 0.000 abstract description 2
- 239000008204 material by function Substances 0.000 abstract description 2
- 239000004411 aluminium Substances 0.000 abstract 1
- 239000010408 film Substances 0.000 description 126
- 239000002131 composite material Substances 0.000 description 22
- 230000008859 change Effects 0.000 description 8
- 238000003860 storage Methods 0.000 description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000003989 dielectric material Substances 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 239000010409 thin film Substances 0.000 description 3
- 230000007704 transition Effects 0.000 description 3
- 229910052726 zirconium Inorganic materials 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000013329 compounding Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- LLZRNZOLAXHGLL-UHFFFAOYSA-J titanic acid Chemical compound O[Ti](O)(O)O LLZRNZOLAXHGLL-UHFFFAOYSA-J 0.000 description 2
- 229910000859 α-Fe Inorganic materials 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIPNSKYNPDTRPC-UHFFFAOYSA-N N-[2-oxo-2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)ethyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 NIPNSKYNPDTRPC-UHFFFAOYSA-N 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000006386 neutralization reaction Methods 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
Classifications
-
- 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
-
- 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
-
- 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
-
- 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
-
- 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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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Wood Science & Technology (AREA)
- Inorganic Insulating Materials (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
A lead zirconate nano-composite dielectric film and a preparation method thereof belong to the technical fields of electronic materials, functional materials and intelligent materials, and Al of the materials is as follows: pbZrO (PbZrO-based alloy) 3 The volume ratio is 0.5-2.0%:99.5-98.0%, and the aluminium-rich nano particles are distributed on the lead zirconate matrix in a layered manner, and the breakdown electric field strength and the energy storage density are respectively improved by about 182% and 68% compared with the lead zirconate film. The material is prepared by vacuum evaporation and chemical solution deposition, has the advantages of simple process, low cost, capability of uniformly forming films in a large area and the like, and can be widely applied to the field of pulse power devices.
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 nanocomposite dielectric film and a preparation method thereof.
Background
With the proposal of the concept of carbon neutralization and carbon peak, the importance of new energy is increasingly highlighted. In addition to the development of new energy sources such as solar energy, wind energy and tidal power generation, energy storage technologies are increasingly receiving attention, and the key of the energy storage technologies is to develop energy storage materials meeting application requirements. DielectricThe container has the advantages of high dielectric constant, low dielectric loss, high power density, high charge/discharge speed, high working voltage/current, good reliability, good temperature stability and the like, and has been applied to the field of pulse power devices. With zirconium titanate (PbZrO) 3 ) The typical antiferroelectric dielectric materials have high energy storage densities due to their unique electric field induced antiferroelectric-ferroelectric phase transition properties, and are considered to be one of the most promising dielectric materials. In general, the energy storage density of the antiferroelectric material is determined by the parameters of remnant polarization, maximum polarization, antiferroelectric ‒ ferroelectric phase transition field strength, breakdown field strength, and the like. Although the maximum polarization intensity and the residual polarization intensity of the zirconium titanic acid have larger difference, the breakdown electric field intensity is lower, so that the energy storage density still cannot meet the requirements of practical application.
Disclosure of Invention
The invention aims to: the breakdown electric field strength of the zirconium titanic acid is low, and the energy storage density can not meet the application requirement; thus, a lead zirconate nano-composite dielectric film and a preparation method thereof are provided.
The technical scheme is as follows:
a lead zirconate nanocomposite dielectric film characterized by: the components of the film material meet the following requirements: al: pbZrO (PbZrO-based alloy) 3 The volume ratio is 0.5-2.0%:99.5-98.0%; the microstructure of the film material is that aluminum-rich nano particles are distributed in a layered manner in a lead zirconate matrix.
The preparation method of the lead zirconate nano-composite dielectric film is characterized by comprising the following steps:
(1) With acetic acid (CH) 3 COOH) as a solvent, lead acetate (Pb (CH) 3 COO) 2 •3H 2 O) and zirconium n-propoxide (Zr (OCH) 2 CH 2 CH 3 ) 4 ) Preparing a lead zirconate precursor solution for a solute, weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1:1, adding the lead acetate and the zirconium n-propoxide into acetic acid according to the standard that the concentration of lead zirconate is 0.3-0.5M, distilling at the constant temperature of 120 ℃ for 90 minutes, and then cooling to the room temperature; deionized water is added according to the proportion of 175ml/L, and the solution is magnetically stirred until the solution is clear and transparent; thenLactic acid (CH) was added at a ratio of 42g/L 3 Adding ethylene glycol (CH) in a ratio of CH (OH) COOH to 25g/L 2 OH) 2 Stirring 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 μm filter, aging for 20 hours, and using;
(2) In Pt/Ti/SiO 2 Depositing 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, controlling the evaporation rate of the metal Al layer to be 0.15-0.30A/s, and obtaining the metal Al layer with the thickness of 2.5-10 nm on the substrate by regulating the evaporation time;
(3) Al/Pt/Ti/SiO with metal Al layer prepared in step (2) 2 Placing the Si substrate on a spin coater, and dripping the lead zirconate precursor solution prepared in the step (1) to Al/Pt/Ti/SiO 2 Spin coating is carried out on the Si substrate, the rotating speed is 2500-3500 r/min, the time is 30-50 seconds, and a raw material film of lead zirconate is obtained;
(4) Drying the raw material film prepared in the step (3) on a hot plate at 110-150 ℃ for 10 minutes, then placing the raw material film into an electric furnace for thermal decomposition treatment, and firstly placing the raw material film in a furnace for 300-400 ℃ for thermal decomposition o C heating for 10-15 min, and then at 550-600 min o C, heating 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 DEG C o C, heating for 20-40 minutes; in the annealing process, the lead zirconate film is completely crystallized into a perovskite phase, and metal aluminum is diffused into the lead zirconate film to form a microstructure with aluminum-rich nano particles distributed on a lead zirconate substrate in a layered manner, so that the lead zirconate nanocomposite dielectric film is obtained.
Preferably, the evaporation rate of the metal Al in the step (2) is 0.2A/s, and 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 nanocomposite dielectric film obtained in the step (6) has an aluminum to lead zirconate volume ratio of 1.0% and an antiferroelectric property; maximum and remnant polarization of 79.8. Mu.C/cm, respectively 2 、18.8 μC/cm 2 The electric field breakdown strength and the energy storage density are 1858kV/cm and 25J/cm respectively 3 。
Compared with the prior art, the invention has the following advantages and effects:
the invention prepares the nano composite film by utilizing vacuum evaporation and chemical solution deposition, and can effectively improve the breakdown electric field strength and the energy storage density of the lead zirconate dielectric film material by embedding the layered aluminum-rich nano particles on the lead zirconate substrate. The breakdown electric field strength and the energy storage density of the material are respectively improved by 182 percent and 68 percent compared with the lead zirconate film. The material has the advantages of simple preparation method, low cost, capability of uniformly forming films on a large area and the like, and can be widely applied to the field of pulse power devices.
Drawings
FIG. 1 is a schematic diagram showing the microstructure change of a lead zirconate nanocomposite film according to the invention before and after annealing;
FIG. 2 is a transmission electron microscope photograph of a microstructure of a section of the lead zirconate nanocomposite film prepared by the invention;
fig. 3 is Al: pbZrO (PbZrO-based alloy) 3 A hysteresis loop of the lead zirconate nanocomposite film of 1 vol% after annealing at 600-750 ℃;
fig. 4 is Al: pbZrO (PbZrO-based alloy) 3 Polarization intensity of 1 vol% nanocomposite film with annealing temperature;
fig. 5 shows different Al: pbZrO (PbZrO-based alloy) 3 A hysteresis loop of the nanocomposite film in volume ratio; wherein fig. 5 (a) is: a hysteresis loop of the nanocomposite film of 0 vol% Al; fig. 5 (b) is: 0.5 A hysteresis loop of the Vol% Al nanocomposite film; fig. 5 (c) is: 1.5 A hysteresis loop of the Vol% Al nanocomposite film; fig. 5 (d) is: a hysteresis loop of the nanocomposite film of 2 vol% Al;
FIG. 6 shows the best mode of the lead zirconate nanocomposite film according to the inventionLarge polarization, remnant polarization, difference between maximum polarization and remnant polarization with Al: pbZrO (PbZrO-based alloy) 3 A change map of the volume ratio;
FIG. 7 shows the breakdown field strength and the energy storage density of the lead zirconate nanocomposite film prepared according to the invention as a function of Al: pbZrO (PbZrO-based alloy) 3 A change chart of the volume ratio.
Detailed Description
A lead zirconate nano-composite dielectric film comprises the following components in percentage by weight: pbZrO (PbZrO-based alloy) 3 The volume ratio is 0.5-2.0%:99.5-98.0%.
The film material structure is that aluminum-rich nano particles are distributed on a lead zirconate matrix in a layered manner.
The preparation method of the lead zirconate nano composite dielectric film comprises the following steps:
(1) With acetic acid (CH) 3 COOH) as a solvent, lead acetate (Pb (CH) 3 COO) 2 •3H 2 O) and zirconium n-propoxide (Zr (OCH) 2 CH 2 CH 3 ) 4 ) Preparing lead zirconate precursor solution for solute. Weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1:1, adding the lead acetate and the zirconium n-propoxide into acetic acid according to the standard of lead zirconate concentration of 0.4M, distilling at a constant temperature of 120 ℃ for 90 minutes, and then cooling to room temperature. Then, lactic acid (CH) was added at a ratio of 42g/L 3 Adding ethylene glycol (CH) in a ratio of CH (OH) COOH to 25g/L 2 OH) 2 The 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 0.4 to M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45 μm filter, aging for 20 hours, and using;
(2) In Pt/Ti/SiO 2 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 90-110A and 1.0V respectively, controlling the evaporation rate of the metal Al layer to be 0.2A/s, and obtaining the metal Al layer with the thickness of 2.5-10 nm by controlling the evaporation time to be 125-500 s;
(3) Al/Pt/Ti/SiO prepared in the step (2) 2 Placing Si substrate on spin coater, dropping the lead zirconate precursor solution prepared in step (1) to step%2) Prepared Al/Pt/Ti/SiO 2 Spin coating is carried out on the Si substrate, the rotating speed is 2500-3500 r/min, the time is 30-50 seconds, and a raw material film of lead zirconate is obtained;
(4) Drying the raw material film prepared in the step (3) on a hot plate at 110-150 ℃ for 10 minutes, then placing the raw material film into an electric furnace for thermal decomposition treatment, and firstly placing the raw material film in a furnace for 300-400 ℃ for thermal decomposition o C heating for 10-15 min, and then at 550-600 min o C, heating 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 into a perovskite phase, and aluminum diffuses into the lead zirconate layer to form aluminum-rich nanoparticles, thereby obtaining the lead zirconate nanocomposite dielectric film.
The invention is described in further detail below, with reference to the attached drawings and to specific examples, which are intended to illustrate, but not to limit the invention.
Example 1
Step (1):
with acetic acid (CH) 3 COOH) as a solvent, lead acetate (Pb (CH) 3 COO) 2 •3H 2 O) and zirconium n-propoxide (Zr (OCH) 2 CH 2 CH 3 ) 4 ) Preparing lead zirconate precursor solution for solute. Weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1:1, adding the lead acetate and the zirconium n-propoxide into acetic acid according to the standard of lead zirconate concentration of 0.4M, distilling at a constant temperature of 120 ℃ for 90 minutes, and then cooling to room temperature. Then, lactic acid (CH) was added at a ratio of 42g/L 3 Adding ethylene glycol (CH) in a ratio of CH (OH) COOH to 25g/L 2 OH) 2 The 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 0.4 to M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45 μm filter, aging for 20 hours, and using;
step (2):
using Pt/Ti/SiO 2 Si (100) substrate. In Pt/Ti/SiO 2 An Al metal layer is deposited on the Si substrate by vacuum thermal evaporation. The working current and the working voltage of the evaporation equipment are respectively set to be 106A and 1.0V, the evaporation rate of the metal Al is controlled to be 0.2A/s, the evaporation time is 250 seconds, and an Al metal layer with the thickness of 5 nm is obtained.
Step (3):
Al/Pt/Ti/SiO prepared in the step (2) 2 Placing the Si substrate on a spin coater, and dripping the lead zirconate precursor solution prepared in the step (1) to Al/Pt/Ti/SiO 2 Spin coating is carried out on the/Si substrate, the rotating speed is 3500 rpm, the time is 30 seconds, and the Al/Pt/Ti/SiO is obtained 2 Raw material film of lead zirconate on Si substrate.
Step (4):
drying the lead zirconate raw material film prepared in the step (3) on a hot plate at 120 ℃ for 10 minutes, and then carrying out thermal decomposition treatment, wherein the lead zirconate raw material film is firstly prepared in the step 300 o Heating in furnace C for 10 min, and adding 600 o Heating in an electric furnace for 10 minutes;
step (5):
the spin coating in the step (3) and the drying and thermal decomposition in the step (4) are repeated for 4 times, and the lead zirconate film with the thickness of 500nm is prepared.
Step (6):
PbZrO obtained in step (5) 3 /Al/Pt/Ti/SiO 2 Annealing the Si multilayer film in an electric furnace at 700 deg.f o C, heating for 30 minutes; in the annealing process, the lead zirconate film is completely crystallized into a perovskite phase, and metal aluminum is diffused into the lead zirconate film to form a microstructure in which aluminum-rich nano particles are discontinuously diffused and distributed on a lead zirconate substrate in a layered manner, so that the lead zirconate nanocomposite dielectric film is obtained.
As shown in FIG. 1, the lead zirconate nanocomposite film prepared in example 1 was completely crystallized into perovskite phase during annealing, and aluminum metal was diffused into the lead zirconate film to form aluminum-rich nanoparticles distributed in layers on the lead zirconate matrix. Figure 2 is a cross-sectional transmission electron micrograph of the composite film,shows the microstructure characteristics of the aluminum-rich nano particles distributed on the lead zirconate matrix in a layered manner. The thickness of the Al metal layer for preparing the composite film is 5 nm, pbZrO 3 The film thickness was 500 a nm a, so the composite film had Al: pbZrO (PbZrO-based alloy) 3 The volume ratio is 1%. As shown in FIG. 3, the polarization of the composite film and the electric hysteresis loop of the electric field have antiferroelectric characteristics, and when the electric field strength is zero, the residual polarization strength is obviously reduced, namely double electric hysteresis loops appear. The maximum polarization and the residual polarization of the composite film were 79.8. Mu.C/cm, respectively 2 、18.8 μC/cm 2 (see FIG. 4) electric field breakdown strength and storage density of 1858kV/cm and 25J/cm, respectively 3 (see FIG. 7).
Example 2
Step (1):
with acetic acid (CH) 3 COOH) as a solvent, lead acetate (Pb (CH) 3 COO) 2 •3H 2 O) and zirconium n-propoxide (Zr (OCH) 2 CH 2 CH 3 ) 4 ) Preparing lead zirconate precursor solution for solute. Weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1:1, adding the lead acetate and the zirconium n-propoxide into acetic acid according to the standard of lead zirconate concentration of 0.4M, distilling at a constant temperature of 120 ℃ for 90 minutes, and then cooling to room temperature. Then, lactic acid (CH) was added at a ratio of 42g/L 3 Adding ethylene glycol (CH) in a ratio of CH (OH) COOH to 25g/L 2 OH) 2 The 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 0.4 to M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45 μm filter, aging for 20 hours, and using;
step (2):
using Pt/Ti/SiO 2 Si (100) substrate. Pt/Ti/SiO by vacuum thermal evaporation 2 An Al metal layer is deposited on the Si substrate. The working current and the working voltage of the evaporation equipment are respectively set to be 106A and 1.0V, the evaporation rate of the metal Al is controlled to be 0.2A/s, the evaporation time is 250 seconds, and an Al metal layer with the thickness of 5 nm is obtained.
Step (3):
Al/Pt/Ti/S prepared in the step (2)iO 2 Placing the Si substrate on a spin coater, and dripping the lead zirconate precursor solution prepared in the step (1) to Al/Pt/Ti/SiO 2 Spin coating is carried out on the/Si substrate, the rotating speed is 3000 rpm, the time is 40 seconds, and the Al/Pt/Ti/SiO is obtained 2 Raw material film of lead zirconate on Si substrate.
Step (4):
drying the lead zirconate raw material film prepared in the step (3) on a hot plate at 120 ℃ for 10 minutes, then placing the lead zirconate raw material film into an electric furnace for thermal decomposition treatment, and firstly placing the lead zirconate raw material film in 300 o C for 10 minutes at 550 o C, heating for 10 minutes;
step (5):
the spin coating in the step (3) and the drying and thermal decomposition in the step (4) are repeated for 4 times, and the lead zirconate film with the thickness of 500nm is prepared.
Step (6):
and (3) putting the lead zirconate film prepared in the step (5) into an electric furnace for annealing, wherein the heating temperatures are 600 ℃, 650 ℃, 700 ℃ and 750 ℃ respectively, and the heating time is 30 minutes. The thickness of the Al metal layer for preparing the composite film is 5 nm, pbZrO 3 The film thickness was 500 a nm a, so the composite film had Al: pbZrO (PbZrO-based alloy) 3 The volume ratio is 1%.
In accordance with the above method, (a) (b) (C) (d) in fig. 3 are hysteresis loops of composite films with annealing temperatures of 600 ℃, 650 ℃, 700 ℃ and 750 ℃, respectively, indicating that these films all have antiferroelectric properties, but the maximum polarization intensity and the remnant polarization intensity are different. As shown in fig. 4, as the annealing temperature increases, the maximum polarization intensity and the remnant polarization intensity increase first and then decrease, and a peak occurs at 700 ℃. As shown in FIG. 1, the annealing temperature is low, pbZrO 3 The perovskite phase cannot be completely crystallized, and the polarization performance is poor; the annealing temperature is high, the aluminum-rich nano particles are enriched and grown, the distribution is uneven, and the polarization performance is also reduced. Thus, the annealing temperature for preparing the composite film can be optimized to 700 ℃.
Example 3
Step (1):
with acetic acid (CH) 3 COOH) is solubleLead acetate (Pb (CH) 3 COO) 2 •3H 2 O) and zirconium n-propoxide (Zr (OCH) 2 CH 2 CH 3 ) 4 ) Preparing lead zirconate precursor solution for solute. Weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1:1, adding the lead acetate and the zirconium n-propoxide into acetic acid according to the standard of lead zirconate concentration of 0.4M, distilling at a constant temperature of 120 ℃ for 90 minutes, and then cooling to room temperature. Then, lactic acid (CH) was added at a ratio of 42g/L 3 Adding ethylene glycol (CH) in a ratio of CH (OH) COOH to 25g/L 2 OH) 2 The 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 0.4 to M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45 μm filter, aging for 20 hours, and using;
step (2):
using Pt/Ti/SiO 2 Si (100) substrate. Pt/Ti/SiO by vacuum thermal evaporation 2 An Al metal layer is deposited on the Si substrate. The operating current and operating voltage of the evaporation equipment were set to 106A and 1.0V, respectively, the evaporation rate of metallic Al was controlled to 0.2 a/s, and the evaporation times were 125 seconds, 250 seconds, 375 seconds, and 500 seconds, respectively, to obtain Al metal layers having thicknesses of 2.5 nm, 5 nm, 7.5 nm, and 10nm, respectively.
Step (3):
Al/Pt/Ti/SiO with different thickness Al metal layers prepared in the step (2) 2 Placing the/Si substrate on a spin coater respectively, and dripping the lead zirconate precursor solution prepared in the step (1) to Al/Pt/Ti/SiO 2 And spin coating is carried out on the Si substrate, the rotating speed is 3000 rpm, and the time is 40 seconds, so that the lead zirconate raw material film of the Al metal layers with different thicknesses is obtained.
Step (4):
drying the lead zirconate raw material film prepared in the step (3) on a hot plate at 120 ℃ for 10 minutes, and then respectively drying the lead zirconate raw material film at 300 o C and 600 o Heating in an electric furnace for 10 min, and performing thermal decomposition treatment;
step (5):
the spin coating in the step (3) and the drying and thermal decomposition in the step (4) are repeated for 4 times, and the lead zirconate film with the thickness of 500nm is prepared.
Step (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 into a perovskite phase, and aluminum diffuses into the lead zirconate layer to form aluminum-rich nanoparticles, thereby obtaining the lead zirconate nanocomposite dielectric film. Al/PbZrO of lead zirconate nanocomposite films prepared with 2.5 nm thick Al metal layers 3 The volume ratio was 0.5 Vol%, and as shown in FIG. 5 (b), the polarization and the electric hysteresis loop of the electric field had typical antiferroelectric characteristics, and the maximum polarization and the remnant polarization were 69.3. Mu.C/cm, respectively 2 And 11.4. Mu.C/cm 2 (see FIG. 6), electric field breakdown strength and storage density were 1557 kV/cm and 16.0J/cm, respectively 3 (see FIG. 7). Al/PbZrO of lead zirconate nanocomposite films prepared with 5 nm thick Al metal layers 3 The volume ratio was 1.0 Vol%. As shown in FIG. 3 (C), the composite film had antiferroelectric properties with maximum and remnant polarization of 77.6. Mu.C/cm, respectively 2 、24.8 μC/cm 2 (see FIG. 6), electric field breakdown strength and storage density of 1980 kV/cm and 19.4J/cm, respectively 3 (see FIG. 7). Al/PbZrO of lead zirconate nanocomposite films prepared with 7.5. 7.5 nm thick Al metal layers 3 The volume ratio was 1.5 Vol%. As shown in FIG. 5 (C), the composite film still had antiferroelectric properties with maximum and remnant polarization of 77.6. Mu.C/cm, respectively 2 、24.8 μC/cm 2 (see FIG. 6), electric field breakdown strength and storage density of 1980 kV/cm and 19.4J/cm, respectively 3 (see FIG. 7). Al/PbZrO of lead zirconate nanocomposite dielectric film material prepared with 10nm thick Al metal layer 3 The volume ratio was 2.0 Vol%. As shown in fig. 5 (d), the hysteresis loop of the composite film has typical ferroelectric characteristics, and the remnant polarization is not significantly reduced when the electric field strength is zero. Its maximum polarization and remnant polarization were 53.4. Mu.C/cm, respectively 2 、36.7 μC/cm 2 (see FIG. 6) electric field breakdown strength and storage density of 2043 kV/cm and 7.8J/cm, respectively 3 (see FIG. 7).
Comparative example 1
Step (1):
with acetic acid (CH) 3 COOH) as a solvent, lead acetate (Pb (CH) 3 COO) 2 •3H 2 O) and zirconium n-propoxide (Zr (OCH) 2 CH 2 CH 3 ) 4 ) Preparing lead zirconate precursor solution for solute. Weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1:1, adding the lead acetate and the zirconium n-propoxide into acetic acid according to the standard of lead zirconate concentration of 0.4M, distilling at a constant temperature of 120 ℃ for 90 minutes, and then cooling to room temperature. Then, lactic acid (CH) was added at a ratio of 42g/L 3 Adding ethylene glycol (CH) in a ratio of CH (OH) COOH to 25g/L 2 OH) 2 The 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 0.4 to M, and obtaining a light yellow transparent solution; filtering the solution with a 0.45 μm filter, aging for 20 hours, and using;
step (2):
using Pt/Ti/SiO 2 Si (100) substrate. The lead zirconate precursor solution prepared in the step (1) is dripped on a substrate to be spin-coated, the rotating speed is 3000 r/min, and the time is 40 seconds, so that a raw material film of lead zirconate is obtained;
step (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 respectively drying the raw material film at 300 o C and 600 o Heating in a muffle furnace for 10 min, and performing thermal decomposition treatment;
step (4):
the spin coating and drying and thermal decomposition of the step (2) are repeated 4 times to obtain the lead zirconate film with the thickness of 500 and nm.
Step (5):
putting the lead zirconate film prepared in the step (4) into an electric furnace for annealing, wherein the heating temperature is 700 DEG C o And C, heating for 30 minutes, and completely crystallizing the lead zirconate film into a perovskite phase. As shown in fig. 5 (a), the polarization of the film has typical antiferroelectric characteristics with the hysteresis loop of the electric field, and when the electric field strength is zero, the remnant polarization strength becomes significantly smaller, i.e., a double hysteresis loop occurs. The film isThe remnant polarization was only 2.5. Mu.C/cm 2 . However, the maximum polarization and electric field breakdown strength were 63.3. Mu.C/cm, respectively 2 (fig. 6) and 659 kV/cm (fig. 7), significantly less than Al: pbZrO (PbZrO-based alloy) 3 The maximum polarization strength and the electric field breakdown strength of the lead zirconate nano composite film with the volume ratio of 0.5 percent, 1.0 percent and 1.5 percent are respectively that of the lead zirconate nano composite film, so the energy storage density is only 14.9J/cm 3 And also significantly lower than the storage density of the lead zirconate nanocomposite film (fig. 7).
In contrast to the lead zirconate film material of the comparative example, the lead zirconate nanocomposite film has a microstructure feature in which aluminum-rich nanoparticles are distributed in layers on a lead zirconate matrix (see fig. 1 and 2). PbZrO layered in perovskite phase 3 The aluminum-rich nano particles in the matrix can generate a local electric field to improve the maximum polarization intensity on one hand and break PbZrO on the other hand 3 The antiferroelectric has long-range order, and the breakdown electric field strength of the film is increased, and both are beneficial to improving the energy storage density of the film. In addition, the polarization characteristics of the lead zirconate nanocomposite film may be based on Al: pbZrO (PbZrO-based alloy) 3 The volume ratio is regulated and controlled. As shown in FIG. 5, the hysteresis loop of the composite film follows the Al/PbZrO 3 The volume ratio is increased gradually from pure PbZrO 3 The antiferroelectric character of the film evolves into Al: pbZrO (PbZrO-based alloy) 3 Ferroelectric characteristics of a lead zirconate nanocomposite film with a volume ratio of 2.0%. The breakdown field strength of the composite film also follows the Al: pbZrO (PbZrO-based alloy) 3 The volume ratio increases gradually (see fig. 7), while the maximum polarization intensity increases with Al: pbZrO (PbZrO-based alloy) 3 The volume ratio increases first and then decreases, at Al: pbZrO (PbZrO-based alloy) 3 The peak occurs at a volume ratio of 1.0% (see fig. 6). Therefore, the energy storage density of the composite film is also at Al: pbZrO (PbZrO-based alloy) 3 The peak occurs at a volume ratio of 1.0% (see fig. 7). In contrast to pure lead zirconate film, al: pbZrO (PbZrO-based alloy) 3 The breakdown electric field strength 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.
ExperimentThe following is indicated: FIG. 2 is Al/PbZrO 3 A transmission electron microscope section photograph of the composite film with the volume ratio of 1.0 percent shows that the aluminum-rich nano particles are distributed in a layered manner in a lead zirconate matrix; fig. 3 is Al: pbZrO (PbZrO-based alloy) 3 The ferroelectric hysteresis loop of the nanocomposite film with a volume ratio of 1.0% indicates that the nanocomposite film has antiferroelectric properties. FIG. 4 is Al/PbZrO 3 The change of the polarization intensity of the nano composite film with the volume ratio of 1.0 percent along with the annealing temperature shows that the polarization performance is increased firstly and then decreased along with the increase of the annealing temperature, and the polarization performance is improved at 700 oC A peak occurs. FIG. 5 shows a different Al/PbZrO 3 A hysteresis loop of the nanocomposite film in volume ratio; wherein fig. 5 (a) is: 0 Vol; fig. 5 (b) is: 0.5 Vol; fig. 5 (c) is: 1.5 Vol; fig. 5 (d) is: 2 Vol, showing the effect of Al/PbZrO 3 The volume ratio is increased, and the electric hysteresis loop of the polarization and the electric field is gradually changed from pure PbZrO 3 The antiferroelectric characteristics of the film evolve into Al/PbZrO 3 Ferroelectric characteristics of a 2% volume lead zirconate nanocomposite film. FIG. 6 shows the maximum polarization, the remnant polarization, and the difference between the maximum polarization and the remnant polarization of the composite film with Al/PbZrO 3 The volume ratio change diagram shows Al/PbZrO 3 The composite film with the volume ratio of 1.0 percent has the maximum polarization performance; FIG. 7 shows the electric field breakdown strength and the energy storage density of the composite film with Al/PbZrO 3 The volume ratio change diagram shows Al/PbZrO 3 The composite film with the volume ratio of 1.0% has the maximum energy storage density.
The prior art shows that the breakdown electric field strength and the energy storage density of the dielectric thin film material can be effectively improved through nano material compounding. For example, au ‒ PbZrO prepared by chemical solution deposition method 3 The 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 600 kV/cm 3 And 60% compared to the PZO film, 42% and 25% improvement. PbZrO homogeneously distributed in perovskite phase 3 Au nano particles in a matrix can generate a local electric field to improve the maximum polarization intensity and can lead PbZrO 3 The antiferroelectric ‒ ferroelectric phase change process has the characteristic of dispersion phase change, and improves the energy storage efficiency. Using chemical solutionsPrepared by depositionα-Fe 2 O 3 ‒PbZrO 3 The antiferroelectric nano composite film is distributed in perovskite phase PbZrO in a layered manner 3 In a matrixα-Fe 2 O 3 The local electric field influence around the nanoparticles increased their maximum polarization and storage density by 69.6% and 65.7% respectively compared to the PZO film.
Unlike the above-mentioned nanomaterial composite techniques, we deposit Al metal layer by vacuum evaporation and then deposit amorphous PbZrO thereon by chemical solution deposition 3 Thin films, pbZrO amorphous during annealing 3 Transition to perovskite phase with Al metal layer diffusing into PbZrO 3 The perovskite phase matrix forms layered aluminum-rich nano particles, so that the lead zirconate nanocomposite dielectric film material containing the aluminum-rich nano particles is prepared. The nano material compounding method can effectively improve the breakdown electric field strength and the energy storage density of the dielectric thin film material. Al/PbZrO of example 1 3 The breakdown electric field strength and the energy storage density of the lead zirconate composite film with the volume ratio of 1.0 percent are respectively improved by about 182 percent and 68 percent compared with those of the lead zirconate film of the comparative example. The material has the advantages of simple preparation method, low cost, capability of uniformly forming films on a large area and the like, and can be widely applied to the field of pulse power devices.
Claims (5)
1. A lead zirconate nanocomposite dielectric film characterized by: the components of the film material meet the following requirements: al: pbZrO (PbZrO-based alloy) 3 The volume ratio is 0.5-2.0%:99.5-98.0%; the microstructure of the film material is that aluminum-rich nano particles are distributed in a layered manner in a lead zirconate matrix.
2. A method for preparing the lead zirconate nanocomposite dielectric film according to claim 1, characterized by the steps of:
(1) With acetic acid (CH) 3 COOH) as a solvent, lead acetate (Pb (CH) 3 COO) 2 ·3H 2 O) and zirconium n-propoxide (Zr (OCH) 2 CH 2 CH 3 ) 4 ) Is a solutePreparing a lead zirconate precursor solution, weighing lead acetate and zirconium n-propoxide according to the atomic ratio of Pb to Zr of 1:1, adding the lead acetate and the zirconium n-propoxide into acetic acid according to the standard that the concentration of lead zirconate is 0.3-0.5M, distilling at the constant temperature of 120 ℃ for 90 minutes, and then cooling to room temperature; deionized water is added according to the proportion of 175ml/L, and the solution is magnetically stirred until the solution is clear and transparent; then, lactic acid (CH) was added at a ratio of 42g/L 3 Adding ethylene glycol (CH) in a ratio of CH (OH) COOH to 25g/L 2 OH) 2 Stirring 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 μm filter, aging for 20 hours, and using;
(2) In Pt/Ti/SiO 2 Depositing 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 beThe metal Al layer with the thickness of 2.5-10 nm on the substrate is obtained by regulating and controlling the evaporation time;
(3) Al/Pt/Ti/SiO with metal Al layer prepared in step (2) 2 Placing the Si substrate on a spin coater, and dripping the lead zirconate precursor solution prepared in the step (1) to Al/Pt/Ti/SiO 2 Spin coating is carried out on the Si substrate, the rotating speed is 2500-3500 r/min, the time is 30-50 seconds, and the raw material film of lead zirconate is obtained;
(4) Drying the raw material film prepared in the step (3) on a hot plate at 110-150 ℃ for 10 minutes, then placing the raw material film into an electric furnace for thermal decomposition treatment, heating the raw material film at 300-400 ℃ for 10-15 minutes, and heating the raw material film at 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 into a perovskite phase, and metal aluminum is diffused into the lead zirconate film to form a microstructure with aluminum-rich nano particles distributed on a lead zirconate substrate in a layered manner, so that the lead zirconate nanocomposite dielectric film is obtained.
3. The method for preparing the lead zirconate nanocomposite dielectric film according to claim 2, wherein: the evaporation rate of the metal Al layer in the step (2) isThe vapor deposition time is 125-500 s.
4. The method for preparing the lead zirconate nanocomposite dielectric film according to claim 2, wherein: and (3) the annealing heating temperature in the step (6) is 700 ℃ and the time is 30 minutes.
5. The method for preparing the lead zirconate nanocomposite dielectric film according to claim 2, wherein: 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 antiferroelectric property; maximum and remnant polarization of 79.8. Mu.C/cm, respectively 2 、18.8μC/cm 2 The electric field breakdown strength and the energy storage density are 1858kV/cm and 25J/cm respectively 3 。
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