CN113277845A - Method for preparing ultrathin dielectric ceramic film based on particle-free dielectric ceramic ink - Google Patents
Method for preparing ultrathin dielectric ceramic film based on particle-free dielectric ceramic ink Download PDFInfo
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Abstract
The invention discloses a method for preparing an ultrathin dielectric ceramic film based on particle-free dielectric ceramic ink. The particle-free ink comprises the following components in percentage by mass: 5-40% of titanium precursor component, 5-40% of barium precursor component, 10-70% of complexing agent, 0-10% of organic additive, 0-10% of ethyl cellulose and the balance of solvent. Firstly, fully dissolving a chelating agent or a complexing agent in a solvent according to the proportion, and then adding a barium precursor and a titanium precursor into the mixed solution until the barium precursor and the titanium precursor are completely dissolved to obtain the particle-free ink. The ceramic ink may include an additive component. The ceramic ink can be printed (e.g., gravure, roll-to-roll, inkjet) onto a variety of substrates and decomposed at low temperature to form ultra-thin barium titanate films having the advantages of high dielectric constant, low dielectric loss, and the like. The preparation method is simple, the curing temperature is low, the time is short, the stability is high, the green and pollution-free effects are achieved, and the preparation method is widely applied to electronic devices such as electronic ceramics, thermistor elements and capacitors.
Description
Technical Field
The invention belongs to the technical field of ceramic film preparation, and relates to a method for preparing an ultrathin dielectric ceramic film based on particle-free dielectric ceramic ink.
Background
The printing electronic technology is a precision additive manufacturing technology with the advantages of strong stability, high printing speed, wide substrate selection, environmental protection, flexibility, light weight, large-area manufacturing and the like, and is favored by the industry. The preparation and application of the functionalized ink are widely concerned as the core of the printed electronic technology. Barium titanate, which is the first perovskite ferroelectric to be discovered, is known as the pillar in the electronic ceramic industry, has high dielectric constant, low dielectric loss, and excellent ferroelectric, piezoelectric, voltage-withstanding and insulating properties, is one of the most widely used materials in electronic ceramics, and is widely used in the manufacture of ceramic sensitive elements, such as multilayer ceramic capacitors (MLCCs), piezoelectric ceramics, crystal ceramic capacitors, electro-optic display panels, memory materials, polymer-based composite materials, and coatings.
Functional inks for printed electronics can be generally classified into two types, a particle type and a particle-free type. Particulate inks have a number of inherent disadvantages in preparation and storage: the preparation of the particles is complex; agglomeration/deposition is easy to form in storage, so that the film is uneven in thickness, not tight enough in adhesion with the surface of the electronic element and not good in compatibility; the ink is not easy to store and poor in stability, the added dispersing agent can enable the decomposition temperature of the ink to be higher, the performance of a product is reduced, and in addition, the particle type ceramic ink can block a spray head in printing due to the problems of particle sedimentation, agglomeration and the like and enables the printed product to be deposited unevenly. The particle-free ink is generally a metal precursor solution, and because metal exists in the solution in an ion form, the ink has good stability and uniformity, high metal content, no need of a dispersing agent, can form a smooth and uniform film after sintering of the precursor, and has the characteristic of high resolution.
The barium titanate dielectric inks which are reported at present and are suitable for printing electronic ceramics are all nanoparticle type inks. However, the nano barium titanate particle-type ink is not only expensive, but also requires complicated additives and long-term ball milling to maintain the particle-type ink's inherent defects such as dispersibility. Meanwhile, most of reported barium titanate ceramic ink is pigment ink, and the ink consists of a large amount of dye and additives. The range of applications for products is limited to the packaging, labeling, magazine and textile printing industries. And there is no mention of the suitability of these inks in printed electronics.
Therefore, the development of the particle-free barium titanate dielectric ceramic ink suitable for printing electronic ceramics can greatly fill the blank of the dielectric ceramic ink at the present stage.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a method for preparing an ultrathin dielectric ceramic film based on particle-free dielectric ceramic ink, which aims to solve the blank and the defects of the existing particle-free dielectric ceramic ink suitable for the electronic ceramic printing technology. The specific technical scheme of the invention provides a barium titanate particle-free dielectric ceramic ink for printing electronics. The ink adopts titanium precursor, barium precursor component and amine to form stable complex, and is dissolved in organic solvent to form ink. Organic matters and the like are added for preparing the printing ink with different printing modes, and simultaneously, the microstructure of the sintered film is adjusted, and the quality of the printed pattern is improved. The ink has strong stability, can be stored for 6 months under room temperature natural light without generating precipitates, and has the advantages of simple and easy preparation method, low cost, environmental protection, no pollution and easy realization of industrialization.
The specific scheme is as follows: the method for preparing the ultrathin dielectric ceramic film based on the particle-free dielectric ceramic ink comprises the following steps:
step 1, preparing barium titanate dielectric ceramic ink;
the ink comprises the following components in percentage by mass: 5-40% of a titanium precursor component, 5-40% of a barium precursor component, 10-70% of a complexing agent, 0-10% of an organic additive, 0-10% of ethyl cellulose and the balance of a solvent; wherein the complexing agent is an amine compound;
firstly, fully dissolving ethyl cellulose in a solvent according to a proportion, and magnetically stirring until the solution is clear; secondly, adding a titanium precursor and a barium precursor into the clarified solution, and then adding a complexing agent according to a proportion until the complexing agent is completely dissolved to form basic barium titanate ink;
then adding the organic additive into the basic barium titanate ink according to the proportion, and stirring for 0.5-30h at 0-25 ℃ until no particles are dissolved to obtain barium titanate dielectric ceramic ink;
step 2, preparing the particle-free barium titanate dielectric ceramic ink;
filtering the barium titanate dielectric ceramic ink prepared in the step 1 by a microporous filter membrane of 0.22-10 microns to obtain particle-free barium titanate dielectric ceramic ink for printing;
step 3, preparing a dielectric ceramic film;
coating or printing the particle-free barium titanate dielectric ceramic ink prepared in the step 2 on a substrate to form a pattern layer or a pattern; drying and decomposing the film to form a dielectric ceramic film on the substrate.
Further, the complexing agent is one or a mixture of more than two of aliphatic amine, alcohol amine, amide and aromatic amine. The amount of the complexing agent is 10-35%, when the content of the complexing agent is higher than 35%, the barium titanate film is uneven and compact, and when the content of the complexing agent is lower than 10%, stable ink cannot be formed.
Further, the complexing agent may be one or more of ethylamine, ethylenediamine, isopropylamine, cyclohexylamine, formamide, diethylamine, triethylamine, n-butylamine, n-octylamine, ethanolamine, diethanolamine, triethanolamine, 2- (ethylamino) ethanol, 2- (dimethylamino) ethanol, 2- (diethylamino) ethanol, 1-amino-2-propanol (isopropanolamine), ethyldiethanolamine, and butyldiethanolamine.
Further, the titanium precursor is one or a mixture of more than two of titanium oxide, titanium chloride, titanium bromide, titanium sulfate, titanium phosphate, titanium nitrate, titanium carboxylate or titanium titanate; the amount of the titanium precursor is 5-40%, when the content of the titanium precursor is higher than 40%, the barium titanate film can generate a heterogeneous phase, and when the content of the titanium precursor is lower than 5%, the stable ink cannot be formed. The carboxylate in the titanium carboxylate is one or a mixture of more than two of aliphatic carboxylate, aromatic carboxylate, hydroxyl carboxylate or alicyclic carboxylate; wherein the aliphatic carboxylic acid titanium, the aromatic carboxylic acid titanium, the hydroxy carboxylic acid titanium or the alicyclic carboxylic acid titanium has 1-3 carboxyl groups, 0-2 hydroxyl groups and 1-17 carbon atoms.
Further, the barium precursor is one or a mixture of more than two of barium oxide, titanium barium chloride, barium bromide, barium sulfate, barium phosphate, barium nitrate or barium carboxylate; the amount of the barium precursor is 5-40%, when the content is higher than 40%, the barium titanate film can generate a heterogeneous phase, and when the content is lower than 5%, the stable ink can not be formed. The carboxylate in the barium carboxylate is one or a mixture of more than two of aliphatic carboxylate, aromatic carboxylate, hydroxyl carboxylate or alicyclic carboxylate; wherein the aliphatic barium carboxylate, the aromatic barium carboxylate, the hydroxy barium carboxylate or the alicyclic barium carboxylate has 1-3 carboxyl groups, 0-2 hydroxyl groups and 1-17 carbon atoms.
Further, the solvent is water or an organic solvent; the organic solvent is aliphatic alcohol, aromatic solvent, non-aromatic solvent or the mixture of aromatic solvent and non-aromatic solvent; wherein the fatty alcohols all contain 1-3 hydroxyl functional groups and 1-12 carbon atoms.
Further, the organic additive is one or a mixture of more than two of a viscosity regulator, a surface tension modifier and a film forming agent; wherein, the viscosity regulator is mainly used for regulating the viscosity of the ink and improving the fluidity and the printing effect. Is one or a mixture of more than two of polyalcohol, silicone, polyurethane, epoxy resin, phenolic resin, phenol formaldehyde resin, styrene allyl alcohol and polyalkylene carbonate; the organic polymer in the viscosity modifier is a homopolymer or a copolymer; the dosage of the viscosity regulator is 0.001 to 5 weight percent;
wherein the surface tension modifier is a proper additive for improving the fluidity and the leveling property of the printing ink, and is one or a mixture of more than two of a cationic surfactant, an anionic surfactant, alcohol, glycolic acid and lactic acid, and the dosage of the additive is 0.001 to 5 weight percent;
the film forming agent is used for preventing the ink composition from depositing so as to ensure the stability of the ink composition in the storage process, and is one or a mixture of more than two of starch, Arabic gum, pectin, agar, gelatin, alginate jelly, carrageenan, general gelatin, soluble starch, polysaccharide derivatives, carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, casein, sodium polyacrylate, polyoxyethylene and polyvinylpyrrolidone, and the amount of the film forming agent is 0.001-5 wt%.
Further, the base material in step 3 is organic polymer, silicon, quartz, glass or ceramic; specifically, the substrate can be selected from, but not limited to, the following materials: polyethylene terephthalate (PET), polyolefins, Polydimethylsiloxane (PDMS), polystyrene, polyacrylonitrile/butadiene/styrene, polycarbonate, polyimide (e.g., kapton (tm)), polyetherimide (e.g., ultem (tm)), Thermoplastic Polyurethane (TPU), silicone film, printed wiring board substrate (e.g., FR4), wool, silk, cotton, linen, jute, modal, bamboo, nylon, polyester, acrylic, aramid, spandex, polylactide, paper, glass, metal, dielectric coatings, and the like.
Further, the method for printing the dielectric ink coated on the substrate by using the particle-free barium titanate dielectric ink is one of dripping, spraying, laminating, spin coating, brushing and printing.
Further, the drying process includes: and (3) carrying out heat treatment drying and vacuum drying, wherein the decomposition treatment comprises one or more of photon sintering and microwave sintering, so that the pattern layer or the pattern is dried and decomposed to form the barium titanate layer. Furthermore, drying and decomposition may be accomplished by any suitable technique, the specific technique and conditions of which may be determined depending on the type of substrate (heat resistance of the substrate) and the specific composition of the ink.
Further, in the step 2, the prepared particle-free barium titanate dielectric ceramic ink has the solid content of 5-80 wt%, the viscosity of 1-50 mPa & s and the surface tension of 5-70 mN/m; the non-particle barium titanate dielectric ceramic ink has no precipitate after being stored for 6 months under room temperature and natural light.
The invention has the beneficial effects that: (1) the particle-free barium titanate dielectric ink prepared by the invention fills the blank of the barium titanate particle-free dielectric ink in printed electronics. (2) The viscosity and surface tension of the barium titanate dielectric ink can be fully adjusted and are suitable for different printing modes. (3) The ink is of the particle-free type and does not block the spray head, especially in the full printing electronic technology/digital ink jet printing technology. (4) The obtained barium titanate dielectric film has performance similar to that of bulk ceramic, thickness as low as 200 nm or less, and excellent adhesion to substrate. Through testing, the barium titanate film formed on the base material has good adhesion with the base material, and no film falls off after being torn by a 3M adhesive tape or a 600M adhesive tape; the barium titanate film produced on the flexible substrate has no obvious damage after 50 times of bending. (5) The coordination principle is adopted, so the decomposition temperature is low, the process is simple, and the method is suitable for large-scale production.
Drawings
FIG. 1 is an XRD pattern of a barium titanate thin film of example 3.
FIG. 2 is an SEM photograph of a barium titanate thin film of example 4.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments.
The titanium carboxylate, the barium carboxylate, the complexing agent, the organic additive and the solvent adopted in the embodiment of the invention are all commercial products. (examples with some substrates, curing mode changes, show that dielectric films can be made on other substrates)
The ink comprises the following components in percentage by mass: 5-40% of a titanium precursor component, 5-40% of a barium precursor component, 10-70% of a complexing agent, 0-10% of an organic additive, 0-10% of ethyl cellulose and the balance of a solvent; wherein the complexing agent is an amine compound. After the ink is prepared, the amount of the ink which is spun on a quartz glass plate is 100-400 mu L; the spin-coating speed is 500-2000 rpm, and the spin-coating time is comprehensively determined according to the ink viscosity and the spin-coating speed and is 10-25 s. And (3) placing the spin-coated glass substrate on a hot plate, heating and curing the spin-coated ink film for 3-6 minutes at 100-200 ℃, and then dropwise adding 100-200 mu L of ink again on the cured film to thicken the film. And then heating the film to 500-900 ℃ at a heating rate of 2-5 ℃/min in a tube furnace, keeping the temperature for 5-25 min, taking out the film after the tube furnace is cooled, and testing the crystal form of the film by utilizing X-ray diffraction.
Example 1
The embodiment provides a high-stability particle-free barium titanate ink, which contains 7.8% of titanium tetraisopropoxide (titanium precursor), 7.1% of barium acetate (barium precursor), 65.6% of triethanolamine (complexing agent), 0.79% of ethyl cellulose and the balance of ethylene glycol monomethyl ether (solvent).
The preparation method comprises the following steps:
firstly, adding ethyl cellulose into ethylene glycol monomethyl ether serving as an ink solvent, and magnetically stirring for 2 hours until the mixture is dissolved and clarified; secondly, titanium tetraisopropoxide and barium acetate are added into a solvent (the amount of the two substances is 1: 1), then triethanolamine is added, magnetic stirring is carried out for 5 hours until the liquid is clear and transparent, and microporous membrane (0.22 mu m) is used for filtering to obtain the high-stability particle-free barium titanate ink of the embodiment, wherein the viscosity is 74.98mPa & s. 200 μ L of the ink was spin-coated on a quartz glass substrate and spun at 1000rpm for 20 s. The spin-coated glass substrate was placed on a hot plate, the spin-coated ink film was cured by heating at 150 ℃ for 5 minutes, and then 200ul of ink was dropped again onto the cured film and cured again at the same temperature for 10 minutes to thicken the film. And then, the film is put in a tube furnace, the temperature is increased to 500 ℃ at the temperature increase rate of 2.5 ℃/min, the constant temperature is kept for 15min, the film is taken out after the tube furnace is cooled, and the crystal form of the film is obtained through an X-ray diffraction test.
Example 2
The embodiment provides a high-stability particle-free barium titanate ink, which contains 8.1% of titanium tetraisopropoxide (titanium precursor), 9.3% of barium acetate (barium precursor), 55.4% of triethanolamine (complexing agent), 1.0% of ethyl cellulose and the balance of ethylene glycol monomethyl ether (solvent).
The preparation method comprises the following steps:
firstly, adding ethyl cellulose into ethylene glycol monomethyl ether serving as an ink solvent, and magnetically stirring for 4 hours until the mixture is dissolved and clarified; secondly, titanium tetraisopropoxide and barium acetate (the amount of the titanium tetraisopropoxide and the barium acetate is 1: 1) are added into a solvent, then triethanolamine is added, magnetic stirring is carried out for 6 hours until the liquid is clear and transparent, and microporous membrane (0.22 mu m) is filtered to obtain the high-stability particle-free barium titanate ink of the embodiment, wherein the viscosity is 80.17mPa & s. 200ul of the ink was spin-coated on a quartz glass substrate at 1000rpm for 15 s. And (3) placing the glass substrate on a hot plate, heating and curing the spin-coated ink film for 3 minutes at 100 ℃, then dropwise adding 200ul of ink again on the cured film, and curing for 8 minutes again at the same temperature to achieve the purpose of thickening the barium titanate film. And then, the film is put in a tube furnace, the temperature is increased to 600 ℃ at the temperature rise rate of 2.5 ℃/min, the constant temperature is kept for 15min, the film is taken out after the tube furnace is cooled, and the crystal form of the film is obtained through an X-ray diffraction test.
Example 3
The embodiment provides a high-stability particle-free barium titanate ink, which contains 14.1% of titanium tetraisopropoxide (titanium precursor), 8.0% of barium acetate (barium precursor), 65.3% of triethanolamine (complexing agent), 1.2% of ethyl cellulose and the balance of ethylene glycol monomethyl ether (solvent).
The preparation method comprises the following steps:
firstly, adding ethyl cellulose into ethylene glycol monomethyl ether serving as an ink solvent, and magnetically stirring for 6 hours until the mixture is dissolved and clarified; secondly, titanium tetraisopropoxide and barium acetate (the amount of the titanium tetraisopropoxide and the barium acetate is 1: 1) are added into a solvent, then triethanolamine is added, magnetic stirring is carried out for 8 hours until the liquid is clear and transparent, and microporous membrane (0.22 mu m) is used for filtering to obtain the high-stability particle-free barium titanate ink of the embodiment, wherein the viscosity is 87.28mPa & s. 200 μ l of the ink was applied dropwise to the center of a quartz glass substrate, and the glass substrate was placed on a hot plate, and the ink droplets were cured by heating at 100 ℃ for 6 minutes. And then, the film is put in a box furnace, the temperature is increased to 700 ℃ at the heating rate of 5 ℃/min, the constant temperature is kept for 15min, the film is taken out after the box furnace is cooled, and the crystal form of the film is obtained through an X-ray diffraction test.
Example 4
The embodiment provides a high-stability particle-free barium titanate ink, which contains 21.9% of titanium formate (a titanium precursor), 10.3% of barium acetate (a barium precursor), 45.3% of n-butylamine (a complexing agent), 1.5% of ethyl cellulose and the balance of ethylene glycol methyl ether (a solvent).
The preparation method comprises the following steps:
firstly, adding ethyl cellulose into ethylene glycol monomethyl ether serving as an ink solvent, and magnetically stirring for 8 hours until the mixture is dissolved and clarified; secondly, adding titanium formate and barium acetate (the amount of the titanium formate and the barium acetate is 1: 1) into the solvent, then adding n-butylamine, magnetically stirring for 12 hours until the liquid is clear and transparent, and filtering by a microporous membrane (0.22 mu m) to obtain the high-stability particle-free barium titanate ink of the embodiment, wherein the viscosity is 93.12mPa & s. 200 μ l of the ink was applied dropwise to the center of a quartz glass substrate, and the glass substrate was placed on a hot plate, and the ink droplets were cured by heating at 100 ℃ for 6 minutes. And then, the film is put in a box furnace, the temperature is increased to 800 ℃ at the heating rate of 5 ℃/min, the constant temperature is kept for 15min, the film is taken out after the box furnace is cooled, and the crystal form of the film is obtained through an X-ray diffraction test.
Example 5
The embodiment provides a high-stability particle-free barium titanate ink, which contains 30.0% of titanium formate (titanium precursor), 16.2% of barium acetate (barium precursor), 37.5% of n-ethylamine (complexing agent), 1.5% of ethyl cellulose, 0.1% of methyl cellulose, 0.001% of polyvinylpyrrolidone (organic additive), 0.001% of agar (organic additive) and the balance of ethylene glycol methyl ether (solvent).
The preparation method comprises the following steps:
firstly, adding ethyl cellulose into ethylene glycol monomethyl ether serving as an ink solvent, and magnetically stirring for 10 hours until the mixture is dissolved and clarified; secondly, adding titanium formate and barium acetate (the amount of the titanium formate and the barium acetate is 1: 1) into a solvent, then adding n-ethylamine, polyvinylpyrrolidone and agar, magnetically stirring for 12 hours until the liquid is clear and transparent, and filtering by a microporous membrane (0.22 mu m) to obtain the high-stability particle-free barium titanate ink of the embodiment, wherein the viscosity is 101.39mPa & s. 200ul of the ink was spin-coated on a quartz glass substrate at 800rpm for 20 seconds. And (3) placing the glass substrate on a hot plate, heating and curing the spin-coated film for 5 minutes at 150 ℃, then dripping 200ul of ink on the cured film again, and curing the ink again for 2 minutes at the same temperature to achieve the purpose of thickening the barium titanate film. And then placing the film in a tube furnace, keeping the interior of the tube furnace communicated with the outside air, heating to 800 ℃ at the heating rate of 5 ℃/min, keeping the constant temperature for 20min, taking out the film after the tube furnace is cooled, and obtaining the crystal form of barium titanate through an X-ray diffraction test.
Example 6
The embodiment provides a high-stability particle-free barium titanate ink, which contains 35.4% of titanium formate (a titanium precursor), 16.2% of barium acetate (a barium precursor), 30% of ethylenediamine (a complexing agent), 1.8% of ethyl cellulose, 0.1% of methyl cellulose, 0.01% of liquid paraffin (an organic additive), 0.001% of polyvinylpyrrolidone (an organic additive), 0.001% of polyoxyethylene (an organic additive) and the balance of ethanol (a solvent).
The preparation method comprises the following steps:
firstly, adding ethyl cellulose into ethanol serving as an ink solvent, and magnetically stirring for 10 hours until the mixture is dissolved and clarified; secondly, adding titanium formate and barium acetate (the amount of the titanium formate and the barium acetate is 1: 1) into a solvent, then adding ethylenediamine, methyl cellulose, liquid paraffin, polyvinylpyrrolidone and polyoxyethylene, magnetically stirring for 12 hours until the liquid is clear and transparent, and filtering by a microporous membrane (0.22 mu m) to obtain the high-stability particle-free barium titanate ink of the embodiment, wherein the viscosity is 101.39mPa & s. 200ul of the ink was spin-coated on a quartz glass substrate at 800rpm for 20 seconds. And (3) placing the glass substrate on a hot plate, heating and curing the spin-coated film for 5 minutes at 150 ℃, then dripping 200ul of ink on the cured film again, and curing the ink again for 2 minutes at the same temperature to achieve the purpose of thickening the barium titanate film. And then placing the film in a tube furnace, keeping the interior of the tube furnace communicated with the outside air, heating to 900 ℃ at the heating rate of 5 ℃/min, keeping the constant temperature for 20min, taking out the film after the tube furnace is cooled, and obtaining the crystal form of barium titanate through an X-ray diffraction test.
Claims (9)
1. The method for preparing the ultrathin dielectric ceramic film based on the particle-free dielectric ceramic ink is characterized by comprising the following steps of:
step 1, preparing barium titanate dielectric ceramic ink;
the ink comprises the following components in percentage by mass: 5-40% of a titanium precursor component, 5-40% of a barium precursor component, 10-70% of a complexing agent, 0-10% of an organic additive, 0-10% of ethyl cellulose and the balance of a solvent; wherein the complexing agent is an amine compound;
firstly, fully dissolving ethyl cellulose in a solvent according to a proportion, and magnetically stirring until the solution is clear; secondly, adding a titanium precursor and a barium precursor into the clarified solution, and then adding a complexing agent according to a proportion until the complexing agent is completely dissolved to form basic barium titanate ink;
then adding the organic additive into the basic barium titanate ink according to the proportion, and stirring for 0.5-30h at 0-25 ℃ until no particles are dissolved to obtain barium titanate dielectric ceramic ink;
step 2, preparing the particle-free barium titanate dielectric ceramic ink;
filtering the barium titanate dielectric ceramic ink prepared in the step 1 by a microporous filter membrane of 0.22-10 microns to obtain particle-free barium titanate dielectric ceramic ink for printing;
step 3, preparing a dielectric ceramic film;
coating or printing the particle-free barium titanate dielectric ceramic ink prepared in the step 2 on a substrate to form a pattern layer or a pattern; drying and decomposing the film to form a dielectric ceramic film on the substrate.
2. The method for preparing an ultra-thin dielectric ceramic film based on the particle-free dielectric ceramic ink of claim 1, wherein the complexing agent is one or a mixture of more than two of aliphatic amine, alcohol amine, amide and aromatic amine.
3. The method for preparing an ultra-thin dielectric ceramic film based on the particle-free dielectric ceramic ink according to claim 1, wherein the titanium precursor is one or a mixture of two or more of titanium oxide, titanium chloride, titanium bromide, titanium sulfate, titanium phosphate, titanium nitrate, titanium carboxylate, or titanium titanate; the carboxylate in the titanium carboxylate is one or a mixture of more than two of aliphatic carboxylate, aromatic carboxylate, hydroxyl carboxylate or alicyclic carboxylate; wherein the aliphatic carboxylic acid titanium, the aromatic carboxylic acid titanium, the hydroxy carboxylic acid titanium or the alicyclic carboxylic acid titanium has 1-3 carboxyl groups, 0-2 hydroxyl groups and 1-17 carbon atoms.
4. The method for preparing an ultra-thin dielectric ceramic film based on the particle-free dielectric ceramic ink of claim 1, wherein the barium precursor is one or a mixture of two or more of barium oxide, titanium barium chloride, barium bromide, barium sulfate, barium phosphate, barium nitrate, or barium carboxylate; the carboxylate in the barium carboxylate is one or a mixture of more than two of aliphatic carboxylate, aromatic carboxylate, hydroxyl carboxylate or alicyclic carboxylate; wherein the aliphatic barium carboxylate, the aromatic barium carboxylate, the hydroxy barium carboxylate or the alicyclic barium carboxylate has 1-3 carboxyl groups, 0-2 hydroxyl groups and 1-17 carbon atoms.
5. The method for preparing an ultra-thin dielectric ceramic film based on the particle-free dielectric ceramic ink according to claim 1, wherein the solvent is water or an organic solvent; the organic solvent is aliphatic alcohol, aromatic solvent, non-aromatic solvent or the mixture of aromatic solvent and non-aromatic solvent; wherein the fatty alcohols all contain 1-3 hydroxyl functional groups and 1-12 carbon atoms.
6. The method for preparing an ultra-thin dielectric ceramic film based on the particle-free dielectric ceramic ink of claim 1, wherein the organic additive is one or a mixture of two or more of a viscosity modifier, a surface tension modifier, and a film former; wherein the viscosity regulator is one or more of polyalcohol, silicone, polyurethane, epoxy resin, phenolic resin, phenol formaldehyde resin, styrene allyl alcohol and polyalkylene carbonate; the organic polymer in the viscosity modifier is a homopolymer or a copolymer; the dosage of the viscosity regulator is 0.001 to 5 weight percent;
wherein the surface tension modifier is one or a mixture of more than two of cationic surfactant, anionic surfactant, alcohol, glycolic acid and lactic acid, and the dosage of the surface tension modifier is 0.001-5 wt%;
wherein the film forming agent is one or a mixture of more than two of starch, Arabic gum, pectin, agar, gelatin, seaweed gel, carrageenan, general gelatin, soluble starch, polysaccharide derivatives, carboxymethyl cellulose, propylene glycol alginate, methyl cellulose, sodium starch phosphate, sodium carboxymethyl cellulose, sodium alginate, casein, sodium polyacrylate, polyoxyethylene and polyvinylpyrrolidone, and the dosage of the film forming agent is 0.001-5 wt%.
7. The method for preparing an ultra-thin dielectric ceramic film based on the particle-free dielectric ceramic ink according to claim 1, wherein the substrate in step 3 is an organic polymer, silicon, quartz, glass or ceramic; the method for printing the dielectric ink coated or printed on the substrate by using the particle-free barium titanate dielectric ink is one of dripping, spraying, laminating, spin coating, brushing and printing.
8. The method for preparing an ultra-thin dielectric ceramic film based on the particle-free dielectric ceramic ink according to claim 1, wherein the drying process comprises: and (3) carrying out heat treatment drying and vacuum drying, wherein the decomposition treatment comprises one or more of photon sintering and microwave sintering, so that the pattern layer or the pattern is dried and decomposed to form the barium titanate layer.
9. The method for preparing an ultra-thin dielectric ceramic film based on the particle-free dielectric ceramic ink according to claim 1, wherein in the step 2, the prepared particle-free barium titanate dielectric ceramic ink has a solid content of 5-80 wt%, a viscosity of 1-50 mPa · s, and a surface tension of 5-70 mN/m; the non-particle barium titanate dielectric ceramic ink has no precipitate after being stored for 6 months under room temperature and natural light.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113990844A (en) * | 2021-10-25 | 2022-01-28 | 西安交通大学 | Preparation method of anti-counterfeit label based on multilayer quasi-amorphous photon heterostructure |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1787119A (en) * | 2004-12-07 | 2006-06-14 | 三星电机株式会社 | Sol composition for dielectric ceramic, dielectric ceramic and multilayered ceramic capacitor using the same |
| CN101215172A (en) * | 2008-01-09 | 2008-07-09 | 华中科技大学 | Method for preparing bismuth sodium titanate base leadless piezoelectricity thick film |
| JP2009177171A (en) * | 2007-12-28 | 2009-08-06 | Mitsubishi Materials Corp | Dielectric film, its manufacturing method and use |
| CN104946022A (en) * | 2015-07-10 | 2015-09-30 | 东北大学 | High-stability particle free type silver-based conductive ink and preparation method thereof |
| CN106810253A (en) * | 2015-12-01 | 2017-06-09 | 意法半导体股份有限公司 | Precursor solution and method from anhydrous or dehydration precursor for preparing leadless piezoelectric material material |
| US20170221648A1 (en) * | 2016-01-29 | 2017-08-03 | Usa As Represented By The Administrator Of The National Aeronautics And Space Administration | Solid State Ultracapacitor |
-
2021
- 2021-06-25 CN CN202110712045.1A patent/CN113277845A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1787119A (en) * | 2004-12-07 | 2006-06-14 | 三星电机株式会社 | Sol composition for dielectric ceramic, dielectric ceramic and multilayered ceramic capacitor using the same |
| JP2009177171A (en) * | 2007-12-28 | 2009-08-06 | Mitsubishi Materials Corp | Dielectric film, its manufacturing method and use |
| CN101215172A (en) * | 2008-01-09 | 2008-07-09 | 华中科技大学 | Method for preparing bismuth sodium titanate base leadless piezoelectricity thick film |
| CN104946022A (en) * | 2015-07-10 | 2015-09-30 | 东北大学 | High-stability particle free type silver-based conductive ink and preparation method thereof |
| CN106810253A (en) * | 2015-12-01 | 2017-06-09 | 意法半导体股份有限公司 | Precursor solution and method from anhydrous or dehydration precursor for preparing leadless piezoelectric material material |
| US20170221648A1 (en) * | 2016-01-29 | 2017-08-03 | Usa As Represented By The Administrator Of The National Aeronautics And Space Administration | Solid State Ultracapacitor |
Non-Patent Citations (2)
| Title |
|---|
| DJORDJIJE TRIPKOVIC ET. AL: "Inkjet patterning of in situ sol–gel derived barium titanate thin films", 《CERAMICS INTERNATIONAL》 * |
| 姜兆华等: "《应用表面化学》", 30 September 2018, 哈尔滨工业大学出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113990844A (en) * | 2021-10-25 | 2022-01-28 | 西安交通大学 | Preparation method of anti-counterfeit label based on multilayer quasi-amorphous photon heterostructure |
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