CN112521802A - Particle-free nickel-based conductive ink and preparation method thereof - Google Patents
Particle-free nickel-based conductive ink and preparation method thereof Download PDFInfo
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- CN112521802A CN112521802A CN202011356780.5A CN202011356780A CN112521802A CN 112521802 A CN112521802 A CN 112521802A CN 202011356780 A CN202011356780 A CN 202011356780A CN 112521802 A CN112521802 A CN 112521802A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D5/00—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures
- B05D5/12—Processes for applying liquids or other fluent materials to surfaces to obtain special surface effects, finishes or structures to obtain a coating with specific electrical properties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/24—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials for applying particular liquids or other fluent materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/0023—Digital printing methods characterised by the inks used
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M7/00—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock
- B41M7/009—After-treatment of prints, e.g. heating, irradiating, setting of the ink, protection of the printed stock using thermal means, e.g. infrared radiation, heat
Abstract
The invention relates to a particle-free nickel-based conductive ink, which comprises 5-40% of a nickel precursor, 10-55% of a chelating agent or a complexing agent, 0-10% of a reducing agent, 0.001-10% of an organic additive and the balance of a solvent; the chelating or complexing agent is ammonia or an amine compound. The particle-free nickel-based conductive ink disclosed by the invention fills the blank of the nickel-based particle-free conductive ink in printed electronics. The nickel-gold thin film formed by the nickel-based conductive ink has the same order of magnitude of conductivity as the silver conductive film, but only has the cost of about 2 percent of the silver conductive ink, has better oxidation resistance, corrosion resistance, mechanical strength and the like compared with the copper conductive film, can be dried and decomposed in air, has the resistivity of a metal nickel conductive layer formed on a base material of 22 mu omega cm-500 mu omega cm, has good adhesion with the base material, does not fall off a nickel film after being torn and pulled by a 3M adhesive tape or a 600M adhesive tape, and has no obvious damage after the metal nickel conductive thin film generated on a flexible base material is bent for 50 times.
Description
Technical Field
The invention relates to the technical field of conductive ink, in particular to particle-free nickel-based conductive ink for printing electronics and a preparation method thereof.
Background
The printed electronic technology has the advantages of high precision, strong stability, high printing speed, wide substrate selection, environmental protection, flexibility, large-area manufacturing and the like, and gradually becomes an important innovation in the field of microelectronics. The traditional etching method has the problems of serious material waste, complex preparation process, high cost, serious environmental pollution and the like. The preparation and application of the functionalized conductive ink are widely concerned as the core of the printed electronic technology. The conductive ink reported at present mainly comprises silver ink and copper ink: although silver has the advantages of high conductivity, oxidation resistance and the like, the stability of the whole device is limited by the lower electron mobility; in addition, silver is a noble metal, and the large-scale commercial application of the silver is limited due to low yield and high price. Copper, as an ideal alternative material, is as much electrically conductive as silver, but much cheaper. However, copper is easily oxidized in air, and particularly, in the fields of batteries and thin film transistors, the conductive layer needs to have high heat resistance and corrosion resistance, so that the copper-based conductive ink brings great challenges to commercial development.
Conductive inks 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 conductive particles is complex, agglomeration/deposition is easy to form in storage, the added dispersing agent can cause the decomposition temperature of the ink to be higher, the conductivity of the product is reduced, and in addition, the problems of particle sedimentation, agglomeration and the like of the particle type conductive ink can block a spray head in printing and cause the deposition of the printed product to be uneven. The particle-free conductive ink is generally a solution of a metal precursor, and a required conductive film is formed through simple heat treatment after printing, so that the preparation process is simple and flexible. Because the metal exists in the solution in the form of ions, the ink has good stability and uniformity, high metal content, no need of a dispersing agent and relatively low sintering temperature, and meanwhile, a smooth and uniform metal film can be formed after the metal precursor is sintered, and the high-resolution characteristic is generated.
Compared with silver and copper, the nickel-gold has excellent properties, including conductivity with the same order of magnitude as that of silver, but much cheaper price, high corrosion resistance, high temperature resistance, oxidation resistance, better mechanical strength and the like, but various documents reported at present do not really obtain the nickel-based particle-free conductive ink suitable for the full-printing electronic process. Few attempts (such as Thin Solid Films,2017,642) have not only failed to achieve printable, particle-free nickel-based inks, but also achieved desirable electrical conductivity. Currently, nickel-based inks produced by suppliers on the market and suitable for printed electronics are all nano nickel particle type inks (such as Applied Nanotech Holding, Inc.) however, the nano nickel particle type inks are not only expensive, have inherent defects of particle type inks, and are not suitable for producing thin films requiring thicker layers, but also have a relatively large difference in resistance from predictable high conductive silver and copper inks.
Therefore, the development of the particle-free nickel-based conductive ink suitable for printing electronics can greatly make up for the defects of the types of the conductive ink at the present stage.
Disclosure of Invention
Technical problem to be solved
In view of the above disadvantages and shortcomings of the prior art, the present invention provides a particle-free nickel-based conductive ink and a method for preparing the same, so as to solve the technical problems of the existing particle-free conductive ink suitable for the printed electronic technology, such as the expensive price of the conductive silver ink, the low electron mobility, the easy oxidation in the air of the film prepared from the copper ink, etc. The invention also relates to a use method of the particle-free nickel-based conductive ink.
(II) technical scheme
In order to achieve the purpose, the invention adopts the main technical scheme that:
in a first aspect, the present invention provides a particle-free nickel-based conductive ink, comprising: 5-40% of nickel precursor, 10-55% of chelating agent or complexing agent, 0-10% of reducing agent, 0.001-10% of organic additive and the balance of solvent; wherein the chelating agent or complexing agent is ammonia or amine compound.
According to a preferred embodiment of the present invention, the chelating agent or the complexing agent is one or a mixture of two or more of ammonia water, aliphatic amine, alcohol amine, amide and aromatic amine. The dosage of the chelating agent or the complexing agent is 10-55%, when the content of the chelating agent or the complexing agent is higher than 55%, the microstructure of the film is loose, no connection junction exists among particles, and a conductive path cannot be formed; and when the content is less than 10%, the coordination condition cannot be satisfied to form stable ink. The amount of chelating or complexing agent is preferably 10-15%, 15-20%, 20-25%, 25-30%, 30-35%, 35-40%, 40-45% or 45-50%.
The complexing agent can be one or more of ammonia water, 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.
According to a preferred embodiment of the present invention, the nickel precursor is one or more of nickel oxide, nickel chloride, nickel bromide, nickel sulfate, nickel phosphate, nickel nitrate, or nickel carboxylate. The dosage of the nickel precursor is 5-40%, and when the content of the nickel precursor is higher than 40%, the coordination condition cannot be met to form stable ink. When the content is less than 5%, the microstructure of the film is loose, no connection junction exists among particles, and a conductive path cannot be formed. The content of the nickel precursor is preferably 5-10%, 10-15%, 15-20%, 20-25%, 25-30%, 30-35% or 35-40%.
Preferably, the carboxylate in the nickel carboxylate is one or more of aliphatic carboxylate, aromatic carboxylate, hydroxycarboxylic acid or alicyclic carboxylate. The aliphatic nickel carboxylate, the aromatic nickel carboxylate, the nickel hydroxy carboxylate or the alicyclic nickel carboxylate each has 1 to 3 carboxyl groups, 0 to 2 hydroxyl groups and 1 to 17 carbon atoms.
According to a preferred embodiment of the present invention, the organic additive is one or a mixture of any several of a viscosity modifier, a surface tension modifier, a film forming agent and a defoaming agent.
Wherein, the viscosity regulator is mainly used for regulating the viscosity of the ink and improving the fluidity and the printing effect. For example: paraffin wax, microcrystalline wax, polyethylene wax, oxidized polyethylene wax, polypropylene wax, saso wax, hyperbranched polymer, cellulose polymer, polyacrylate, polystyrene, polyolefin, polyvinylpyrrolidone, polyvinyl acetal, polyester, polyimide, polyetherimide, polyol, silicone, polyurethane, epoxy resin, phenolic resin, phenol formaldehyde resin, styrene allyl alcohol and polyalkylene carbonate, or a mixture of any of them. Preferably, the organic polymer in the viscosity modifier may be a homopolymer or a copolymer. The viscosity modifier is preferably used in an amount of 0.001 wt% to 5 wt%.
Among these, the surface tension modifier is any suitable additive that can improve the fluidity and leveling of the ink, and is preferably used in an amount of 0.001 wt% to 5 wt%. For example, the surface tension modifier may be any one or a mixture of any several of a cationic surfactant, an anionic surfactant, an alcohol, glycolic acid, and lactic acid.
Wherein, the film forming agent is used for preventing the ink composition from depositing, thereby ensuring the stability of the ink composition during the storage process, and the amount of the film forming agent is preferably 0.001 wt% to 5 wt%. For example, the film forming agent is any one or a mixture of any several of starch, acacia, pectin, agar, gelatin, seaweed gum, 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.
Among them, the antifoaming agent is an additive which can reduce surface tension, prevent foam formation, and reduce or eliminate the original foam, and the amount thereof is preferably 0.001 wt% to 5 wt%. For example, the defoaming agent is any one or a mixture of any several of fluorosilicone, mineral oil, vegetable oil, polysiloxane, ester wax, fatty alcohol, glycerin, stearate, silicone, and polypropylene-based polyether.
According to a preferred embodiment of the present invention, 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.
According to the preferred embodiment of the present invention, wherein the reducing agent is selected from one or any combination of several of the following substances: glycerol, propylene glycol, tetrahydric alcohol, pentahydric alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, dimer alcohol acetate, 1, 4-butanediol, 1, 2-butanediol, 2, 3-butanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 8-octanediol, 1, 2-propanediol, 1, 3-butanediol, 1, 2-pentanediol, glucose, tartaric acid, citric acid, ascorbic acid, formic acid, formaldehyde. Wherein the reducing agent is an optional additive. For example, in the case of a conductive ink, when the amount of the reducing agent is 0, it is preferable to use a reducing atmosphere (H) when the drying decomposition is carried out after the coating or printing on the substrate2) The process is carried out as follows. If the conductive ink contains a reducing agent, the subsequent drying and decomposition may be carried out in air or an inert atmosphere. When the reducing agent is added, the amount of the reducing agent is preferably 0 to 10%, more preferably 2 to 3%, 3 to 4%, 4 to 5%, 5 to 6%, 6 to 7%, 7 to 8%, 8 to 9%, 9 to 10%.
According to a preferred embodiment of the present invention, the particle-free nickel-based conductive ink has a solid content of 5 to 80 wt%, a viscosity of 1 to 20mPa · s, and a surface tension of 10 to 50 mN/m; the particle-free nickel-based conductive ink is free of sediment after being stored for 6 months under room temperature natural light; the particle-free nickel-based conductive ink can be dried and decomposed by heat treatment and/or photon sintering and/or microwave sintering to obtain a metal nickel conductive layer.
On the other hand, the invention provides a preparation method of the particle-free nickel-based conductive ink, which comprises the following steps:
s1, preparing raw materials according to the following components and preparing basic nickel-based ink;
5-40% of nickel precursor, 10-55% of chelating agent or complexing agent, 0-10% of reducing agent, 0.001-10% of organic additive and the balance of solvent;
the nickel precursor is one or a mixture of more of nickel oxide, nickel chloride, nickel bromide, nickel sulfate, nickel phosphate, nickel nitrate or nickel carboxylate; the chelating agent or complexing agent is one or a mixture of more than two of ammonia water, aliphatic amine, alcohol amine, amide and aromatic amine;
fully dissolving a chelating agent or a complexing agent into a solvent, and adding a nickel precursor into the mixed solution until the nickel precursor is completely dissolved to form basic nickel-based ink;
and S2, adding a reducing agent and an organic additive into the basic nickel-based ink, stirring at 0-25 ℃ until no particles are dissolved, and filtering by using a microporous filter membrane to obtain the particle-free nickel-based conductive ink for printing.
Preferably, the organic additive is one or a mixture of any several of a viscosity regulator, a surface tension modifier, a film forming agent and a defoaming agent.
Wherein, the reducing agent is added to reduce the decomposition temperature, increase the speed of reducing nickel into metal simple substance and improve the microstructure of the film after heat treatment. The type and amount of the added organic additives can be selected according to the ink of different printing modes or the physical and mechanical properties of the printed pattern.
In still another aspect, the present invention also provides a method for using a particle-free nickel-based conductive ink, including: and coating or printing the particle-free nickel-based conductive ink for printing on a substrate to form a layer or a pattern, and drying and decomposing the layer or the pattern to form a metal nickel conductive layer on the substrate.
Tests show that the resistivity of the metallic nickel conducting layer formed on the base material is 22-500 mu omega cm, the adhesion of the metallic nickel conducting layer to the base material is good, and no nickel film falls off after the metallic nickel conducting layer is torn by a 3M or 600M adhesive tape; the metal nickel conductive film generated on the flexible substrate has no obvious damage after being bent for 50 times.
The method for coating or printing the particle-free nickel-based conductive ink for printing on the substrate can be any one of dripping, spraying, laminating, spin coating, brushing and printing.
Wherein the substrate is organic polymer, silicon, quartz, glass, ceramic or any other suitable material. 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.
Wherein the drying and decomposing process comprises: one or more of heat treatment, photon sintering and microwave sintering are combined to dry and decompose the pattern layer or pattern to form the metallic nickel conducting 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.
In one embodiment, the drying and decomposition process is a heat treatment of the dried layer or pattern followed by a heat treatment of sintering. The first drying of the ink layer or pattern may be carried out at any suitable temperature, for example, in the range of 20 to 150 c for a period of 5min to 36 hours, with lower temperatures and longer drying times, higher temperatures and shorter drying times. The sintering decomposition ink is prepared by sintering decomposition of ink under inert atmosphere (such as nitrogen and/or argon), reducing atmosphere (such as hydrogen, especially when no reducing agent is contained in conductive ink) or vacuum condition, wherein the temperature range of the decomposition ink is 150-800 ℃, and the time is 5min-10 h. The time for sintering and decomposing the ink is temperature dependent, and the higher the temperature, the shorter the sintering and decomposing time. In addition, the higher the amount of reducing agent used in the conductive ink, the lower the decomposition temperature.
In another embodiment, when the substrate is made of transparent plastic (allowing microwave penetration), the dried pattern or pattern is first heat-treated and then microwave-sintered. Drying is carried out for 5min-36h at 20-150 ℃, microwave sintering refers to that microwave directly interacts with materials, and a sample directly absorbs microwave energy so as to be heated and sintered.
(III) advantageous effects
The invention has the beneficial effects that:
the invention makes up the blank of insufficient types of the particle-free conductive ink, and can obtain the conductive nickel film with high conductive performance by simple heat treatment and/or photon sintering and/or microwave sintering, and the particle-free nickel-based ink which is convenient to use has good commercial value. Specifically, it is expressed in the following aspects:
(1) the particle-free nickel-based conductive ink provided by the invention supplements the types of the existing particle-free conductive ink and fills the blank of the nickel-based particle-free conductive ink in printed electronics. (2) The viscosity and the surface tension of the nickel-based conductive ink can be suitable for different printing modes by adjusting the organic additive. (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 resistivity of the obtained metallic nickel thin film is 22 mu omega cm-10m omega cm, is only 3.2 times of the resistance of the nickel metal block, has excellent conductivity, and has good adhesion between the nickel metal thin film and the substrate. (5) The preparation process of the particle-free nickel-based conductive ink is simple and is suitable for large-scale production.
Drawings
FIG. 1 is the XRD pattern of the nickel thin film of example 3, and 3 diffraction peaks in the pattern are completely matched with the characteristic peaks of XRD standard card (JCPDS 04-0850), which shows that the prepared thin film is simple nickel and has good crystallinity.
Fig. 2 is an SEM image of the nickel thin film of example 3, showing that the nickel thin film has a very uniform particle size (about 70nm) and a very uniform density.
FIG. 3 is a graph showing the resistivity of the nickel film subjected to the heat treatment at 400 ℃ as a function of the heat treatment time in example 6.
Detailed Description
For the purpose of better explaining the present invention and to facilitate understanding, the present invention will be described in detail by way of specific embodiments with reference to the accompanying drawings.
The particle-free nickel-based conductive ink disclosed by the invention adopts an oxide, a chloride, a bromide, a sulfate, a nitrate or a carboxylate of nickel as a precursor, can form a stable complex with ammonia or an amine compound, and is dissolved in water or an organic solvent to form the particle-free conductive ink. In addition, a proper amount of reducing agent is added according to the requirement, and one or more of a viscosity regulator, a surface tension modifier, a film forming agent and a defoaming agent are added for preparing the printing ink with different printing modes/printing requirements, and meanwhile, the decomposition temperature is reduced, the microstructure of the sintered film is adjusted, and the quality of the printed pattern is improved. The particle-free conductive ink disclosed by the invention is strong in stability, free of precipitate generation after being stored for 6 months under room temperature natural light, simple and easy to operate in a preparation method, low in cost, green and pollution-free, and easy to realize industrialization.
As an element which is good in electrical conductivity, high in heat resistance coefficient, corrosion-resistant and magnetic, the metal nickel is a nickel-based high-temperature alloy which shows high mechanical strength, excellent oxidation resistance and corrosion resistance at the use temperature of 950-1100 ℃. The corrosion resistance of the nickel is 20-50% higher than that of the zinc. Nickel as a conductive layer has better conductivity, mechanical strength and hydrophilicity than graphitized carbon materials. Nickel has the same order of magnitude of conductivity as gold and silver, but is only one-fiftieth as expensive as silver. It can be seen that nickel is an ideal alternative material to silver, which is much cheaper, but has the same order of conductivity. The inventor is based on the excellent performance of nickel metal (compared with silver, the nickel metal has conductivity of the same order of magnitude, but is much cheaper, and has high corrosion resistance, high temperature resistance, oxidation resistance, better mechanical strength and the like), and is limited by the sensitivity of a printing electronic technology, especially a full printing electronic technology/digital ink-jet printing technology to a nozzle, so the inventor is dedicated to developing a novel nickel-based particle-free conductive ink. Meanwhile, because the particle-free nickel-based ink has lower heating temperature, the selection of the base material is wider, for example, the base material can be selected from paper, plastic, fabric and the like, and meanwhile, the particle-free nickel-based ink is also suitable for the currently developed novel sintering modes, such as microwave sintering and photon sintering.
In order to better understand the above technical solutions, exemplary embodiments of the present invention will be described in more detail below with reference to the accompanying drawings. It should be noted that the nickel carboxylate, the chelating agent or the complexing agent, the reducing agent, the organic additive, and the solvent used in the examples of the present invention are commercially available products. The percentage of the conductive ink in this application (including the examples below) is referred to as mass percent.
Example 1
This example provides a high-stability particle-free nickel-based conductive ink, which contains 20% of nickel acetate (nickel precursor), 18% of ammonia (complexing agent), 2% of formaldehyde (reducing agent), 0.1% of sodium carboxymethylcellulose (organic additive), 0.001% of polyvinylpyrrolidone (organic additive), 0.001% of gelatin (organic additive), 0.001% of digoorbyk-1802 tps (organic additive), and the balance of ethanol. The preparation method comprises the following steps:
dissolving ammonia water in ethanol according to the proportion, adding nickel acetate into the mixed solution after uniformly mixing, stirring for 3h at 20 ℃ until the nickel acetate is dissolved, and respectively adding formaldehyde and an organic additive until the nickel acetate is completely dissolved. The high-stability, particle-free nickel-based conductive ink of this example was obtained by filtration through a microporous membrane (pore size 0.22 μm), having a viscosity of 1.9 mPas and a surface tension of 30 mN/m.
And (3) taking 400 mu L of the ink and spin-coating the ink on a 2 cm-2 cm glass substrate, wherein the spin-coating parameters are set to be uniform coating rotating speed of 500rpm and uniform coating time of 15s, the spin-coating rotating speed is 1000-5000rpm, and the spin-coating time is 20s in the spin-coating process. And under the air atmosphere, heating to 400 ℃ at the heating rate of 20 ℃/min, and carrying out heat treatment for 30min to obtain the metallic nickel film with the resistivity of 4.9m omega cm.
Example 2
This example provides a high-stability particle-free nickel-based conductive ink, which contains 35% of nickel oxalate (nickel precursor), 26% of ethylamine (complexing agent), 2% of glycerol (reducing agent), 0.02% of phenolic resin (organic additive), 0.001% of polyvinylpyrrolidone (organic additive), 0.001% of methylcellulose (organic additive), 0.001% of DISPERBYK-2015 (organic additive), and the balance ethanol. The preparation method comprises the following steps:
dissolving ethylamine in ethanol according to the proportion, uniformly mixing, adding nickel oxalate into the mixed solution, stirring for 3 hours at 20 ℃ until the nickel oxalate is dissolved, and adding glycerol and an organic additive until the nickel oxalate is completely dissolved. The high-stability particle-free nickel-based conductive ink of the embodiment is obtained by filtering through a microporous membrane (0.22 μm), and has the viscosity of 1.4 mPas and the surface tension of 24 mN/m.
400 mu L of the ink is taken and spin-coated on a 2 cm-by-2 cm glass substrate, the suspension coating parameters are the same as those of the embodiment 1, and the metal nickel film is heated to 400 ℃ at the heating rate of 20 ℃/min for heat treatment for 30min under the nitrogen atmosphere, so that the resistivity of the metal nickel film is 6.9m omega cm.
Example 3
This example provides a high-stability particle-free nickel-based conductive ink, which contains 40% nickel acetate (nickel precursor), 38% isopropylamine (complexing agent), 7% ethylene glycol (reducing agent), 0.02% polyvinylpyrrolidone (organic additive), 0.001% agar (organic additive), 0.001% urea (organic additive), 0.001% DISPERBYK-2015 (organic additive), and the balance ethanol. The preparation method comprises the following steps:
dissolving isopropylamine in ethanol solution according to the proportion, uniformly mixing, adding nickel acetate into the mixed solution, stirring for 2h at the temperature of 20 ℃ until the nickel acetate is dissolved, and respectively adding ethylene glycol and an organic additive until the nickel acetate is completely dissolved. The high-stability particle-free nickel-based conductive ink of the embodiment was obtained by filtering through a microporous membrane (0.22 μm), and the viscosity was 3.4 mPas and the surface tension was 34 mN/m.
400 mu L of the ink is taken and coated on a 2 cm-by-2 cm glass substrate in a spin mode, the suspension coating parameters are the same as those of the embodiment 1, and the temperature is raised to 400 ℃ at the temperature raising rate of 20 ℃/min for heat treatment for 30min under the air atmosphere, so that the resistivity of the metallic nickel film is 800 mu omega cm.
As shown in fig. 1, which is an XRD pattern of the metallic nickel thin film of this example, as seen from fig. 1,3 diffraction peaks in the pattern completely match with characteristic peaks of XRD standard card (JCPDS 04-0850), indicating that the prepared thin film is elemental nickel and has good crystallinity. Fig. 2 is an SEM image of the metallic nickel thin film of the present example, showing that the nickel thin film has a very uniform particle size (about 70nm) and very good densification.
Example 4
The example provides a high-stability particle-free nickel-based conductive ink, which contains 21.9% of nickel acetate (nickel precursor), 30% of n-butylamine (complexing agent), 3% of ascorbic acid (reducing agent), 0.02% of sodium carboxymethylcellulose (organic additive), 0.001% of paraffin (organic additive), 0.001% of Dispers650 (organic additive), 0.001% of DISPERBYK-2015 (organic additive), and the balance of ethanol. The preparation method comprises the following steps:
dissolving n-butylamine in an ethanol solution according to the proportion, uniformly mixing, adding nickel acetate into the mixed solution, stirring at 20 ℃ for 0.5h until the nickel acetate is dissolved, and respectively adding ascorbic acid and an organic additive until the ascorbic acid and the organic additive are completely dissolved. Filtering with a microporous membrane (0.22 μm) to obtain the high-stability particle-free nickel-based conductive ink of the embodiment, wherein the viscosity of the high-stability particle-free nickel-based conductive ink is 3.7mPa & s, and the surface tension of the high-stability particle-free nickel-based conductive ink is 30 mN/m; the metal nickel film is printed on a glass substrate by adopting an ink-jet printing (Epson R330) mode, and the resistivity of the metal nickel film is 1.3m omega cm by adopting a photon sintering mode.
Example 5
The embodiment provides a high-stability particle-free nickel-based conductive ink, which comprises 23% of nickel formate (nickel precursor), 30% of ethylamine (complexing agent), 2% of polyethylene glycol (reducing agent), 0.1% of methylcellulose (organic additive), 0.001% of polyvinylpyrrolidone (organic additive), 0.001% of agar (organic additive), 0.001% of Pic DISPERBYK-199 (organic additive) and the balance of water. The preparation method comprises the following steps:
dissolving ethylamine in water according to the proportion, uniformly mixing, adding nickel formate into the mixed solution, stirring at 20 ℃ for 0.5h until the nickel formate is dissolved, and respectively adding polyethylene glycol and an organic additive until the nickel formate is completely dissolved. The high-stability particle-free nickel-based conductive ink of the embodiment was obtained by filtering through a microporous membrane (0.22 μm), and the high-stability particle-free nickel-based conductive ink had a viscosity of 6.3 mPas and a surface tension of 42 mN/m.
The metal nickel film is printed on a glass substrate by adopting an ink-jet printing (Epson R330) mode, and is heated to 300 ℃ at a heating rate of 20 ℃/min for heat treatment for 30min under the air atmosphere, so that the resistivity of the metal nickel film is 600 mu omega cm.
Example 6
The embodiment provides a high-stability particle-free nickel-based conductive ink, which comprises 25% of nickel formate (nickel precursor), 30% of ethylenediamine (complexing agent), 2% of formic acid (reducing agent), 0.01% of liquid paraffin (organic additive), 0.001% of polyvinylpyrrolidone (organic additive), 0.001% of polyoxyethylene (organic additive), 0.001% of piper DISPERBYK-199 (organic additive), and the balance of ethanol. The preparation method comprises the following steps:
dissolving ethylenediamine in the ethanol solution according to the proportion, uniformly mixing, adding nickel formate into the mixed solution, stirring at 20 ℃ for 0.5h until the nickel formate is dissolved, and respectively adding formic acid and the organic additive until the nickel formate is completely dissolved. The high-stability particle-free nickel-based conductive ink of the embodiment was obtained by filtering through a microporous membrane (0.22 μm), and the viscosity was 5.2 mPas, and the surface tension was 37 mN/m.
The metal nickel film is printed on a glass substrate by adopting an ink-jet printing (Epson R330) mode, and is heated to 500 ℃ at a heating rate of 10 ℃/min for heat treatment for 30min under a nitrogen atmosphere, so that the resistivity of the metal nickel film is 24 mu omega cm.
As shown in fig. 3, the initial resistivity value of the metallic nickel thin film of the present example is larger than that of bulk nickel metal (6.93 μ Ω · cm) according to the change curve of the thermal decomposition time, and the resistivity of the metallic nickel thin film decreases with the lapse of the thermal decomposition time, and is substantially stabilized at 23.8 μ Ω · cm at 30min of thermal decomposition, which is only about 3.4 times as large as that of bulk nickel metal (6.93 μ Ω · cm). Therefore, the particle-free nickel-based conductive ink is suitable for the full-printing electronic process, can meet the printing requirement, has ideal conductivity and has a commercial application prospect.
Example 7
This example is based on example 3, except that the reducing agent ethylene glycol is removed (i.e. the amount of reducing agent is 0), and the amount of isopropylamine is increased accordingly. Other operations and conditions were the same as in example 3. The highly stable, particle-free nickel-based conductive ink of this example was obtained, having a viscosity of 3.1 mPas and a surface tension of 33 mN/m.
400 mu L of the ink is taken and spin-coated on a 2 cm-by-2 cm glass substrate, the suspension coating parameters are the same as those of the embodiment 1, and the metal nickel film is heated to 400 ℃ at the heating rate of 20 ℃/min for heat treatment for 30min under the hydrogen atmosphere (reducing atmosphere), so that the resistivity of the metal nickel film is 820 mu omega cm.
Comparative example 1
This comparative example was conducted in the same manner as in example 3 except that nickel acetate was replaced with copper acetate in the same manner as in example 3. And filtering to obtain the high-stability particle-free nickel-based conductive ink of the comparative example, wherein the viscosity of the ink is 5.7mPa & s, and the surface tension of the ink is 41 mN/m. 400 mul of the ink is taken and spin-coated on a 2cm by 2cm glass substrate, the suspension coating parameters are the same as those of the embodiment 1, and the temperature is raised to 400 ℃ at the temperature raising rate of 20 ℃/min for heat treatment for 30min under the air atmosphere, so that the resistivity of the metal copper film is 1.35 omega cm. It can be seen that copper is easily oxidized in an air atmosphere, resulting in a copper thin film having a large resistivity.
Comparative example 2
This comparative example is based on example 3, and the nickel acetate was replaced with silver acetate, and the other conditions were the same as in example 3. The cost of the conductive ink prepared was 40 times that of the conductive ink of example 3. Therefore, although silver conductive thin films with low resistivity can be obtained by using silver, the cost is too high, and the silver conductive thin films are not suitable for commercial popularization and application.
Comparative example 3
This comparative example is based on example 3, replacing isopropylamine with citric acid, and the other conditions are the same as in example 3. The viscosity of the prepared conductive ink is 2.9 mPas, and the surface tension is 30 mN/m. 400 mu L of the ink is taken and coated on a 2 cm-by-2 cm glass substrate in a spin mode, the suspension coating parameters are the same as those of the embodiment 1, and the temperature is raised to 400 ℃ at the temperature raising rate of 20 ℃/min for heat treatment for 30min under the air atmosphere, so that the resistivity of the metallic nickel film is 4.8 omega cm. Therefore, after the amine compound complexing agent in the conductive ink is replaced by the conventional complexing agent, the metal nickel film with low resistivity suitable for the full-printing electronic process is not obtained.
Comparative example 4
This comparative example is based on example 3, except that the polyvinylpyrrolidone is removed and the amount of isopropylamine is increased accordingly, and the other conditions are the same as in example 3. The prepared conductive ink has the viscosity of 3.2mPa & s and the surface tension of 34 mN/m. 400 mu L of the ink is taken and spin-coated on a 2 cm-by-2 cm glass substrate, the suspension coating parameters are the same as those of the embodiment 1, and the metal nickel film is heated to 400 ℃ at the heating rate of 20 ℃/min for heat treatment for 30min under the air atmosphere, so that the resistivity of the metal nickel film is 872 mu omega cm. It can be seen that the removal of the viscosity modifier affects the uniformity of the nickel film and results in a slight increase in resistivity.
Comparative example 5
This comparative example was based on example 3, except that the agar was removed and the amount of isopropylamine was increased accordingly, as in example 3. The prepared conductive ink has the viscosity of 3.3mPa & s and the surface tension of 34 mN/m. 400 mu L of the ink is taken and coated on a 2 cm-by-2 cm glass substrate in a spin mode, the suspension coating parameters are the same as those of the embodiment 1, and the temperature is raised to 400 ℃ at the temperature raising rate of 20 ℃/min for heat treatment for 30min in the air atmosphere, so that the resistivity of the metallic nickel film is 853 mu omega cm. It can be seen that the removal of the film former affects the uniformity of the nickel film and results in a slight increase in resistivity.
Comparative example 6
This comparative example is based on example 3, with urea removed and isopropylamine added accordingly, and the other conditions are the same as in example 3. The prepared conductive ink has the viscosity of 3.3mPa & s and the surface tension of 34 mN/m. 400 mu L of the ink is taken and coated on a 2 cm-by-2 cm glass substrate in a spin mode, the suspension coating parameters are the same as those of the embodiment 1, and the temperature is raised to 400 ℃ at the temperature raising rate of 20 ℃/min for heat treatment for 30min under the air atmosphere, so that the resistivity of the metallic nickel film is 900 mu omega cm. It can be seen that removal of the tension modifier affects the uniformity of the nickel film and results in a slight increase in resistivity.
Comparative example 7
This comparative example was made by removing DISPERBYK-2015 from example 3 and increasing the amount of isopropylamine accordingly, all other conditions being the same as in example 3. The prepared conductive ink has the viscosity of 3.4mPa & s and the surface tension of 34 mN/m. 400 mu L of the ink is taken and coated on a 2 cm-by-2 cm glass substrate in a spin mode, the suspension coating parameters are the same as those of the embodiment 1, and the metal nickel film is heated to 400 ℃ at the heating rate of 20 ℃/min for heat treatment for 30min in the air atmosphere, so that the resistivity of the metal nickel film is 831 mu omega cm. It can be seen that the removal of the dispersant affects the uniformity of nickel dispersion in the conductive ink, and the uniformity of the decomposed nickel film is affected by the anisotropy, resulting in a slight increase in resistivity.
The particle-free nickel-based conductive ink disclosed by the invention is simple in preparation method, low in curing temperature, short in time, high in stability and good in conductivity, and can be widely applied to optoelectronic devices such as thin film transistor elements, solar cells and supercapacitor elements.
Finally, it should be noted that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. A particle-free nickel-based conductive ink, comprising: 5-40% of nickel precursor, 10-55% of chelating agent or complexing agent, 0-10% of reducing agent, 0.001-10% of organic additive and the balance of solvent; wherein the chelating agent or complexing agent is ammonia or amine compound.
2. The particle-free nickel-based conductive ink as claimed in claim 1, wherein the chelating or complexing agent is one or a mixture of two or more of ammonia, aliphatic amine, alcohol amine, amide, and aromatic amine.
3. The particle-free nickel-based conductive ink according to claim 1, wherein the nickel precursor is one or more of nickel oxide, nickel chloride, nickel bromide, nickel sulfate, nickel phosphate, nickel nitrate, and nickel carboxylate.
4. The particle-free nickel-based conductive ink as claimed in claim 1, wherein the organic additive is one or a mixture of any of a viscosity modifier, a surface tension modifier, a film forming agent and a defoaming agent.
5. The particle-free nickel-based conductive 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 particle-free nickel-based conductive ink as claimed in claim 1, wherein the reducing agent is selected from one or any combination of the following substances: glycerol, propylene glycol, tetrahydric alcohol, pentahydric alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, dimer alcohol acetate, 1, 4-butanediol, 1, 2-butanediol, 2, 3-butanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 8-octanediol, 1, 2-propanediol, 1, 3-butanediol, 1, 2-pentanediol, glucose, tartaric acid, citric acid, ascorbic acid, formic acid, formaldehyde.
7. A preparation method of particle-free nickel-based conductive ink comprises the following steps:
s1, preparing raw materials according to the following components and preparing basic nickel-based ink;
5-40% of nickel precursor, 10-55% of chelating agent or complexing agent, 0-10% of reducing agent, 0.001-10% of organic additive and the balance of solvent;
the nickel precursor is one or a mixture of more of nickel oxide, nickel chloride, nickel bromide, nickel sulfate, nickel phosphate, nickel nitrate or nickel carboxylate;
the chelating agent or the complexing agent is one or a mixture of more of ammonia water, aliphatic amine, alcohol amine, amide and aromatic amine;
fully dissolving a chelating agent or a complexing agent into a solvent, and adding a nickel precursor into the mixed solution until the nickel precursor is completely dissolved to obtain the basic nickel-based ink;
and S2, adding a reducing agent and an organic additive into the basic nickel-based ink, stirring at 0-25 ℃ until no particles are dissolved, and filtering by using a microporous filter membrane to obtain the particle-free nickel-based conductive ink for printing.
8. The preparation method of claim 7, wherein the organic additive is one or a mixture of any of a viscosity regulator, a surface tension modifier, a film forming agent and a defoaming agent.
9. The production method according to claim 7, 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 contain 1-3 hydroxyl functional groups and 1-12 carbon atoms;
the reducing agent is selected from one or any combination of several of the following substances: glycerol, propylene glycol, tetrahydric alcohol, pentahydric alcohol, ethylene glycol, diethylene glycol, polyethylene glycol, propylene glycol, dipropylene glycol, dimer alcohol acetate, 1, 4-butanediol, 1, 2-butanediol, 2, 3-butanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 8-octanediol, 1, 2-propanediol, 1, 3-butanediol, 1, 2-pentanediol, glucose, tartaric acid, citric acid, ascorbic acid, formic acid, formaldehyde.
10. A method for using particle-free nickel-based conductive ink is characterized by comprising the following steps: coating or printing the particle-free nickel-based conductive ink according to any one of claims 1 to 6 or the particle-free nickel-based conductive ink prepared by the preparation method according to any one of claims 7 to 9 on a substrate to form a layer or a pattern, and drying and decomposing the layer or the pattern to form a metal nickel conductive layer on the substrate.
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