CN112466665B - Flexible solid dielectric film capacitor and preparation method thereof - Google Patents
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- 239000003990 capacitor Substances 0.000 title claims abstract description 54
- 239000007787 solid Substances 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 20
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000011888 foil Substances 0.000 claims abstract description 19
- 239000000758 substrate Substances 0.000 claims abstract description 19
- 239000002243 precursor Substances 0.000 claims abstract description 17
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000576 coating method Methods 0.000 claims abstract description 10
- 229910052751 metal Inorganic materials 0.000 claims abstract description 9
- 239000002184 metal Substances 0.000 claims abstract description 9
- 239000011248 coating agent Substances 0.000 claims abstract description 7
- 230000003647 oxidation Effects 0.000 claims abstract description 6
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 4
- 238000004806 packaging method and process Methods 0.000 claims abstract description 4
- 239000010408 film Substances 0.000 claims description 98
- 239000011575 calcium Substances 0.000 claims description 25
- 238000003756 stirring Methods 0.000 claims description 25
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000010409 thin film Substances 0.000 claims description 17
- 238000000137 annealing Methods 0.000 claims description 11
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 claims description 10
- XQKKWWCELHKGKB-UHFFFAOYSA-L calcium acetate monohydrate Chemical compound O.[Ca+2].CC([O-])=O.CC([O-])=O XQKKWWCELHKGKB-UHFFFAOYSA-L 0.000 claims description 10
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 10
- 229960000583 acetic acid Drugs 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 7
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical compound [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 6
- 238000000227 grinding Methods 0.000 claims description 5
- 238000001704 evaporation Methods 0.000 claims description 3
- 230000008020 evaporation Effects 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000001755 magnetron sputter deposition Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 15
- 238000001035 drying Methods 0.000 description 6
- 238000004146 energy storage Methods 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 5
- 229910052710 silicon Inorganic materials 0.000 description 5
- 239000010703 silicon Substances 0.000 description 5
- 238000007738 vacuum evaporation Methods 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- 239000001639 calcium acetate Substances 0.000 description 2
- 229960005147 calcium acetate Drugs 0.000 description 2
- 235000011092 calcium acetate Nutrition 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000004528 spin coating Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
- C01F7/00—Compounds of aluminium
- C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
- C01F7/021—After-treatment of oxides or hydroxides
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G13/00—Apparatus specially adapted for manufacturing capacitors; Processes specially adapted for manufacturing capacitors not provided for in groups H01G4/00 - H01G11/00
-
- 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
- H01G4/33—Thin- or thick-film capacitors
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- Engineering & Computer Science (AREA)
- Power Engineering (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Manufacturing & Machinery (AREA)
- Chemical & Material Sciences (AREA)
- Inorganic Chemistry (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Fixed Capacitors And Capacitor Manufacturing Machines (AREA)
- Semiconductor Integrated Circuits (AREA)
- Ceramic Capacitors (AREA)
Abstract
The invention relates to the technical field of capacitors, in particular to a flexible solid dielectric film capacitor which comprises an upper electrode, an oxide dielectric film and an inorganic flexible substrate which are sequentially arranged from top to bottom. The preparation method comprises the following preparation steps: (1) preparation of Al2CaxO3Sol precursor; (2) mixing Al2CaxO3Coating the sol precursor on aluminum foil or titanium foil to form Al2CaxO3A flexible film; (3) in the presence of Al2CaxO3Preparing a metal film with anodic oxidation capacity on the flexible film to be used as an upper electrode to obtain a capacitor unit; (4) and packaging and curing the capacitor unit, and then leading wires at two ends to obtain the flexible solid dielectric film capacitor. The capacitor has the characteristics of high withstand voltage, low leakage conductance and stability; the breakdown field strength can reach 500MV/m, and the leakage current density before breakdown is lower than 1 x 10‑3 A/cm3. The invention has simple preparation process, compact and uniform film and excellent electrical property.
Description
Technical Field
The invention relates to the technical field of capacitors, in particular to a flexible solid dielectric film capacitor and a preparation method thereof.
Background
In the world today, technology is rapidly developing. In particular, in recent years, smaller, faster, and bendable flexible electronic devices have become more and more popular. The capacitor is used as an essential component of electronic equipment, which requires the characteristics of small volume and flexibility. In addition, high stability and high energy storage are important as a key index for measuring the working stability and performance of the electronic device. Most of the flexible capacitors currently under study are made of organic materials. Although this class of materials meets the requirement of the capacitor to be flexible, the stability of this class of materials in harsh environments is poor, thereby limiting its further applications.
The oxide dielectric material is used as an inorganic substance and has high stability. The device can realize the characteristics of high energy storage, flexibility and low leakage conductance while keeping high stability, and has excellent development prospect. In the case of inorganic oxides, the storage density of a capacitor using the inorganic oxide as a dielectric is proportional to the square of the breakdown field strength. Therefore, in order to obtain a capacitor with a high energy storage density, a dielectric material having a high breakdown voltage is inevitably selected by increasing the breakdown field strength of the dielectric thin film. In addition, in order to reduce the energy loss of the flexible dielectric film capacitor in the using process, the leakage conductance of the dielectric film should be reduced as much as possible on the basis of improving the energy storage density.
Disclosure of Invention
The invention aims to solve the technical defects and provide a flexible solid dielectric film capacitor and a preparation method thereof, wherein the flexible solid dielectric film capacitor has the characteristics of inorganic property, high energy storage density and high voltage resistance.
In order to achieve the purpose, the invention designs a flexible solid dielectric film capacitor which comprises an upper electrode, an oxide dielectric film and an inorganic flexible substrate which are sequentially arranged from top to bottom.
The oxide dielectric film is: al (Al)2CaxO3Wherein x is mole fraction percentage, x =0.5-10, and the thickness of the oxide dielectric film is 200-300 nm. The film is used as an inorganic film and has excellent stability under strict conditions. In addition, the structural stability of the film can be enhanced due to the doping of Ca macroions, so that the breakdown field intensity of the film is enhanced, and the leakage conductance of the film is reduced. The breakdown field is strong by 500MV/m, and the leakage current density is lower than 1 x 10-3 A/cm3。
The inorganic flexible substrate is an aluminum foil or a titanium foil, and the thickness of the inorganic flexible substrate is 0.1-0.2 mm.
The upper electrode is a valve metal film with anodic oxidation capability, and the thickness of the valve metal film is 150-250 nm.
Preferably, the upper electrode is one of an Al thin film, a Ti thin film, a Zr thin film, a Cu thin film, and a Ni thin film.
An upper electrode is deposited on the oxide dielectric film.
A preparation method of a flexible solid dielectric film capacitor comprises the following preparation steps:
(1) preparation of Al2CaxO3Sol precursor:
(1-1) grinding 0.01-0.02 mol of aluminum nitrate into powder, then adding the powder into 20-50 ml of glacial acetic acid for ultrasonic dispersion for 10-30 min, and stirring the powder for 0.5-1 h at the temperature of 70-80 ℃;
(1-2) adding 4-10 mL of acetic acid into the solution obtained in the step (1-1), and stirring at the temperature of 60-80 ℃ for 0.5-1 h to obtain a light yellow transparent solution;
(1-3) adding 0.03-0.06 mol of acetylacetone into the light yellow transparent solution obtained in the step (1-2), and stirring at room temperature for 0.5-1 h to obtain a solution;
(1-4) adding 0-0.01 mol of calcium acetate hydrate into the solution obtained in the step (1-3), and stirring at the temperature of 60-80 ℃ for 0.5-1 h to obtain a solution; wherein when the added amount of calcium acetate hydrate is 0, this step is deleted.
(1-5) adding 5-6 g of PVA with the mass fraction of 6% into the solution obtained in the step (1-4), and stirring at the temperature of 60-80 ℃ for 4-6 h to obtain Al2CaxO3Sol precursor;
(2) mixing Al2CaxO3Coating the sol precursor on an aluminum foil or a titanium foil, and performing heat treatment to obtain 1 layer of the oxide film; repeating the above steps for 5-9 times with the former layer as substrate, and annealing at 450 deg.C for 3 hr to obtain Al formed on aluminum foil or titanium foil2CaxO3A flexible film;
(3) by adopting an evaporation coating method or a magnetron sputtering method on Al2CaxO3Preparing a metal film with anodic oxidation capacity on the flexible film to be used as an upper electrode to obtain a capacitor unit;
(4) and packaging and curing the prepared capacitor units or the capacitor units in combination through an insulating medium, and then leading wires at two ends to obtain the flexible solid dielectric film capacitor.
The addition amount of the calcium acetate hydrate in the step (1-4) is 0.5-10, which is mole percentage.
The heat treatment equipment in the step (2) is a tubular furnace, the heat treatment condition is a nitrogen condition, and the heat treatment system comprises treatment at 150 ℃ for 2-10 min, treatment at 350 ℃ for 2-10 min and treatment at 450 ℃ for 2-10 min in sequence.
The required annealing equipment in the step (2) is a tubular furnace, and the annealing system is that the temperature is raised to 450-550 ℃ at the temperature raising rate of 3 ℃/min under the condition of nitrogen, and the temperature is kept for 3-4 h at the temperature of 450-550 ℃.
Al prepared in step (2)2CaxO3The thickness of the film is 200-300 nm.
According to the flexible solid dielectric film capacitor and the preparation method thereof, aluminum oxide with low cost is selected as a main matrix, and calcium is added to the main matrix to obtain Al2CaxO3A film. The film has improved structural stability due to the doping of Ca ions, thereby improving the breakdown field strength and reducing the leakage conductance. Unlike the organic flexible solid-state capacitors currently under considerable research. The invention selects the dielectric film as the inorganic film, the substrate as the aluminum foil or titanium foil inorganic flexible substrate, and the upper electrode as the metal film, thereby realizing the preparation of the all-inorganic flexible device.
Compared with the prior art, the invention has the advantages that:
the oxide dielectric film (1) prepared by the invention is an all-inorganic flexible film, and has better weather resistance and stability; (2) is an alumina-based dielectric film with low cost; (3) has excellent dielectric properties such as high withstand voltage and low leakage conductance.
The flexible solid dielectric film capacitor prepared by the invention has high energy storage density, high voltage resistance and very high use limit.
The flexible solid dielectric film capacitor prepared by the invention has the advantages of simple preparation process, short time period and easy mass production.
Drawings
FIG. 1 is a schematic structural diagram of a capacitor according to the present invention;
FIG. 2 is Al2CaxO3A surface topography map of the film;
FIG. 3 is a box-type distribution diagram of the J-E characteristic curve and the breakdown field strength of the flexible capacitor with different Ca ion doping amounts.
Detailed Description
The invention is further described by way of example with reference to the accompanying drawings.
Example 1:
as shown in fig. 1, the flexible solid dielectric thin film capacitor includes an upper electrode 1, an oxide dielectric layer 2, and a flexible substrate 3. In fig. 1, the upper electrode 1 is an aluminum film (200 nm), the flexible substrate 3 is an aluminum foil, and the thickness is 0.1 mm; the oxide dielectric film 2 is Al2Ca0.005O3And the thickness is 300 nm.
The preparation method of the flexible solid dielectric film capacitor described in this embodiment includes the following steps:
grinding 0.02 mol of aluminum nitrate into powder, adding the powder into 20 ml of ethylene glycol ethyl ether, performing ultrasonic treatment for 10 min, and stirring the mixture for 30 min at 70 ℃; adding 4 mL of acetic acid, and stirring for 30 minutes at 60 ℃; adding 0.04 mol of acetylacetone, and stirring for 30 minutes at room temperature; adding 0.005 mol of calcium acetate, and continuing stirring for 30 minutes at 80 ℃; and finally, adding 5.3g of PVA with the mass fraction of 6%, stirring for 4 hours at 80 ℃, gradually cooling to room temperature, and finally filtering to obtain 60 ml of sol precursor. The method comprises the steps of flatly placing an aluminum foil with a clean and dry surface on a silicon wafer, placing the silicon wafer on a spin coater, dripping a sol precursor on the surface of the substrate, uniformly coating the sol on the surface of the aluminum foil at a rotating speed of 3000 r/min, placing a sample in a tubular furnace for drying heat treatment, wherein the process conditions of pre-drying treatment comprise 150 ℃ treatment for 2 minutes under a nitrogen condition, 350 ℃ treatment for 2 minutes, 450 ℃ treatment for 2 minutes, swinging to 7 layers, placing the prepared amorphous oxide film with the required thickness in the tubular furnace for heat treatment for 3 hours, the heating rate of the prepared amorphous oxide film with the required thickness is 3 ℃/min under the nitrogen condition of a required annealing system, and keeping the temperature for 4 hours at 450 ℃.
An aluminum film with the diameter of 1 millimeter and the thickness of 120 nanometers is prepared on the surface of an oxide film sample by adopting vacuum evaporation equipment and is used as an electrode, and the breakdown field strength and the leakage conductance of the aluminum oxide-based film are researched.
FIG. 2 is a surface topography of an oxide film, showing that the prepared film is uniform and dense.
FIG. 3 is a box-type distribution diagram of the J-E characteristic curve and breakdown field strength of the flexible capacitor, which shows that the prepared film has high voltage resistance and low leakage conductance.
Example 2:
in this embodiment, the oxide dielectric thin film is made of soft Al with a thickness of 300nm2Ca0.02O3A film.
And preparing a 300nm flexible oxide dielectric film on the surface of the aluminum foil by adopting a spin coating method. The preparation process specifically comprises the following steps:
1) the preparation of the sol precursor was the same as in example 1;
2) preparing a flexible oxide film:
the preparation steps of the film are as follows:
the method comprises the steps of flatly placing an aluminum foil with a clean and dry surface on a silicon wafer, placing the aluminum foil on a spin coater, dripping a sol precursor on the surface of the substrate, uniformly coating the sol on the surface of the substrate at a rotating speed of 3000 r/min, placing a sample in a tubular furnace for drying heat treatment, wherein the process conditions of pre-drying treatment comprise 150 ℃ treatment for 2 minutes under a nitrogen condition, 350 ℃ treatment for 2 minutes, 450 ℃ treatment for 2 minutes, throwing to 10 layers, placing the prepared amorphous oxide film with the required thickness in the tubular furnace for heat treatment for 3 hours, wherein the heating rate of the prepared amorphous oxide film with the required thickness is 3 ℃/min under the nitrogen condition of a required annealing system, and keeping the temperature for 3 hours at 550 ℃.
The procedure for forming an upper electrode aluminum film was the same as in example 1.
Example 3:
flexible solid dielectric capacitors are fabricated on titanium foil.
The steps of fabricating the oxide dielectric film are as follows:
preparing 210 nm flexible Al on the surface of a titanium foil by adopting a spin coating method2Ca0.005O3A dielectric thin film. The preparation process specifically comprises the following steps:
grinding 0.02 mol of aluminum nitrate, adding the ground aluminum nitrate into 20 ml of ethylene glycol ethyl ether, performing ultrasonic treatment for 10 min, and stirring the mixture for 30 min at 70 ℃; adding 4 mL of acetic acid, and stirring for 30 minutes at 60 ℃; adding 0.04 mol of acetylacetone, and stirring for 30 minutes at room temperature; adding 0.005 mol of calcium acetate, and continuing stirring for 30 minutes at 80 ℃; and finally, adding 5.3g of PVA with the mass fraction of 6%, stirring for 4 hours at 80 ℃, gradually cooling to room temperature, and finally filtering to obtain 60 ml of sol precursor. The method comprises the steps of flatly placing a titanium foil with a clean and dry surface on a silicon wafer, placing the silicon wafer on a spin coater, dripping a sol precursor on the surface of the substrate, uniformly coating the sol on the surface of the substrate at a rotating speed of 3000 r/min, placing a sample in a tubular furnace for drying heat treatment, wherein the process conditions of pre-drying treatment comprise 150 ℃ treatment for 2 minutes under a nitrogen condition, 350 ℃ treatment for 2 minutes, 450 ℃ treatment for 2 minutes, throwing to 7 layers, placing the prepared amorphous oxide film with the required thickness in the tubular furnace for heat treatment for 3 hours, the heating rate of the prepared amorphous oxide film with the required thickness is 3 ℃/min under the nitrogen condition of a required annealing system of annealing equipment, and keeping the temperature for 3 hours at 450 ℃.
An aluminum film with the diameter of 1 millimeter and the thickness of 120 nanometers is prepared on the surface of an oxide dielectric film sample by adopting vacuum evaporation equipment and is used as an upper electrode, and the breakdown field strength and the leakage conductance of the aluminum oxide-based film are researched.
Example 4:
a flexible solid dielectric capacitor whose upper electrode is a Cu film is prepared.
The procedure for forming an oxide dielectric thin film was the same as in example 1.
A Cu film with the diameter of 1 millimeter and the thickness of 120 nanometers is prepared on the surface of an oxide dielectric film sample by adopting vacuum evaporation equipment and is used as an upper electrode, and the breakdown field strength and the leakage conductance of the alumina-based film are researched.
Example 5:
a flexible solid dielectric capacitor whose upper electrode is a Ti film was prepared.
The procedure for forming an oxide dielectric thin film was the same as in example 1.
A Ti film with the diameter of 1 mm and the thickness of 120 nanometers is prepared on the surface of an oxide dielectric film sample by adopting vacuum evaporation equipment and is used as an upper electrode, and the breakdown field strength and the leakage conductance of the alumina-based film are researched.
Example 6:
a flexible solid dielectric capacitor whose upper electrode is a Ni film is prepared.
The procedure for forming an oxide dielectric thin film was the same as in example 1.
A Ni film with the diameter of 1 millimeter and the thickness of 120 nanometers is prepared on the surface of an oxide dielectric film sample by adopting vacuum evaporation equipment and is used as an upper electrode, and the breakdown field strength and the leakage conductance of the alumina-based film are researched.
Claims (9)
1. A preparation method of a flexible solid dielectric film capacitor is characterized by comprising the following steps: the preparation method comprises the following steps:
(1) preparation of Al2CaxO3Sol precursor:
(1-1) grinding 0.01-0.02 mol of aluminum nitrate into powder, then adding the powder into 20-50 mL of glacial acetic acid for ultrasonic dispersion for 10-30 min, and stirring for 0.5-1 h at the temperature of 70-80 ℃;
(1-2) adding 4-10 mL of acetic acid into the solution obtained in the step (1-1), and stirring at the temperature of 60-80 ℃ for 0.5-1 h to obtain a light yellow transparent solution;
(1-3) adding 0.03-0.06 mol of acetylacetone into the light yellow transparent solution obtained in the step (1-2), and stirring at room temperature for 0.5-1 h to obtain a solution;
(1-4) adding 0-0.01 mol of calcium acetate hydrate into the solution obtained in the step (1-3), and stirring at the temperature of 60-80 ℃ for 0.5-1 h to obtain a solution, wherein the added calcium acetate hydrate is not equal to 0;
(1-5) adding 5-6 g of PVA with the mass fraction of 6% into the solution obtained in the step (1-4), and stirring at the temperature of 60-80 ℃ for 4-6 h to obtain Al2CaxO3Sol precursor;
(2) mixing Al2CaxO3Coating the sol precursor on an aluminum foil or a titanium foil, and performing heat treatment to obtain 1 layer of the oxide film; repeating the above steps for 5-9 times with the former layer as substrate, and annealing at 450 deg.C for 3 hr to obtain Al formed on the aluminum foil or titanium foil2CaxO3A flexible film;
(3) by adopting an evaporation coating method or a magnetron sputtering method on Al2CaxO3Preparing a layer of metal film with anodic oxidation capacity on the flexible film to serve as an upper electrode, and obtaining a capacitor unit;
(4) and packaging and curing the prepared capacitor units or the capacitor units in combination through an insulating medium, and then leading wires at two ends to obtain the flexible solid dielectric film capacitor.
2. The method of claim 1, wherein the flexible solid dielectric film capacitor is prepared by: the addition amount of the calcium acetate hydrate in the step (1-4) is 0.5-10, which is mole percentage.
3. The method of claim 1, wherein the flexible solid dielectric film capacitor is prepared by: the heat treatment equipment in the step (2) is a tubular furnace, the heat treatment condition is a nitrogen condition, and the heat treatment system comprises treatment at 150 ℃ for 2-10 min, treatment at 350 ℃ for 2-10 min and treatment at 450 ℃ for 2-10 min in sequence.
4. The method of claim 1, wherein the flexible solid dielectric film capacitor is prepared by: the required annealing equipment in the step (2) is a tubular furnace, and the annealing system is that the temperature is raised to 450-550 ℃ at the temperature raising rate of 3 ℃/min under the condition of nitrogen, and the temperature is kept for 3-4 h at the temperature of 450-550 ℃.
5. A flexible solid dielectric film capacitor, characterized by: the device comprises an upper electrode, an oxide dielectric film and an inorganic flexible substrate which are sequentially arranged from top to bottom; the oxide dielectric film is: al (Al)2CaxO3The thickness of the oxide dielectric film is 200-300 nm; the preparation method comprises the following steps:
(1) preparation of Al2CaxO3Sol precursor:
(1-1) grinding 0.01-0.02 mol of aluminum nitrate into powder, then adding the powder into 20-50 ml of glacial acetic acid for ultrasonic dispersion for 10-30 min, and stirring the powder for 0.5-1 h at the temperature of 70-80 ℃;
(1-2) adding 4-10 mL of acetic acid into the solution obtained in the step (1-1), and stirring at the temperature of 60-80 ℃ for 0.5-1 h to obtain a light yellow transparent solution;
(1-3) adding 0.03-0.06 mol of acetylacetone into the light yellow transparent solution obtained in the step (1-2), and stirring at room temperature for 0.5-1 h to obtain a solution;
(1-4) adding 0-0.01 mol of calcium acetate hydrate into the solution obtained in the step (1-3), and stirring at the temperature of 60-80 ℃ for 0.5-1 h to obtain a solution, wherein the added calcium acetate hydrate is not equal to 0;
(1-5) adding 5-6 g of PVA with the mass fraction of 6% into the solution obtained in the step (1-4), and stirring at the temperature of 60-80 ℃ for 4-6 h to obtain Al2CaxO3Sol precursor;
(2) mixing Al2CaxO3Coating the sol precursor on an aluminum foil or a titanium foil, and performing heat treatment to obtain 1 layer of the oxide film; repeating the above steps for 5-9 times with the former layer as substrate, and annealing at 450 deg.C for 3 hr to obtain Al formed on aluminum foil or titanium foil2CaxO3A flexible film;
(3) by adopting an evaporation coating method or a magnetron sputtering method on Al2CaxO3Preparing a metal film with anodic oxidation capacity on the flexible film to be used as an upper electrode to obtain a capacitor unit;
(4) and packaging and curing the prepared capacitor units or the capacitor units in combination through an insulating medium, and then leading wires at two ends to obtain the flexible solid dielectric film capacitor.
6. A flexible solid state dielectric film capacitor as claimed in claim 5, wherein: the inorganic flexible substrate is an aluminum foil or a titanium foil, and the thickness of the inorganic flexible substrate is 0.1-0.2 mm.
7. A flexible solid state dielectric film capacitor as claimed in claim 5, wherein: the upper electrode is a valve metal film with anodic oxidation capability, and the thickness of the valve metal film is 150-250 nm.
8. A flexible solid state dielectric film capacitor as claimed in claim 7, wherein: the upper electrode is one of an Al thin film, a Ti thin film, a Zr thin film, a Cu thin film and a Ni thin film.
9. A flexible solid dielectric film capacitor as claimed in any one of claims 5 to 8, wherein: an upper electrode is deposited on the oxide dielectric film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011303291.3A CN112466665B (en) | 2020-11-19 | 2020-11-19 | Flexible solid dielectric film capacitor and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202011303291.3A CN112466665B (en) | 2020-11-19 | 2020-11-19 | Flexible solid dielectric film capacitor and preparation method thereof |
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| Publication Number | Publication Date |
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