CN115171945A - Copper paste for large-area preparation and preparation method - Google Patents
Copper paste for large-area preparation and preparation method Download PDFInfo
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- CN115171945A CN115171945A CN202210608748.4A CN202210608748A CN115171945A CN 115171945 A CN115171945 A CN 115171945A CN 202210608748 A CN202210608748 A CN 202210608748A CN 115171945 A CN115171945 A CN 115171945A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- 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
- H01B13/0016—Apparatus or processes specially adapted for manufacturing conductors or cables for heat treatment
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- 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
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- Nanotechnology (AREA)
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- Condensed Matter Physics & Semiconductors (AREA)
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- Crystallography & Structural Chemistry (AREA)
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- Dispersion Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Conductive Materials (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The invention discloses copper paste capable of being prepared in a large area and a preparation method thereof, wherein the copper paste comprises copper particles and a melting medium, wherein the melting medium is nanoparticles with a melting point of 180-600 ℃. According to the copper paste, the melting medium is arranged, so that a large amount of substances which are easily heated and melted into liquid state can be on the surfaces of the copper particles or among the dried copper particles, the whole copper film can be in a deformable state in the secondary xenon lamp process, the copper film breakage caused by the deformation of the base material can be counteracted, and the copper film can be in a continuous conductive state after cooling; the method can bear secondary xenon lamp sintering, thereby completing the preparation of large-area copper conducting circuits.
Description
Technical Field
The invention relates to the technical field of printing, in particular to copper paste for large-area preparation and a preparation method thereof.
Background
Printing electronics is an emerging technology that combines traditional printing techniques with electronic manufacturing techniques, and is the science and technology of manufacturing electronic devices and systems using traditional printing techniques. Compared with the traditional electronic manufacturing technology, the method comprises the following steps: for vacuum evaporation, photolithography, and the like, the printed electronics technology can greatly simplify the manufacturing process, and a patterned functional layer can be obtained by an additive manufacturing method. Therefore, the greatest features and advantages of printed electronics are low cost, low pollution, large area, high throughput, and the like. Among the printable materials, the printable conductive material (commonly referred to as conductive ink) plays a very important role in electronic devices because it can be used as an electrode, a wire, etc., and thus, its application is very wide. Therefore, the formulation of conductive inks is also the focus of research.
Among the common metal conductive inks, silver ink is the most widely used conductive ink due to its good stability and high conductivity. However, silver conductive ink/paste has two fatal disadvantages, which greatly limits the further development of silver-based conductive ink: (1) the price of silver is relatively high; (2) If the metallic silver is in a humid environment, electromigration and ion migration are particularly likely to occur, which may cause open and short circuits of the lines. The reserves of metallic copper on earth are 1000 times that of silver, so the price is only 1% of that of silver. At the same time, it exhibits very high intrinsic conductivity (slightly lower than silver and higher than gold), which is the second-ranked metal material of conductivity. And under some humid environments, ion migration of copper does not occur. Copper-based conductive inks are therefore a superior alternative to silver-based conductive inks. However, copper, as a conductive particle in the ink, cannot be used in a conventional baking manner because copper is easily oxidized to form insulating copper oxide. Thus, photonic sintering is a good solution for copper inks.
Photonic sintering is the sintering of particles using light radiation (from ultraviolet to infrared). By matching the wavelength of the emitted light with the absorption wavelength of the particles in the ink, the light energy released by the sintering equipment can be fully and effectively absorbed by the particles in the sintering process, thereby greatly improving the sintering efficiency and minimizing the influence on the substrate. The photon sintering comprises infrared sintering, ultraviolet sintering, laser sintering and pulse intense light sintering. These sintering methods have been successfully used for sintering of a variety of electronic inks. At present, the method of laser sintering and pulse strong light sintering has the advantages that the sintering speed is very high, the pulse strong light can complete the sintering only in milliseconds, and the infrared and ultraviolet sintering needs several seconds to dozens of minutes. Since the copper particles absorb light energy and convert the light energy into heat energy, the sintering mode has little damage to the substrate, and therefore, laser sintering and pulse strong light sintering are widely applied in the field of printed flexible electronics.
The xenon lamp sintering technology is one of photon sintering, and the xenon lamp sintering area is much larger than that of laser sintering, so that the xenon lamp sintering technology is more suitable for industrial large-area production. However, for copper paste, the area of a single xenon lamp sintering cannot be made large for reasons of cost and stability. Therefore, large area copper samples are basically produced by sintering and splicing small areas, for example, the xenon lamp area is 25cm x 4cm, and the sample size is 25cm x 8cm, the process can be completed by using the xenon lamp three times, and each time, the area of 25cm x 2c is exposed to secondary xenon lamp sintering. The current copper ink cannot bear secondary sintering, so that the area of a sample is very small, and the large demand of large-area sample preparation cannot be met. Therefore, it is important to develop a copper paste which can withstand the secondary xenon lamp. The reason why the secondary xenon lamp sintering cannot be endured is that the copper particles sintered for the first time are fused into a whole due to the sintering action (the base material is generally flexible PET), and the copper particles are connected to each other to be rigid due to the shrinkage of the base material caused by the heating for the second time, so that a large number of cracks are generated due to the inconsistent expansion and shrinkage of the copper and the base material.
Disclosure of Invention
Aiming at the defects and defects of the prior art, the copper paste for large-area preparation and the preparation method thereof are provided, and secondary xenon lamp sintering can be borne, so that the preparation of large-area copper conducting circuits is completed.
In order to achieve the above object, the present invention provides the following technical solutions.
A copper paste for large-area preparation comprises copper particles and a melting medium, wherein the melting medium is nanoparticles with a melting point of 180-600 ℃.
The invention has the beneficial effects that: according to the copper paste, the melting medium is arranged, so that a large amount of substances which are easily heated and melted into liquid state can be on the surfaces of the copper particles or among the dried copper particles, the whole copper film can be in a deformable state in the secondary xenon lamp process, the copper film breakage caused by the deformation of the base material can be counteracted, and the copper film can be in a continuous conductive state after cooling; the method can bear secondary xenon lamp sintering, thereby completing the preparation of large-area copper conducting circuits.
As an improvement of the invention, the melting medium is metal Sn, copper sulfate, copper chloride and a compound Cu thereof x Cl y Copper nitrate, metal nanoparticles.
A manufacturing method based on the copper paste capable of being prepared in a large area comprises the following steps:
a. mixing copper particles with a melting medium or forming a core-shell structure;
b. placing a mixture of copper particles and a molten medium into a polymer resin solution;
c. the polymer resin solution containing the mixture was printed on a substrate, and the substrate was continuously sintered by a xenon lamp.
As a refinement of the invention, in step a, the molten medium is silver nanoparticles.
As an improvement of the invention, the weight ratio of the copper particles to the silver nanoparticles is 9:1.
As a refinement of the invention, the silver nanoparticles have a diameter of 20nm.
In the step b, a surfactant and a leveling agent are further added to the polymer resin solution.
In step c, the printing is performed on the substrate by screen printing.
In step c, the solvent on the substrate is removed by drying at 25-150 ℃ before continuous sintering.
As a modification of the invention, in step c, the overlap region of the continuous sintering is 50% of the area of single xenon lamp sintering.
Drawings
FIG. 1 is a schematic diagram of the secondary sintering of the present invention.
FIG. 2 is a schematic diagram of the secondary xenon lamp sintering offset stress of the present invention.
Detailed Description
The invention is further explained with reference to the drawings.
Referring to fig. 1 to 2, a copper paste for large area production includes copper particles and a melting medium, wherein the melting medium is nanoparticles having a melting point of 180-600 ℃.
For the present embodiment, the melting medium may be metallic Sn, copper sulfate, copper chloride and Cu complex thereof x Cl y Copper nitrate, metal nanoparticles. The metal nanoparticles can be silver nanoparticles, gold nanoparticles and the like, and after the first sintering, the molten medium serves as a bridge connected among the copper particles. In the second sintering process, the copper particles are heated to cause the melting medium to melt, so that the copper particles can shrink along with the base material, after the temperature drops, the melting medium is cooled and solidified, and the copper particles are connected again to form a conductive channel.
According to the copper paste, the melting medium is arranged, so that a large amount of substances which are easily heated and melted into liquid state can be on the surfaces of the copper particles or among the dried copper particles, the whole copper film can be in a deformable state in the secondary xenon lamp process, the copper film breakage caused by the deformation of the base material can be counteracted, and the copper film can be in a continuous conductive state after cooling; the method can bear secondary xenon lamp sintering, thereby completing the preparation of large-area copper conducting circuits.
The manufacturing method of the copper paste capable of being used for large-area preparation is characterized by comprising the following steps of: the method comprises the following steps:
a. mixing copper particles with a melting medium or forming a core-shell structure; wherein the melting medium is silver nanoparticles, the diameter of the silver nanoparticles is 20nm, and the melting point of the silver nanoparticles is 400 ℃; the weight ratio of the copper particles to the silver nanoparticles is 9:1.
b. Putting the mixture of the copper particles and the molten medium into a polymer resin solution, further adding auxiliary agents such as a surfactant, a flatting agent and the like, and uniformly stirring by three rollers;
c. and printing the polymer resin solution containing the mixture on a base material by adopting a screen printing mode, wherein the base material is PET in the embodiment, drying at 25-150 ℃ to remove the solvent on the base material, and continuously sintering the base material by using a xenon lamp, wherein the overlapped area of the continuous sintering is 50% of the area sintered by using a single xenon lamp.
According to the preparation method, the sintering of the copper paste adopts xenon lamp sintering, the sintering time is short, and the instantaneous energy is large; by arranging the melting medium, the melting medium on the surfaces of copper particles or among the copper particles is easy to melt in the secondary sintering process of the conveyed copper slurry, so that the stress generated in the sintering process is counteracted, the generation of cracks is avoided, and the large-area copper wire can be prepared; the sintering area is a large-area sample and is larger than the effective area of single xenon lamp sintering; the melting medium has better conductivity, the melting temperature is between 180 and 600 ℃, namely the temperature range which can be reached by single xenon lamp sintering, the melting medium can be in a liquid state after reaching the melting temperature, so that the stress generated in the copper film due to the deformation of the base material is counteracted, and in addition, the base material is generally a flexible material and is characterized in that the shrinkage of the film material can be caused by heating; finally, the conductive copper film is obtained, the copper film has no cracking phenomenon, and the resistivity of the copper film is about 7 to 12 times that of the bulk silver.
The above description is only a preferred embodiment of the present invention, and all equivalent changes or modifications of the structure, characteristics and principles described in the present patent application are included in the present patent application.
Claims (10)
1. A copper paste for large-area preparation is characterized in that: comprises copper particles and a melting medium, wherein the melting medium is nanoparticles with a melting point of 180-600 ℃.
2. The copper paste for large area production according to claim 1, wherein: the melting medium is metal Sn, copper sulfate, copper chloride and compound Cu thereof x Cl y Copper nitrate, metal nanoparticles.
3. A method for manufacturing copper paste for large area production according to any one of claims 1 to 2, wherein the method comprises the following steps: the method comprises the following steps:
a. mixing copper particles with a melting medium or forming a core-shell structure;
b. placing a mixture of copper particles and a molten medium into a polymer resin solution;
c. the polymer resin solution containing the mixture was printed on a substrate, and the substrate was continuously sintered by a xenon lamp.
4. The manufacturing method according to claim 3, characterized in that: in step a, the molten medium is silver nanoparticles.
5. The manufacturing method according to claim 4, characterized in that: the weight ratio of the copper particles to the silver nanoparticles was 9:1.
6. The manufacturing method according to claim 4, characterized in that: the diameter of the silver nanoparticles is 20nm.
7. The manufacturing method according to claim 3, characterized in that: in the step b, a surfactant and a leveling agent are further added into the polymer resin solution.
8. The manufacturing method according to claim 3, characterized in that: in step c, the printing is performed on the substrate by screen printing.
9. A method of manufacture according to claim 3, characterized in that: in step c, the solvent on the substrate is removed by baking at 25-150 ℃ before continuous sintering.
10. The manufacturing method according to claim 3, characterized in that: in step c, the overlap region for the continuous sintering is 50% of the area of the single xenon lamp sintering.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210608748.4A CN115171945A (en) | 2022-05-31 | 2022-05-31 | Copper paste for large-area preparation and preparation method |
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| Application Number | Priority Date | Filing Date | Title |
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| CN202210608748.4A CN115171945A (en) | 2022-05-31 | 2022-05-31 | Copper paste for large-area preparation and preparation method |
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| CN115171945A true CN115171945A (en) | 2022-10-11 |
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| CN202210608748.4A Pending CN115171945A (en) | 2022-05-31 | 2022-05-31 | Copper paste for large-area preparation and preparation method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115642000A (en) * | 2022-12-23 | 2023-01-24 | 西北工业大学 | Preparation method of conductive copper paste capable of being subjected to photon sintering |
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| US20080286488A1 (en) * | 2007-05-18 | 2008-11-20 | Nano-Proprietary, Inc. | Metallic ink |
| JP2010277974A (en) * | 2009-06-01 | 2010-12-09 | Dainippon Printing Co Ltd | Conductive thin film substrate, and method of manufacturing the same |
| US20120204950A1 (en) * | 2009-11-02 | 2012-08-16 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Transparent conductive coatings for optoelectronic and electronic devices |
| KR101350507B1 (en) * | 2013-01-09 | 2014-01-17 | (주)쎄미시스코 | Electro-conductive ink comprising metal nano-particle and light sintering method of the same |
| US20180312709A1 (en) * | 2015-10-26 | 2018-11-01 | Korea Research Institute Of Chemical Technology | Ink composition for photonic sintering and method for producing same |
| US20190177565A1 (en) * | 2016-07-28 | 2019-06-13 | National Research Council Of Canada | Copper ink and conductive solderable copper traces produced therefrom |
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| JP2010277974A (en) * | 2009-06-01 | 2010-12-09 | Dainippon Printing Co Ltd | Conductive thin film substrate, and method of manufacturing the same |
| US20120204950A1 (en) * | 2009-11-02 | 2012-08-16 | Yissum Research Development Company Of The Hebrew University Of Jerusalem | Transparent conductive coatings for optoelectronic and electronic devices |
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| US20180312709A1 (en) * | 2015-10-26 | 2018-11-01 | Korea Research Institute Of Chemical Technology | Ink composition for photonic sintering and method for producing same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115642000A (en) * | 2022-12-23 | 2023-01-24 | 西北工业大学 | Preparation method of conductive copper paste capable of being subjected to photon sintering |
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