CN111117367B - Photosensitive silver-based conductive ink, method for preparing silver conductive structure by using photosensitive silver-based conductive ink and flexible conductive material - Google Patents
Photosensitive silver-based conductive ink, method for preparing silver conductive structure by using photosensitive silver-based conductive ink and flexible conductive material Download PDFInfo
- Publication number
- CN111117367B CN111117367B CN201811279202.9A CN201811279202A CN111117367B CN 111117367 B CN111117367 B CN 111117367B CN 201811279202 A CN201811279202 A CN 201811279202A CN 111117367 B CN111117367 B CN 111117367B
- Authority
- CN
- China
- Prior art keywords
- silver
- ink
- conductive ink
- conductive
- visible light
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/004—Photosensitive materials
- G03F7/0047—Photosensitive materials characterised by additives for obtaining a metallic or ceramic pattern, e.g. by firing
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/0026—Apparatus for manufacturing conducting or semi-conducting layers, e.g. deposition of metal
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
- H01B13/003—Apparatus or processes specially adapted for manufacturing conductors or cables using irradiation
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B5/00—Non-insulated conductors or conductive bodies characterised by their form
- H01B5/14—Non-insulated conductors or conductive bodies characterised by their form comprising conductive layers or films on insulating-supports
Abstract
A photosensitive silver-based conductive ink, a method for preparing a silver conductive structure from the photosensitive silver-based conductive ink, and a flexible conductive material. Each liter of ink comprises 0.1-5.0 mol of silver precursor, 0.01-0.20 mol of visible light photosensitive reagent auxiliary agent, 0.01-0.20 mol of surfactant and 1-20 mol of organic solvent. The invention realizes the one-time forming of the two-dimensional conductive silver structure by controlling the visible light surface light source and projecting the digital pattern of the target silver structure to be used as a photomask. The conductive ink can fully absorb light energy, and a two-dimensional silver conductive structure is constructed on a flexible substrate by adopting a low-light-power-density light source. The materials and methods of the present invention are suitable for use with a variety of polymeric substrate materials including films, sheets and pipes.
Description
Technical Field
The invention belongs to the field of flexible electronic materials, and particularly relates to photosensitive silver-based conductive ink, a method for preparing a silver conductive structure by using the photosensitive silver-based conductive ink, and a flexible conductive material.
Background
In recent years, flexible electronic devices, such as stretchable solar cells, organic light emitting diodes, and the like, have been rapidly developed, and particularly, the fields of touch and flat panel display are industries with high attention. The flexible electrode material is taken as the basis of flexible electronic equipment, and attracts the attention of extensive researchers. The traditional transparent conductive material Indium Tin Oxide (ITO) has not been able to meet the requirements of flexible electronic devices due to its disadvantages of high rigidity, brittleness and high cost. Therefore, conductive ink materials based on flexible printed electronics have been produced.
Conductive ink materials have a wide variety, with metallic conductive inks based on silver materials being of most interest. The particle type conductive ink is prepared by dispersing silver nanoparticles in a solvent system containing multiple components, and the conditions of machine nozzle blockage, particle agglomeration, influence of a dispersing agent on conductivity and the like are often generated in practical application. The particle-free silver conductive ink usually adopts a silver precursor as a silver source, is mixed with other additives and is dissolved in a solvent, and has remarkable advantages compared with the particle-free silver conductive ink. For example, the conductivity of the material can be obviously improved by avoiding the use of a dispersing agent, and the system does not contain any solid, has no problems of agglomeration, instrument blockage and the like. However, the conventional particle-free ink usually needs to be subjected to ink jet printing or screen printing to realize the required electronic circuit patterning, and then silver nanoparticles are prepared by pyrolysis and sintered to realize the conductivity. The method has a complex production process, and the polymer film material used as the substrate of the flexible electronic device can be damaged under high temperature conditions, so that the preparation of the flexible electronic device is not facilitated.
Another approach is light-induced silver nanoparticle formation and patterning thereof. A point light source is usually used to scan and irradiate the silver-containing precursor ink, and the silver precursor is selectively reduced and arranged into a required pattern by controlling the scanning path. Compared with the traditional method, the method has the advantages that the silver nanoparticles are prepared and distributed by in-situ reduction, the preparation steps are reduced, and the production period is greatly shortened. However, the silver in-situ reduction can be realized only by high optical power density, the power of the current commercial light source is generally insufficient, the cost of the high-power light source is high, the requirement of large-scale production and application is difficult to meet, and the system temperature rise caused by the high-power light source can also damage the flexible polymer film substrate. In addition, the point-by-point scanning mode adopted by the illumination arrangement method is not beneficial to constructing complex patterns, and the forming time is long. In some researches, a Digital Micromirror Device (DMD) is added on a high-optical-power-density laser beam device, and a projected laser pattern is used as a photomask, so that the limitation of point-to-point scanning is eliminated. However, the laser light source control system is complex, high in cost, and also cannot be commercially used due to the characteristic that the silver ink needs a high-power laser. Therefore, if silver conductive ink suitable for low-power light source equipment is developed, the series of problems can be well solved, the cost is reduced, and the efficiency of preparing the silver-based flexible conductive device is greatly improved. However, no studies on this aspect have been reported yet.
Disclosure of Invention
The invention provides photosensitive silver-based conductive ink, wherein each liter of ink comprises the following components: 0.1-5.0 mol of silver precursor, 0.01-0.20 mol of visible light photosensitive reagent auxiliary agent, 0.01-0.20 mol of surfactant and 1-20 mol of organic solvent.
According to the invention, in each liter of printing ink, the content of the silver precursor is 0.2-4.0 mol, preferably 0.3-3.0 mol; illustratively, the content of the silver precursor is 0.33mol, 1.25mol, 2.5 mol. Further, the silver precursor may be selected from silver nitrate, silver oxide, silver chloride, silver hexafluorophosphate, silver hexafluoroantimonate, and one, two or more of aliphatic silver carboxylate, aromatic silver carboxylate and alicyclic silver carboxylate. For example, the silver aliphatic carboxylate, the silver aromatic carboxylate and the silver alicyclic carboxylate are selected from the group consisting of silver aliphatic carboxylate, silver aromatic carboxylate and silver alicyclic carboxylate having 1 to 3 carboxyl groups, 0 to 2 hydroxyl groups and 1 to 17 carbon atoms. Preferably, the silver precursor may be at least one of silver hexafluorophosphate and silver nitrate.
According to the invention, in each liter of printing ink, the content of the visible light photosensitive reagent is 0.05-0.15 mol, preferably 0.05-0.10 mol; illustratively, the content of the visible light photosensitive agent is 0.05mol, 0.066mol and 0.10 mol. Further, the visible light photosensitive agent is a compound which is active under the irradiation of laser or monochromatic visible light with a visible light wave band of 415-780 nm. For example, the compound may be selected from one, two or more of the following: quinone compounds, cyclopentadienyl titanium compounds, iodonium salt compounds and sulfonium salt compounds. For example, the quinone compound may be camphorquinone or the like. For example, the titanocene compound may be fluorinated diphenyltitanocene or the like. For example, the iodonium salt compound may be an alkyl iodonium salt. For example, the sulfonium salt compound may be an alkyl sulfonium salt or the like.
According to the invention, in each liter of printing ink, the content of the visible light photosensitive reagent auxiliary agent is 0.02-0.15 mol, preferably 0.02-0.10 mol; illustratively, the visible light photosensitizer assistant is present in an amount of 0.025mol, 0.033mol, 0.04 mol. Further, the visible light photosensitizing agent auxiliary may be one selected from the group consisting of secondary amine compounds, tertiary amine compounds, secondary alcohol compounds, and tertiary alcohol compounds. For example, the secondary amine compound may be diethylamine, and the tertiary amine compound may be triethylamine. For example, the tertiary amine compound may be ethyl 4-dimethylaminobenzoate.
According to the invention, in each liter of printing ink, the content of the surfactant is 0.02-0.12 mol, preferably 0.02-0.10 mol; illustratively, the surfactant content is 0.022mol, 0.033mol, 0.066 mol. Further, the surfactant may be one, two or more selected from the group consisting of sulfate-based surfactants, quaternary ammonium-based surfactants, and amino acid-based surfactants, the segment structure of which is linear, branched, or aromatic. For example, the sulfate-based surfactant may be sodium dodecyl sulfate, sodium dodecyl benzene sulfonate, or the like. For example, the quaternary ammonium salt surfactant may be cetyltrimethylammonium chloride, cetyltrimethylammonium bromide, or the like. For example, the amino acid-based surfactant may be sodium N-lauroyl sarcosinate, sodium N-decanoyl sarcosinate, or the like.
According to the invention, the organic solvent may be present in an amount of 3 to 16mol, for example 5 to 10mol, per liter of ink. Further, the organic solvent may be selected from one, two or more of methanol, ethanol, ethylene glycol, propanol, isopropanol, N-butanol, isobutanol, N-pentanol, N-octanol, acetone, butanone, chloroform, methylene dichloride, diethyl ether, butyl ether, carbon disulfide, 1-methyl-2-pyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, ethyl acetate, dioxane, acetonitrile, benzene, toluene and xylene.
Further, the invention also provides a preparation method of the silver-based conductive ink, which comprises the following steps: and uniformly mixing the silver precursor, the visible light photosensitive reagent auxiliary agent, the surfactant and the organic solvent to obtain the silver-based conductive ink.
For example, the silver-based conductive ink can be obtained by mixing an organic solution of a silver precursor with an organic mixed solution of a visible light photosensitizer, a visible light photosensitizer assistant, and a surfactant in a ratio (for example, a volume ratio of 1:1 to 10, 1:1 to 5, preferably 1:1, 1:2) and stirring uniformly. Wherein the organic solvent in the organic solution and the organic mixed solution is the organic solvent.
The silver-based conductive ink is a photosensitive silver-based conductive ink that can be used under a low-power density visible light source. The inventor creatively discovers that the effective absorption of the visible light photosensitive reagent, the auxiliary agent and the surfactant thereof to the light energy can be greatly improved by introducing the visible light photosensitive reagent, the auxiliary agent and the surfactant into a silver precursor solution system, and the light power density is as low as 10-1000 mW/cm2The in-situ preparation of the high-efficiency silver nanoparticles can be realized by reducing the silver precursor under the light source of (1). The laser power densities employed in the reported studies have generally been higher than 104W/cm210 of a laser used in the present invention4More than twice. The photosensitive silver-based ink provided by the invention can be suitable for common visible light source equipment at present, and greatly promotes the application of a photoinduction patterning method in flexible electronic production.
Further, the present invention also provides a method for preparing a silver conductive structure by light-induced forming, which directly projects (preferably digitally projects) a target pattern entirety onto an interface of a polymer base material and the above-mentioned silver-based conductive ink using a light source, and a silver precursor in the conductive ink in an illuminated area is reduced into silver particles, and the silver conductive structure is formed from silver nanoparticles.
According to the method, the light induction is one-time light induction, the forming is surface forming, and the silver conductive structure is a two-dimensional silver conductive structure.
According to the process of the invention, the silver particles have a diameter of from 70 to 150nm, for example from 80 to 120nm, and illustratively a diameter of 100 nm.
According to the method of the invention, the silver particles are uniformly distributed on the polymeric base material with a coverage of more than 80%, for example more than 85%, or more than 90%; illustratively, the coverage is 95%.
According to the method, the light source can be one, two or three selected from thermoluminescence light sources, gas discharge light sources and solid illumination light sources with the light-emitting wavelength of 415-780 nm. For example, the thermoluminescent light source may be an incandescent lamp, a halogen lamp, or the like. For example, the gas discharge light source may be a fluorescent lamp, a metal halide, or the like. For example, the solid-state illumination light source may be an LD laser, an LED laser, or the like. Preferably, the light source has an emission wavelength of 420 to 500nm, more preferably 430 to 480nm, and even more preferably 440 to 475 nm. Illustratively, the light source may be a 445nm or 470nm blue solid-state illumination light source (e.g., LD laser, LED laser, etc.).
According to the method, the optical power density of the light source can be 10-1000 mW/cm2For example, 100 to 800mW/cm2Illustratively, the optical power density is 300mW/cm2。
According to the method of the present invention, the polymer base material may be selected from at least one of a planar material (e.g., polymer film material, polymer sheet material) and a curved material (e.g., polymer tubing material) of the following polymer materials: parylene, polystyrene, polypropylene, polyethylene, polyvinyl chloride, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, polymethylmethacrylate, polyurethane, polyarylate, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, poly 4-methylpentene-1, polyimide, polymethylsiloxane, polyethersulfone, bisphenol a sulfone, ABS, soluble polytetrafluoroethylene, and the like. For example, the polymer film material may be transparent polypropylene, polyethylene terephthalate, transparent polyimide, polydimethylsiloxane, soluble polytetrafluoroethylene, or the like. For example, the polymer tubing material may be polyethylene terephthalate, soluble polytetrafluoroethylene, polyvinyl chloride, and the like. For example, the polymer sheet material may be polymethyl methacrylate, polycarbonate, polyvinyl chloride, or the like.
According to the method of the present invention, the method employs an apparatus comprising a visible light projection light source, a tank for containing the base material and conductive ink, and the like.
The inventor of the application directly projects the whole target pattern by adopting a visible light source as a photomask. The silver precursor in the ink in the illumination area is reduced into silver particles, and the silver nanoparticles which are closely arranged jointly form a preset silver structure on the substrate. The method gets rid of the limitation of the traditional point light source scanning system, all target silver structures can be formed in one step, the method is simple, convenient and efficient, the obtained silver structures have good conductivity, and the conductivity is 1/10-1/5 of bulk silver. Meanwhile, the used visible light projection equipment is low in cost, portable, and better in visible light safety than common ultraviolet light, and is favorable for flexible commercial application.
The silver conductive structures are formed on the surface of a polymer base material, such as on the surface of a film or sheet, or such as on the inner surface of a tube, which does not change the shape of the polymer base material. Further, the conductive ink and the method for constructing a two-dimensional silver conductive structure of the present invention do not damage the physical and chemical properties of the polymer base material.
The invention further provides a flexible conductive material, which is prepared by preparing the silver-based conductive ink into a polymer material loaded with a silver structure by the photoinduction molding method, and then exposing and fusing silver nanoparticles to obtain the conductive flexible material.
Specifically, the flexible conductive material is prepared by a method comprising the following steps:
1) according to the technical scheme, each liter of printing ink contains 0.1-3.0 mol of silver precursor, 0.01-0.20 mol of visible light photosensitive reagent auxiliary agent, 0.01-0.20 mol of surfactant and 1-20 mol of organic solvent, and the uniform conductive printing ink is obtained by stirring and mixing uniformly;
2) placing the conductive ink into a material groove containing a polymer substrate material, or injecting the conductive ink into a polymer substrate-free material (such as a polymer pipe), and forming a metal silver two-dimensional structure in a visible light source projection area at one step to obtain a silver-containing structure polymer material;
3) and (3) exposing the silver-containing polymer material obtained in the step (2) under the same visible light source in the step (2), and fusing silver nanoparticles to obtain the flexible conductive material.
In the step 2), in the process of forming the metal silver two-dimensional structure in the visible light source projection area at one time, the ink in the exposure area generates silver nanoparticles, and the area which is not illuminated does not generate silver nanoparticles. Preferably, the compact silver layer can be selectively generated to form a target two-dimensional silver structure after 0.1-24 hours of illumination.
Preferably, in the step 3), the silver structure is cleaned before the silver structure-containing polymer material is exposed to the same visible light source in the step 2). Preferably, the exposure time of step 3) is only to make the adjacent silver nanoparticles on the silver structure mutually fused and form a channel, and the exposure time may be 1 to 30 minutes, for example.
For example, the flexible conductive material may conform to the shape of the polymeric substrate material, such as a film, tube, or sheet.
Further, the invention also provides a flexible electronic device containing the flexible conductive material.
The invention has the beneficial effects that:
1. the invention creatively provides visible light photosensitive silver-based conductive ink which can be generated in situ by inducing silver nanoparticles through 415-780 nm laser or monochromatic visible light, and the ink can effectively absorb light energy, so that the ink can be suitable for commercial light source equipment with low optical power density, and the production cost is greatly reduced.
2. The invention creatively provides a method for preparing a silver conductive structure by adopting one-time light induction surface forming for the first time. The method digitally controls the visible light source to project all the patterns at one time to be used as the photomask, and avoids the problems of complex point-by-point scanning system and long time consumption by adopting a point light source.
3. The materials and methods of the present invention can be used to prepare a variety of complex conductive structures on a variety of polymeric substrate materials. The substrate material can be polymer films, sheets, and curved structures such as tubing. The method adopts digital projection, the projection pattern can be randomly regulated, the prepared silver conductive structure is complex and changeable, the silver particles have larger particle size and are uniformly distributed, and the coverage rate on the substrate is high. Therefore, different requirements of different fields on the flexible conductive device can be met, and targeted customization can be realized.
Drawings
Fig. 1 is a schematic view of a method for forming a conductive silver structure by using a one-time photo-induced surface in embodiment 1 of the present invention.
FIG. 2 is an X-ray polycrystalline diffraction pattern of a sample prepared in example 1 of the present invention.
FIG. 3 is a scanning electron micrograph of a sample prepared in example 2 of the present invention.
Fig. 4 is an example of the application of the flexible conductive film with LEDs in embodiment 2 of the present invention.
FIG. 5 shows the results of testing the conductivity of silver structures on various polymer substrates in example 3 of the present invention; wherein A represents a polymer film PET, B represents transparent polyimide, and C represents water-soluble polytetrafluoroethylene.
Fig. 6 is a tubular conductive device in embodiment 4 of the present invention.
FIG. 7 is a scanning electron micrograph of a sample prepared in comparative example 1 of the present invention.
FIG. 8 is a scanning electron micrograph of a sample prepared in comparative example 2 of the present invention.
Fig. 9 is a silver circuit structure film manufactured in example 2 of the present invention.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are only for illustrating the present invention and are not intended to limit the scope of the present invention. In addition, it should be understood that various changes or modifications can be made by those skilled in the art after reading the disclosure of the present invention, and such equivalents also fall within the scope of the invention.
The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Instrument information:
x-ray polycrystal diffractometer: empyrean, Cu target, netherlands;
scanning electron microscope: JSM-7500F field emission scanning electron microscope, JEOL Japan;
four-probe sheet resistance tester: RTS-9, China;
multifunctional multimeters: VC890C+Victory, China.
Example 1 photoinduced in situ generation of silver nanoparticles
1) Mixing 2.5mol/L of ethylene glycol solution of silver hexafluorophosphate with 0.1mol/L of camphorquinone, 0.05mol/L of triethylamine and 0.066mol/L N-sodium lauroyl sarcosinate according to the volume ratio of 1:1, and then uniformly stirring to obtain the conductive ink.
2) Pouring 0.6 ml of the conductive ink in the step 1) into a trough which is formed by polyethylene terephthalate (PET) serving as a substrate and a silica gel plate.
3) The luminous power density of the used light source is 300mW/cm2Light is projected from the lower part of the material groove, penetrates through the transparent substrate and reaches the mixed liquid layer, the photosensitizer is excited, and then reduction of the silver precursor is initiated.
The conductive ink layer in the exposed area gradually darkened from light yellow to dark brown as the exposure time extended, demonstrating the formation of silver nanoparticles. Meanwhile, the sample obtained by the exposure for 1 hour was subjected to the X-ray polycrystalline diffraction test, and the result (shown in fig. 2) showed that characteristic peaks of the silver crystal structure were prominent, corresponding to the (111), (200), (220) and (331) crystal planes of the face-centered cubic lattice, respectively, at 38.1 °,44.3 °,64.4 ° and 77.4 °, respectively, in addition to the characteristic peaks of the polymer substrate at 46.6 ° and 53.7 °. This result is a good demonstration that the silver-based conductive ink and low power light source used can effectively initiate the generation of silver nanoparticles.
Example 2 photo-induced preparation of a Complex conductive silver Structure by one-time surface Molding
1) Mixing 5mol/L silver nitrate glycol solution with 0.1mol/L camphorquinone, 0.05mol/L ethyl 4-dimethylaminobenzoate and 0.066mol/L N-sodium decanoyl sarcosinate glycol mixed solution according to the volume ratio of 1:1, and then uniformly stirring to obtain the conductive ink.
2) 3 ml of the conductive ink in the step 1) is poured into a trough which is composed of a PET film material as a substrate and a silica gel plate.
3) And projecting the pre-generated digital pattern on the interface of the mixed liquid and the substrate through a visible light source device, wherein the ink in the exposed area generates silver nano particles, and the non-illuminated area does not generate silver nano particles. And irradiating for 2 hours to form a preset structure by the selectively generated compact silver layer.
4) After the structure obtained in step 3) is cleaned, exposure is continued for 15 minutes, and adjacent silver nanoparticles are mutually fused and form a passage, so that the structure has good conductivity.
Through the characterization of a scanning electron microscope (as shown in fig. 3), a dense silver nanoparticle layer (the particle size is about 100nm, the coverage rate of silver particles is about 95%) formed on the surface of the PET film and a fused connected structure can be observed. Conductivity tests showed that the conductivity of the silver material was 1/10 for the silver body. The structure is provided with LEDs which can be lighted after being electrified, and meanwhile, the flexible conductive structure is bent, so that the LEDs can well keep a lighted state. The flexible conductive device prepared by the ink system and the forming method can meet the requirements of practical application. A wide variety of silver structures, such as the complex circuit shown in fig. 9, can be prepared by adjusting the preset pattern projected in step 3). Therefore, the material system and the method can be well adapted to different commercialization requirements.
Example 3 preparation of conductive silver structures on different polymer films
1) Mixing 2.5mol/L silver nitrate solution with 0.2mol/L camphorquinone, 0.08 mol/L4-ethyl dimethylaminobenzoate and 0.132mol/L N-sodium decanoyl sarcosinate according to the volume ratio of 1:1, and uniformly stirring to obtain the conductive ink.
2) And (3) respectively pouring the conductive ink in the step (1) into a trough which is formed by respectively taking polymer films A (PET), B (transparent polyimide) and C (water-soluble polytetrafluoroethylene) as substrates and a silica gel plate.
3) and a, projecting a preset pattern on the interface of the mixed solution and the film A, and irradiating for 2 hours to generate a silver structure. b. And projecting a preset pattern on the interface of the mixed solution and the film B, and irradiating for 2 hours to generate a silver structure. c. And projecting a preset pattern on the interface of the mixed solution and the film C, and irradiating for 2 hours to generate a silver structure.
4) After the samples obtained in 3) were washed, they were exposed to light for 20 minutes, respectively, and silver nanoparticles were fused.
The conductivity test shows that the silver structure formed on the three film substrates has good conductivity, and the conductivity is 4 multiplied by 106Siemens are in a meter or more.
The result proves that the photosensitive silver-based ink and the one-time forming method can be used for various polymer film materials and have wide applicability.
Example 4 preparation of conductive silver structures in Polymer tubing
1) Mixing 1mol/L silver nitrate solution with 0.1mol/L camphorquinone, 0.05mol/L ethyl 4-dimethylaminobenzoate and 0.033mol/L N-sodium lauroyl sarcosinate according to the volume ratio of 1:2, and uniformly stirring to obtain the conductive ink.
2) 2 ml of the conductive ink in the step 1) is injected into a soluble polytetrafluoroethylene tube (the inner diameter is 3mm) to form a section of liquid column.
3) Placing the liquid column in 2) transversely above a light source device.
4) And projecting a preset curve pattern on the interface between the inner wall of the polymer tube and the mixed solution from the lower part, and exposing for 3 hours.
5) And 4) cleaning the sample obtained in the step 4), and then continuously exposing for 15 minutes to obtain the device with the conductive silver structure deposited on the inner wall of the tube.
The prepared tubular conductive device can form a conductive loop together with the lamp bead and an external power supply, and the lamp bead is lightened when the power supply is switched on, so that the tubular conductive device is proved to have good conductive performance.
The result proves that the photosensitive silver-based ink and the one-time forming method can be applied to the construction of a conductive structure on a curved surface, and the applicability of the system is further expanded.
Comparative example 1 investigation of preparation of silver Structure Using silver-containing precursor ink alone
1) 1mL of 2.5mol/L silver nitrate ethylene glycol solution was poured into a trough using a PET film as a base.
2) The visible light source projects light from below to the solution layer.
3) After 2 hours of exposure, the polymer film was removed and washed.
The formation of silver nanoparticles was analyzed by scanning electron microscopy, as shown in FIG. 7, and compared to the surface morphology of the original PET film, the ink system obtained silver particles with a particle size of-10 nm, which was much smaller than the particle size (. about.100 nm) prepared with the ink of example 2 with the addition of the photosensitizer and surfactant. And the sample was light treated to fuse silver particles whose resistance was too high to exceed the multimeter range (200M Ω). The ink system cannot be used to prepare conductive silver structures.
Comparative example 2 investigation of preparation of silver Structure Using silver precursor ink containing photosensitive agent and auxiliary agent
1) Mixing 5mol/L silver nitrate glycol solution and 0.1mol/L camphorquinone and 0.05mol/L ethyl 4-dimethylaminobenzoate glycol solution according to the volume ratio of 1:1, and uniformly stirring to obtain the photosensitive ink.
2) Pouring 1ml of the conductive ink in the step 1) into a trough taking a PET film as a substrate.
3) The visible light source projects light from below to the solution layer.
4) After 2 hours of exposure, the polymer film was removed and washed.
The morphology of the silver nanoparticle layer on the surface of the polymer was observed by a scanning electron microscope, and as shown in fig. 8, the size of the obtained silver particles was about 100 nm. This result demonstrates that the addition of a photosensitizing agent and its adjuvants can effectively promote the in situ generation of silver nanoparticles under low power density visible light exposure, as compared to the sample prepared in comparative example 1. The coverage of the nanoparticles on the polymer substrate was about 80% for the silver structure obtained with this photosensitive ink, which was much less than the coverage of the silver particles (-95%) for the material prepared under the same conditions with this photosensitive ink of example 3 with the simultaneous addition of surfactant. The nano particles are dispersed and distributed on the surface of the polymer film, so that the nano particles are not beneficial to mutually fusing and forming a conductive loop, and the silver structure obtained by adopting the photosensitive ink has relatively poor conductive performance.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. A photosensitive silver-based conductive ink usable with a low power density visible light source, comprising, per liter of ink:
the silver precursor is selected from silver nitrate, silver oxide, silver chloride, silver hexafluorophosphate, silver hexafluoroantimonate, and one, two or more of aliphatic silver carboxylate, aromatic silver carboxylate and alicyclic silver carboxylate;
the visible light photosensitive reagent is a compound with activity under the irradiation of laser or monochromatic visible light with a visible light wave band of 415-780 nm: one, two or more selected from quinone compounds, titanocene compounds, iodonium salt compounds and sulfonium salt compounds;
the visible light photosensitive reagent auxiliary is selected from one of secondary amine compounds, tertiary amine compounds, secondary alcohol compounds and tertiary alcohol compounds;
the surfactant is one or two or more selected from sulfate surfactants, quaternary ammonium salt surfactants and amino acid surfactants, wherein the chain segment structure of the surfactant is a straight chain, a branched chain or an aromatic chain.
2. The photosensitive silver-based conductive ink capable of being used under a low-power-density visible light source according to claim 1, wherein the content of the silver precursor is 0.2-4.0 mol per liter of the ink.
3. The conductive ink of claim 1, wherein the visible light sensitizer is present in an amount of 0.05 to 0.15mol per liter of ink.
4. The conductive ink of claim 1, wherein the visible light photosensitizer assistant is present in an amount of 0.02 to 0.15mol per liter of ink.
5. The conductive ink of claim 1, wherein the surfactant is present in an amount of 0.02 to 0.12mol per liter of ink.
6. The conductive ink according to claim 1, wherein the organic solvent is contained in an amount of 3 to 16mol per liter of ink.
7. The conductive ink according to claim 1, wherein the organic solvent is one, two or more selected from the group consisting of methanol, ethanol, ethylene glycol, propanol, isopropanol, N-butanol, isobutanol, N-pentanol, N-octanol, acetone, butanone, chloroform, dichloromethane, diethyl ether, dibutyl ether, carbon disulfide, 1-methyl-2-pyrrolidone, N '-dimethylformamide, N' -dimethylacetamide, dimethylsulfoxide, tetrahydrofuran, ethyl acetate, dioxane, acetonitrile, benzene, toluene and xylene.
8. A method of making a photosensitive silver-based conductive ink according to any one of claims 1 to 7 for use with a low power density visible light source, the method comprising: and uniformly mixing a silver precursor, a visible light photosensitive reagent auxiliary agent, a surfactant and an organic solvent to obtain the photosensitive silver-based conductive ink capable of being used under a low-power-density visible light source.
9. The method for preparing the silver conductive structure by light induction forming adopts a light source to directly project a target pattern entirety to an interface of a polymer substrate material and silver-based conductive ink, a silver precursor in the conductive ink in an illumination area is reduced into silver particles, and the silver conductive structure is formed by silver nano particles;
the light induction is one-time light induction, the molding is surface molding, and the silver conductive structure is a two-dimensional silver conductive structure;
the silver-based conductive ink is the photosensitive silver-based conductive ink which can be used under a low-power-density visible light source and is described in any one of claims 1 to 7;
the light source is one, two or three selected from thermoluminescence light sources, gas discharge light sources and solid illumination light sources with the light-emitting wavelength of 415-780 nm;
the optical power density of the light source is 10-1000 mW/cm2；
The diameter of the silver particles is 70-150 nm, the silver particles are uniformly distributed on the polymer substrate material, and the coverage rate of the silver particles is over 80%.
10. The method of producing conductive silver structures by light-induced molding according to claim 9, wherein the polymer base material is at least one selected from the group consisting of the following planar polymer materials and curved polymer materials: parylene, polystyrene, polypropylene, polyethylene, polyvinyl chloride, styrene-methyl methacrylate copolymer, styrene-acrylonitrile copolymer, polymethylmethacrylate, polyurethane, polyarylate, polycarbonate, polyethylene terephthalate, polyethylene naphthalate, poly 4-methylpentene-1, polyimide, polymethylsiloxane, polyethersulfone, bisphenol a sulfone, ABS, soluble polytetrafluoroethylene.
11. The method for preparing a silver conductive structure by photoinduction molding according to claim 10, wherein the planar polymer material is a polymer film material or a polymer plate material;
the curved polymer material is a polymer tubular material.
12. A flexible conductive material is characterized in that the material is a polymer material loaded with a silver structure prepared by silver-based conductive ink through a photoinduction molding method, and then the polymer material is exposed, fused and combined with silver nanoparticles to obtain the flexible conductive material;
the silver-based conductive ink is the photosensitive silver-based conductive ink which can be used under a low-power-density visible light source and is described in any one of claims 1 to 7;
the light-induced forming method is a method for preparing a silver conductive structure by light-induced forming according to claim 9 or 10.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811279202.9A CN111117367B (en) | 2018-10-30 | 2018-10-30 | Photosensitive silver-based conductive ink, method for preparing silver conductive structure by using photosensitive silver-based conductive ink and flexible conductive material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811279202.9A CN111117367B (en) | 2018-10-30 | 2018-10-30 | Photosensitive silver-based conductive ink, method for preparing silver conductive structure by using photosensitive silver-based conductive ink and flexible conductive material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111117367A CN111117367A (en) | 2020-05-08 |
| CN111117367B true CN111117367B (en) | 2021-06-25 |
Family
ID=70484693
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201811279202.9A Active CN111117367B (en) | 2018-10-30 | 2018-10-30 | Photosensitive silver-based conductive ink, method for preparing silver conductive structure by using photosensitive silver-based conductive ink and flexible conductive material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111117367B (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113755059A (en) * | 2021-09-08 | 2021-12-07 | 深圳大学 | Photosensitive resin-based conductive ink and preparation method and application thereof |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4639661B2 (en) * | 2004-06-25 | 2011-02-23 | 東洋インキ製造株式会社 | Method for producing metal fine particle dispersion, conductive ink using metal fine particle dispersion produced by the method, and non-contact type medium |
| CN101511952B (en) * | 2006-08-07 | 2012-07-25 | 印可得株式会社 | Process for preparation of silver nanoparticles, and the compositions of silver ink containing the same |
| CN102120265B (en) * | 2010-01-07 | 2013-04-10 | 中国科学院化学研究所 | Preparation method of colloid of mono-dispersed silver nano particles and nano silver powder and conductive ink thereof |
| SG183138A1 (en) * | 2010-02-05 | 2012-09-27 | Cambrios Technologies Corp | Photosensitive ink compositions and transparent conductors and method of using the same |
| JP5906027B2 (en) * | 2010-07-30 | 2016-04-20 | トッパン・フォームズ株式会社 | Decorative or mirror surface ink composition, base material, and method for producing a base material provided with a metallic silver layer on the surface |
| CN104754875B (en) * | 2015-03-08 | 2018-01-23 | 北京化工大学 | The preparation method of copper@silver metal conducting films and its application on a printed circuit board |
| CN104887535B (en) * | 2015-05-26 | 2017-10-10 | 中国科学院宁波材料技术与工程研究所 | A kind of low volume is shunk, the preparation method of antibiotic dental resin composite materials |
| CN104946022B (en) * | 2015-07-10 | 2018-03-16 | 东北大学 | A kind of high stability agranular type silver base conductive ink and preparation method thereof |
| CN105419488B (en) * | 2015-12-21 | 2018-05-11 | 山东省科学院新材料研究所 | A kind of agranular type silver base conductive ink and preparation method and application |
| CN107312133A (en) * | 2016-04-26 | 2017-11-03 | 中国科学院化学研究所 | A kind of visible light solidifying material and 3D printing device and product for 3D printing |
| CN107502040A (en) * | 2016-06-14 | 2017-12-22 | 中国科学院化学研究所 | A kind of visible-light curing solvent-free type environment-friendly ink composite |
| CN106735290A (en) * | 2016-11-30 | 2017-05-31 | 华南理工大学 | Nano Silver prepared by a kind of utilization reducing sugar low-temperature reduction and preparation method thereof and the application in electrically conductive ink |
| CN106752381A (en) * | 2016-12-02 | 2017-05-31 | 东北大学 | Without particle silver inks water and preparation method thereof and transparent silver-colored conductive film and preparation method thereof |
| CN108610742A (en) * | 2018-04-11 | 2018-10-02 | 重庆市中光电显示技术有限公司 | The preparation method and conducting wire moulding process of electrically conductive ink for touch screen |
-
2018
- 2018-10-30 CN CN201811279202.9A patent/CN111117367B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN111117367A (en) | 2020-05-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN101503174B (en) | Method for cutting graphite alkene by titanium dioxide photocatalysis | |
| Ren et al. | Preparation of a porous NiO array-patterned film and its enhanced electrochromic performance | |
| CN105350043A (en) | Method for preparing high-performance metallic network transparent conducting electrode through metal plating method | |
| CN107170510A (en) | Metal nanometer line-graphene portal structure composite and preparation method thereof | |
| CN111117367B (en) | Photosensitive silver-based conductive ink, method for preparing silver conductive structure by using photosensitive silver-based conductive ink and flexible conductive material | |
| CN102270524A (en) | Silver nano-wire transparent conducting film based on thermoplastic transparent polymer and preparation method thereof | |
| CN101305648B (en) | Light-transmittable electromagnetic wave shielding film, process for producing the same, film for display panel, optical filter for display panel and plasma display panel | |
| ES2859497T3 (en) | Ink compositions comprising nanoparticles | |
| CN106350847B (en) | It is a kind of that Fe is patterned using laser interference induction electrochemical deposition manufacturing cycle3O4The method of nanoparticle | |
| CN112951486B (en) | Embedded polymer/metal grid flexible transparent electrode and preparation method and application thereof | |
| Masuda et al. | Site-selective deposition and micropatterning of visible-light-emitting europium-doped yttrium oxide thin film on self-assembled monolayers | |
| CN109560206A (en) | The thin-film patterning method of Colloidal Quantum Dots | |
| CN101759374B (en) | Preparation method of visible light frequency band left-hand metamaterial based on three-dimensional nano silver tree dendritic structures | |
| Hasabeldaim et al. | Enhanced green luminescence from ZnO nanorods | |
| US20020182890A1 (en) | Manufacturing method of molecular film pattern, molecular film pattern, manufacturing method of semiconductor device, semicondctor device, manufacturing method of electro-optical device, electro-optical device, manufacturing method of electronic device, and electronic apparatus | |
| CN108806885A (en) | Flexible substrates-GO- metal nanometer line compound transparent electricity conductive films and preparation method thereof | |
| Esakki et al. | Influence on the efficiency of dye-sensitized solar cell using Cd doped ZnO via solvothermal method | |
| JP2011159392A (en) | Composition containing silver ultrafine particles and conductive pattern manufacturing method | |
| CN108275667B (en) | A kind of black phosphorus material and the preparation method and application thereof of rare earth compounding modification | |
| CN103204538A (en) | Preparation method of porous ZnO and ZnO/Ag nanometer free-standing film | |
| Chang et al. | Optoelectronic properties of density-controlled ZnO nanopillar arrays | |
| TW518632B (en) | Manufacturing process of cathode plate for nano carbon tube field emission display | |
| Shen | Combining microwave and ultrasound irradiation for rapid synthesis of nanowires: a case study on Pb (OH) Br | |
| US10999934B2 (en) | Metal oxide nanoparticle ink composition, method of producing same, and method of forming conductive layer pattern using same | |
| CN108659818A (en) | The synthetic method of quantum dot and the quantum dot of application synthetic method synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |