CN118496706A - Composite ink for laser-induced selective copper metallization and process method - Google Patents
Composite ink for laser-induced selective copper metallization and process method Download PDFInfo
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- CN118496706A CN118496706A CN202410643703.XA CN202410643703A CN118496706A CN 118496706 A CN118496706 A CN 118496706A CN 202410643703 A CN202410643703 A CN 202410643703A CN 118496706 A CN118496706 A CN 118496706A
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- copper
- ink
- laser
- composite ink
- metallization
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- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 102
- 239000010949 copper Substances 0.000 title claims abstract description 100
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 100
- 238000000034 method Methods 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 238000001465 metallisation Methods 0.000 title claims abstract description 53
- 230000008569 process Effects 0.000 title abstract description 31
- 239000002245 particle Substances 0.000 claims abstract description 58
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 57
- 239000005751 Copper oxide Substances 0.000 claims abstract description 56
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 56
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 50
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 49
- 238000002360 preparation method Methods 0.000 claims abstract description 25
- 239000000758 substrate Substances 0.000 claims abstract description 24
- 150000001879 copper Chemical class 0.000 claims abstract description 19
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 17
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 17
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 17
- 230000009467 reduction Effects 0.000 claims abstract description 17
- 239000002184 metal Substances 0.000 claims abstract description 15
- 229910052751 metal Inorganic materials 0.000 claims abstract description 15
- 238000002156 mixing Methods 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 15
- 230000001603 reducing effect Effects 0.000 claims description 15
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 12
- 150000001732 carboxylic acid derivatives Chemical class 0.000 claims description 12
- HFDWIMBEIXDNQS-UHFFFAOYSA-L copper;diformate Chemical compound [Cu+2].[O-]C=O.[O-]C=O HFDWIMBEIXDNQS-UHFFFAOYSA-L 0.000 claims description 11
- -1 alkyl primary amine Chemical class 0.000 claims description 10
- 125000000217 alkyl group Chemical group 0.000 claims description 8
- HHLFWLYXYJOTON-UHFFFAOYSA-N glyoxylic acid Chemical compound OC(=O)C=O HHLFWLYXYJOTON-UHFFFAOYSA-N 0.000 claims description 8
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 7
- 238000011161 development Methods 0.000 claims description 7
- 235000019253 formic acid Nutrition 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 7
- 239000012266 salt solution Substances 0.000 claims description 7
- 238000005245 sintering Methods 0.000 claims description 7
- 150000003141 primary amines Chemical class 0.000 claims description 6
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 5
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 5
- 238000000354 decomposition reaction Methods 0.000 claims description 5
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 5
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 3
- 238000004140 cleaning Methods 0.000 claims description 3
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 3
- 238000005516 engineering process Methods 0.000 claims description 3
- 238000000059 patterning Methods 0.000 claims description 3
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-N Heptylamine Chemical compound CCCCCCCN WJYIASZWHGOTOU-UHFFFAOYSA-N 0.000 claims description 2
- YXKOWHMCBBEJPS-UHFFFAOYSA-L copper;oxaldehydate Chemical compound [Cu+2].[O-]C(=O)C=O.[O-]C(=O)C=O YXKOWHMCBBEJPS-UHFFFAOYSA-L 0.000 claims description 2
- FJDUDHYHRVPMJZ-UHFFFAOYSA-N nonan-1-amine Chemical compound CCCCCCCCCN FJDUDHYHRVPMJZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000006722 reduction reaction Methods 0.000 claims description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims 3
- JACMPVXHEARCBO-UHFFFAOYSA-N n-pentylpentan-1-amine Chemical compound CCCCCNCCCCC JACMPVXHEARCBO-UHFFFAOYSA-N 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 22
- 238000012545 processing Methods 0.000 abstract description 11
- 230000000694 effects Effects 0.000 abstract description 9
- 230000006911 nucleation Effects 0.000 abstract description 7
- 238000010899 nucleation Methods 0.000 abstract description 7
- 230000012010 growth Effects 0.000 abstract description 4
- 230000008018 melting Effects 0.000 abstract description 4
- 238000002844 melting Methods 0.000 abstract description 4
- 230000008878 coupling Effects 0.000 abstract description 3
- 238000010168 coupling process Methods 0.000 abstract description 3
- 238000005859 coupling reaction Methods 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 125000002924 primary amino group Chemical class [H]N([H])* 0.000 abstract 1
- 239000000976 ink Substances 0.000 description 106
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 15
- 230000002829 reductive effect Effects 0.000 description 13
- 238000004528 spin coating Methods 0.000 description 13
- 239000008139 complexing agent Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 239000003638 chemical reducing agent Substances 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 230000009471 action Effects 0.000 description 6
- 238000007639 printing Methods 0.000 description 6
- 239000005361 soda-lime glass Substances 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 5
- 239000000523 sample Substances 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000002835 absorbance Methods 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 235000019441 ethanol Nutrition 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000009210 therapy by ultrasound Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 230000006866 deterioration Effects 0.000 description 2
- 238000004880 explosion Methods 0.000 description 2
- 238000011049 filling Methods 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 229940058020 2-amino-2-methyl-1-propanol Drugs 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical group [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- CBTVGIZVANVGBH-UHFFFAOYSA-N aminomethyl propanol Chemical compound CC(C)(N)CO CBTVGIZVANVGBH-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000003618 dip coating Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000001165 hydrophobic group Chemical group 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
-
- 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
- C09D11/02—Printing inks
- C09D11/03—Printing inks characterised by features other than the chemical nature of the binder
- C09D11/033—Printing inks characterised by features other than the chemical nature of the binder characterised by the solvent
-
- 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
- C09D11/02—Printing inks
- C09D11/10—Printing inks based on artificial resins
- C09D11/106—Printing inks based on artificial resins containing macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Manufacturing Of Printed Wiring (AREA)
Abstract
The invention relates to the technical field of selective metallization, in particular to a composite ink for laser-induced selective copper metallization and a process method thereof, comprising the following steps: s1, mixing self-reducing copper salt, primary amine and volatile organic solvent to prepare copper ion ink; s2, mixing the copper ion ink, copper oxide particles and polyvinylpyrrolidone to prepare the composite ink. According to the copper ion and copper oxide composite ink system, gaps among copper oxide nano particles are filled through copper ion reduction, nucleation, growth and laser-induced melting effects; the copper element content is greatly improved through the introduction of the copper oxide nano particles, and finally, the preparation of a metal copper product with high wire height, low porosity and high conductivity is realized; the composite ink system of the invention can further improve the energy coupling efficiency of laser and substances, improve the processing efficiency and avoid damaging the substrate because the forbidden bandwidth of copper oxide is matched with the wavelength of the main stream near infrared laser light source.
Description
Technical Field
The invention relates to the technical field of selective metallization, in particular to a composite ink for laser-induced selective copper metallization and a process method.
Background
Conductive ink has important roles and roles in the fields of printing electronics, flexible electronics, energy sources, medical treatment and the like. Among the existing conductive inks, metallic copper-based conductive inks are attracting attention due to their excellent conductivity and extremely low cost. However, the inherent oxidation-prone nature of copper places many limitations on conventional thermal sintering processes. Therefore, the laser-based unsteady state induction sintering method is widely focused by academia and industry due to the advantages of no mask, high flexibility, high precision and non-contact, and the copper-based ink suitable for laser-induced metallization also becomes a research hot spot.
In the prior art, copper-based inks suitable for laser-induced metallization mainly include copper ion inks, copper oxide nanoparticle inks, copper nanoparticle inks. Although remarkable research results have been achieved, these solutions still have some problems: (1) The existing copper ion ink has optical absorption peaks in ultraviolet band and 600-700 nm red light band, which puts special requirements on laser light source and rear end optical element. The ultraviolet band laser needs nonlinear frequency multiplication generation, has low conversion efficiency, and is extremely easy to cause etching phenomena of a product and a substrate due to high photon energy of the ultraviolet band. And the red light wave band of 600 nm-700 nm lacks a mature high-performance laser source and a rear end beam shaping, focusing and scanning module. (2) For copper ion ink, the inherent content of copper in copper salt and the restriction of solubility of organic copper salt in solvent lead to lower copper content of copper organic decomposition ink, and the mass loss generated in the decomposition process of the ink, the product is thinner, only hundreds of nanometers, so that the preparation of metal copper products with the height of a plurality of micrometers is difficult to realize, and the macroscopic resistance of the products is severely limited. (3) The existing copper nanoparticle ink is extremely easy to oxidize in the storage and use processes of the copper nanoparticle ink due to the higher activity of the nano copper, so that the cost of the copper nanoparticle ink is higher, the laser-induced metal copper loses the cost advantage relative to the conductive silver paste, and the formed copper surface oxide layer seriously influences the conductivity of a copper film or a copper conductive circuit. (4) The existing copper oxide ink mostly depends on ethylene glycol which is difficult to volatilize as a reducing agent, and under the action of laser, the ethylene glycol can be subjected to local high temperature to generate bumping, so that a large number of holes are generated in a product, the porosity of the product is 10% -30%, a large number of holes exist in the product, the resistivity of the product is usually higher than that of massive copper by 2 orders of magnitude, and the product has no application prospect.
Disclosure of Invention
In view of the above, the invention provides a composite ink for laser-induced selective copper metallization and a process method thereof, which are used for solving the problems that in the existing conductive ink, in the process of preparing a metallic copper product by adopting laser direct writing, a substrate and a product are easy to etch, and the preparation of the metallic copper product with a height of a plurality of micrometers is difficult to realize.
The technical scheme of the invention is realized as follows:
in a first aspect, the invention provides a method for preparing a composite ink for laser-induced selective copper metallization, comprising the steps of:
s1, mixing self-reducing copper salt, long alkyl primary amine and volatile organic solvent to prepare copper ion ink;
S2, mixing the copper ion ink, copper oxide particles and polyvinylpyrrolidone to prepare the composite ink.
In the invention, in the step S1, self-reducing copper salt is decomposed and reduced into metallic copper under the action of laser, long alkyl primary amine is used as a complexing agent, and the copper ion reduction nucleation process can be regulated and controlled, so that the copper particles are smaller in particle size and more uniform in distribution. In the step S2, copper ions are reduced and nucleated to generate particles under the induction of near infrared laser by introducing copper oxide nano particles and copper ion ink for compounding, and then the particles are fused and filled into pores among the copper oxide particles, so that the porosity of a product is reduced, and the conductivity is improved; meanwhile, the forbidden bandwidth (about 1.2 eV) of copper oxide in the composite ink system is matched with the wavelength (1000 nm-1100 nm) of the near infrared laser light source, so that the composite ink has strong absorption in the wavelength range, is beneficial to further improving the energy coupling efficiency of laser and substances, improves the processing efficiency and avoids damaging the substrate. The polyvinylpyrrolidone is used as a dispersing agent of the copper oxide nano particles, hydrophilic groups in molecules are adsorbed on the surfaces of the copper oxide particles, hydrophobic groups extend to a solvent, and the particle agglomeration is prevented by the steric hindrance, so that the dispersing and stabilizing effects are achieved. Simultaneously, under the action of laser, polyvinylpyrrolidone can be used as a reducing agent of copper oxide particles. The volatile organic solvent is used as the solvent of the composite ink, can be completely removed by heating before laser processing, avoids micro-explosion of the solvent during laser processing, and reduces the porosity of the product.
Based on the technical scheme, preferably, the mol ratio of the self-reducing copper salt to the long alkyl primary amine is 1:1.5-2.5, and the concentration of copper ions in the copper ion ink is 1-5mol/L.
By adjusting the mole ratio (1:1.5-2.5) of the self-reducing copper salt and the long alkyl primary amine, the complexing degree of copper ions can be optimized, so that not only can enough copper sources be ensured, but also the reduction nucleation process can be controlled, and the metallic copper product with excellent performance can be obtained. The concentration of copper ions is selected to be in the range of 1-5mol/L, and the concentration is high enough, so that the deposition rate of metallic copper and the thickness of a product are improved; however, the concentration should not be too high, which would affect the stability and fluidity of the ink.
On the basis of the technical scheme, preferably, the self-reducing copper salt comprises copper formate or copper glyoxylate, and the long alkyl primary amine comprises one or more of organic primary amines with the alkyl chain length of more than or equal to 5; the volatile organic solvent comprises a volatile alcohol solvent with a boiling point less than or equal to 85 ℃.
In the invention, long alkyl primary amine with the alkyl chain length more than or equal to 5 is used as a complexing agent, and the long alkyl primary amine and copper ions form coordination bonds to generate a relatively stable copper-amine complex, so that the coordination strength is moderate, copper ions can be effectively complexed, and the complex is not excessively stable to cause difficult reduction. The long alkyl chain in the long alkyl primary amine has a steric hindrance effect, and the reduction nucleation speed of copper ions can be controlled. When the copper ions are reduced, long chain alkyl groups form a protective layer around the copper cores, which prevents further growth of the copper cores, thereby obtaining copper nanoparticles with smaller size and more uniform distribution.
On the basis of the technical scheme, preferably, the preparation method of the self-reducing copper salt comprises the following steps: mixing copper metal salt solution and reducing carboxylic acid solution, reacting for 6-12h at 24-28 ℃, and removing solvent to obtain self-reducing copper salt, wherein the pH value of the reducing carboxylic acid solution is 6-8.
Specifically, copper metal salt is dissolved in deionized water to form copper metal salt solution, and reductive carboxylic acid is dissolved in deionized water to form reductive carboxylic acid solution, and the pH value of the reductive carboxylic acid solution is adjusted to 6-8 by using 15-25 wt% of sodium hydroxide solution. The pH of the solution of the reducing carboxylic acid is controlled within a neutral range of 6-8. On the one hand, the neutral environment is favorable for the dissolution and reaction of copper salt; on the other hand, too high a pH value affects the stability of the self-reducing copper salt. On the basis of the technical scheme, preferably, the concentration of the copper metal salt solution is 0.5-1mol/L, and the copper metal salt solution comprises one or more of a copper sulfate solution, a copper nitrate solution and a copper chloride solution; the concentration of the reducing carboxylic acid solution is 1-2mol/L, and the reducing carboxylic acid solution comprises formic acid solution and/or glyoxylic acid solution.
Both formic acid and glyoxylic acid have reducing properties, and they are self-reducing with copper salts formed from copper ions and are capable of self-decomposing under heating to produce metallic copper. On the basis of the technical scheme, preferably, the copper oxide particles are spherical and/or flaky, and the particle size of the copper oxide particles is 20 nm-2 mu m.
Specifically, under near infrared laser irradiation, copper ions are reduced and nucleated to form nano-scale copper particles, and filled into pores among the copper oxide particles in a molten state. The ink prepared by the spherical copper oxide nano particle morphology has better fluidity, and the flaky copper oxide nano particle ink has better conductivity. The particle size range of 20 nm-2 mu m is selected, so that good balance can be achieved in the aspects of cost, dispersibility, optical property, filling effect, rheological property and the like. When the particle size is too small (< 20 nm), the nano particles are easy to agglomerate, the preparation process is complex and difficult, and the cost is high; when the particle diameter is too large (> 2 μm), the particle diameter of the particles becomes large, the specific surface area is reduced, the reduction efficiency is lowered, and the rheological property and the coating quality of the ink may be affected, which is difficult to apply to high-precision application scenes.
On the basis of the technical scheme, preferably, in the composite ink, the copper ion ink is 20-70%, the copper oxide particles are 20-60% and the polyvinylpyrrolidone is 10-20% in percentage by mass.
The higher content of the copper oxide particles is beneficial to improving the copper element content in the ink, reducing the volume shrinkage and the mass loss during laser induction, but the excessively high content leads to the enhancement of the interaction force among the particles, the increase of the viscosity of the ink, the poor fluidity and the disadvantage of obtaining a uniform and flat coating by printing.
The polyvinylpyrrolidone plays roles of a copper oxide dispersing agent and a reducing agent in the ink, the too high polyvinylpyrrolidone content can cause the reduction of copper element content and the waste of polyvinylpyrrolidone, and the too low polyvinylpyrrolidone content can cause the deterioration of copper oxide nano-particle dispersibility, the easy agglomeration of particles and the insufficient laser-induced reduction.
The copper ion ink content is one of the sources of copper in the ink and determines the copper element content. And at the same time, as a main liquid phase component in the ink, determines the fluidity of the ink. Too low a copper ion ink content causes deterioration in ink fluidity. Meanwhile, the copper element in the copper ion ink is far lower than copper oxide particles, so that the copper element content in the ink is reduced due to the excessively high copper ion ink content.
In a second aspect, the invention provides a composite ink prepared by the preparation method described in any one of the above.
In a third aspect, the invention provides the use of a composite ink for the preparation of a selective copper metallization product, the preparation method comprising the steps of:
A1, uniformly forming a film on a target substrate by adopting a solution forming technology, and performing pre-baking to remove an organic solvent, wherein the pre-baking parameter is 60-80 ℃ for 5-15 min; the solution forming technique includes: solution forming methods such as spin coating, drop coating, dip coating, ink jet printing, screen printing and the like; the substrate material can be silicon wafer, quartz wafer, sapphire wafer, polyimide, soda lime glass and the like;
And A2, performing patterning direct writing on the ink film by adopting a laser induction method to induce the decomposition, reduction and sintering of the ink, and then performing cleaning and development to obtain a patterned selective copper metallization product. For heat sensitive substrates, the product after washing development can be used directly. For high temperature resistant substrates, the present invention can further improve product chemistry, porosity, and conductivity by a subsequent heat treatment. Wherein, the later heat treatment specifically comprises: carrying out the subsequent heat treatment on the metallic copper product obtained after the cleaning and developing in a specific atmosphere environment; the special atmosphere environment is an atmosphere environment of argon, nitrogen, hydrogen, argon-hydrogen mixed gas, nitrogen-hydrogen mixed gas and the like; the heat treatment temperature is 300-400 ℃, and the heat treatment time is more than or equal to 10min.
According to the copper ion and copper oxide composite ink system, gaps among copper oxide particles are filled through copper ion reduction, nucleation, growth and laser-induced melting effects; the copper element content is greatly improved by introducing copper oxide particles, and finally, the preparation of the metal copper product with high wire height, low porosity and high conductivity is realized. The method realizes the uniform coating and film forming of the printing ink by a solution forming technology, and then directly writes conductive copper metallization patterns on the printing ink film by utilizing the selective reduction and sintering effect induced by laser. The method is simple to operate, does not need a mask, can realize the rapid and flexible preparation of the copper metallization pattern, and has higher resolution and selectivity. Meanwhile, the invention can also directly form a pattern by a patterning printing means, and the pattern is directly scanned during laser-induced reduction, so that the waste of ink is reduced. The invention has wide application prospect in the fields of flexible electronics, printed electronics and the like.
On the basis of the above technical solution, preferably, in step A2, the parameters of the laser induction method specifically include: the laser center wavelength is the near infrared band of 1000 nm-1100 nm, the laser pulse width is more than or equal to 100fs, the repetition frequency is more than or equal to 500KHz, the laser power is more than or equal to 50mW, and the scanning speed is more than or equal to 1mm/s. The laser pulse width and the laser repetition frequency which are too small can cause the laser single pulse energy to be too high and the peak power to be too high, so that the generated copper product is etched under the action of a plurality of laser pulses, and the low pulse width and the low repetition frequency are not beneficial to the temperature accumulation at the laser focus and the ink decomposition. The scanning speed lower than 1mm/s is low in efficiency and has no practical significance, and the laser power is insufficient to realize good laser-induced reduction sintering at the scanning speed of more than or equal to 1mm/s.
The forbidden bandwidth of copper oxide in the composite ink system is about 1.2eV, and the corresponding photon energy is matched with near infrared laser with the wavelength of 1000-1100 nm. The energy band structure matching can obviously improve the absorption efficiency of the ink to near infrared light, promote the transition of electrons between a valence band and a conduction band, thereby accelerating the generation of photo-generated carriers and the photo-thermal conversion process, improving the efficiency of laser induced reduction and sintering, reducing the light energy loss, reducing the energy permeation to a substrate and avoiding the damage to the substrate.
Compared with the prior art, the composite ink for laser-induced selective copper metallization and the process method have the following beneficial effects:
(1) According to the copper ion and copper oxide composite ink system, gaps among copper oxide particles are filled through copper ion reduction, nucleation, growth and laser-induced melting effects; the copper element content is greatly improved through the introduction of copper oxide particles, and finally, the preparation of a metal copper product with high wire height, low porosity and high conductivity is realized;
(2) Primary amine complexing agents with long alkyl chains are adopted to regulate the reduction nucleation process of copper ions, so that the particle size of the copper ions is smaller and more uniform, the melting under the action of laser is facilitated, and the filling action of the copper ions on pores is enhanced;
(3) Copper oxide is adopted as solid phase particles to be introduced into the copper ion ink, and compared with copper nano particles, the method has the advantages of low cost and easiness in storage and transportation;
(4) The composite ink system of the invention has strong absorption in the wavelength range because the forbidden bandwidth of copper oxide (about 1.2 eV) is matched with the wavelength (1000 nm-1100 nm) of the main stream near infrared laser light source, thereby being beneficial to further improving the energy coupling efficiency of laser and substances, improving the processing efficiency and avoiding damaging the substrate;
(5) According to the invention, the reducing agent and the solvent system in the existing printing ink are optimized, so that the use of a high-boiling point solvent and the reducing agent is avoided, the volatile solvent is removed through a pre-baking process, the micro-explosion phenomenon of the focal position in laser processing is relieved, and the porosity in the product is greatly reduced.
Drawings
In order to more clearly illustrate the embodiments of the invention or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described, it being obvious that the drawings in the following description are only some embodiments of the invention, and that other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is a schematic illustration of a process for preparing a composite ink and copper metallization product for laser induced selective copper metallization in accordance with the present invention;
FIG. 2 is a diagram of a copper metallization product prepared in example 3 of the present invention.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical aspects of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the present invention without making any inventive effort, are intended to fall within the scope of the present invention.
Example 1
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the composite ink comprises the following steps:
(1) Preparing copper sulfate into 1mol/L solution A and anhydrous formic acid into 2mol/L solution B; adjusting the pH value of the solution B to 6-8 by adopting 20wt% sodium hydroxide; mixing the solution A and the solution B according to equal volume, and stirring for 6 hours; concentrating the mixed solution by heating and evaporating, and removing the solvent by filtering and vacuum drying to obtain solid copper formate;
(2) 2mmol of copper formate and 4mmol of isopropylamine are taken as complexing agents and added into 1ml of isopropanol, and then magnetic stirring is carried out for 12 hours (the rotating speed is 800 rpm), so that copper ion ink is obtained; 1.2g of micron-sized spherical copper oxide particles (particle size of 2 μm) and 0.5g of polyvinylpyrrolidone were added, and the mixture was sonicated in a water bath for 30 minutes to obtain a composite ink.
(3) And uniformly forming a film on the soda-lime glass substrate by adopting a spin coating mode, and performing pre-baking, wherein the spin coating speed is 2000rpm, the time is 30s, and the pre-baking temperature is 80 ℃ and the time is 10min.
(4) The laser-induced ink film is selectively metallized by using an infrared skin second laser with the pulse width of 1064nm, the pulse width of 10ps and the repetition frequency of 2MHz, and the laser power is 2W and the scanning speed is 1mm/s. After the processing is completed, the substrate is placed in absolute ethyl alcohol for development for 30min, then is rinsed for 5s by deionized water, and is dried by argon. And (3) putting the obtained product into a mixed gas of 95% and 5% of argon and hydrogen to perform a subsequent heat treatment at 400 ℃ for 30min, so as to obtain a patterned selective copper metallization product.
Example 2
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the specific preparation method is the same as embodiment 1, and the difference is that: in the step (2), the complexing agent is octylamine.
Example 3
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method thereof, wherein the preparation method is shown in fig. 1, and the specific preparation method is the same as that of embodiment 2, and the difference is that: in the step (2), the copper oxide particles are nano spherical particles with the particle size of 100nm, and the prepared copper metallization product is shown in figure 2.
Example 4
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the composite ink comprises the following steps:
(1) Preparing copper sulfate into 0.5mol/L solution A and preparing anhydrous formic acid into 1mol/L solution B; adjusting the pH value of the solution B to 6-8 by adopting 20wt% sodium hydroxide; mixing the solution A and the solution B according to equal volume, and stirring for 8 hours at 25 ℃; concentrating the mixed solution by heating and evaporating, and removing the solvent by filtering and vacuum drying to obtain solid copper formate;
(2) 2mmol of copper formate and 3mmol of octylamine are taken as complexing agents and added into 2ml of isopropanol, and then magnetic stirring is carried out for 12 hours (the rotating speed is 800 rpm), so as to obtain 2.27g of copper ion ink; 6.81g of nano-scale spherical copper oxide particles (particle size is 20 nm) and 2.27g of polyvinylpyrrolidone are added, and water bath ultrasonic treatment is adopted for 30min to obtain the composite ink, wherein the copper ion ink in the composite ink accounts for 20wt%, the copper oxide particles account for 60wt% and the polyvinylpyrrolidone accounts for 20wt%.
(3) And uniformly forming a film on the soda-lime glass substrate by adopting a spin coating mode, and performing pre-baking, wherein the spin coating speed is 2000rpm, the time is 30s, and the pre-baking temperature is 60 ℃ and the time is 5min.
(4) The selective metallization is carried out by adopting an infrared skin second laser induced ink film with 1030nm, a pulse width of 400fs and a repetition frequency of 500KHz, the laser power is 50mW, and the scanning speed is 3mm/s. After the processing is completed, the substrate is placed in absolute ethyl alcohol for development for 30min, then is rinsed for 5s by deionized water, and is dried by argon. And (3) placing the obtained product in an argon-hydrogen mixed gas with the volume percentage of 95% and 5% for 300 ℃ and carrying out the subsequent heat treatment for 10min to obtain the patterned selective copper metallization product.
Example 5
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the composite ink comprises the following steps:
(1) Preparing 0.8mol/L solution A from copper chloride and 1.5mol/L solution B from anhydrous formic acid; adjusting the pH value of the solution B to 6-8 by adopting 20wt% sodium hydroxide; mixing the solution A and the solution B according to equal volume, and stirring for 12 hours at 25 ℃; concentrating the mixed solution by heating and evaporating, and removing the solvent by filtering and vacuum drying to obtain solid copper formate;
(2) 2mmol of copper formate and 5mmol of hexylamine are taken as complexing agents and added into 0.4ml of isopropanol, and then magnetic stirring is carried out for 12 hours (the rotating speed is 800 rpm), so as to obtain 1.13g of copper ion ink; adding 0.32g of nano-scale spherical copper oxide particles (with the particle size of 200 nm) and 0.16g of polyvinylpyrrolidone, and performing water bath ultrasonic treatment for 30min to obtain the composite ink, wherein the copper ion ink in the composite ink accounts for 70wt%, the copper oxide particles account for 20wt% and the polyvinylpyrrolidone accounts for 10wt%.
(3) And uniformly forming a film on the soda-lime glass substrate by adopting a spin coating mode, and performing pre-baking, wherein the spin coating speed is 2000rpm, the time is 30s, and the pre-baking temperature is 70 ℃ and the time is 15min.
(4) Selective metallization was performed using 1030nm, 10ps pulse width, 2MHz repetition rate of the red skin second laser induced ink film, 2W laser power, and 1mm/s scan speed. After the processing is completed, the substrate is placed in absolute ethyl alcohol for development for 30min, then is rinsed for 5s by deionized water, and is dried by argon. And (3) putting the obtained product into an argon-hydrogen mixed gas with the volume percentage of 95% and 5% to perform the subsequent heat treatment for 30min at the temperature of 350 ℃ so as to obtain the patterned selective copper metallization product.
Example 6
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the specific preparation method is the same as embodiment 3, and the difference is that: in the step (1), copper nitrate is taken to prepare 1mol/L solution A, and glyoxylic acid is taken to prepare 1mol/L solution B; in the step (2), the complexing agent is nonylamine, and the organic solvent is ethanol.
Example 7
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the specific preparation method is the same as embodiment 3, and the difference is that: preparing copper chloride into 0.5mol/L solution A in the step (1); in the step (2), the complexing agent is heptylamine, and the organic solvent is ethanol.
Example 8
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the specific preparation method is the same as embodiment 3, and the difference is that: the copper oxide particles in the step (2) are nanoscale flaky particles.
Example 9
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the specific preparation method is the same as embodiment 3, and the difference is that: the copper oxide particles in the step (2) are nanoscale rod-shaped particles.
Example 10
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the specific preparation method is the same as embodiment 3, and the difference is that: the addition amount of the copper oxide particles in the step (2) is 2.5g, namely, the addition amount of the copper oxide particles accounts for 80 percent.
Example 11
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the specific preparation method is the same as embodiment 3, and the difference is that: the addition amount of the copper oxide particles in the step (2) is 0.32g, namely, the addition amount of the copper oxide particles accounts for 10 percent.
Example 12
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, and the specific preparation method is the same as embodiment 3, and the difference is that: in the step (2), the addition amount of copper formate was 2mmol, and the addition amount of octylamine was 8mmol.
Example 13
The embodiment provides a composite ink for laser-induced selective copper metallization and a process method, which are different from embodiment 3 in that: there is no subsequent heat treatment step. The present embodiment can be compatible with thermally sensitive substrates.
Comparative example 1
The comparative example provides pure copper ion ink and a process method, and specifically comprises the following steps:
(1) Preparing copper sulfate into 1mol/L solution A and anhydrous formic acid into 2mol/L solution B; adjusting the pH value of the solution B to 6-8 by adopting 20wt% sodium hydroxide; mixing the solution A and the solution B according to equal volume, and stirring for 6 hours; concentrating the mixed solution by heating and evaporating, and removing the solvent by filtering and vacuum drying to obtain solid copper formate;
(2) 2mmol of copper formate, 2mmol of 2-amino-2-methyl-1-propanol and 2mmol of octylamine were taken as complexing agents and added to 1ml of isopropanol, followed by magnetic stirring for 12 hours (rotation speed of 800 rpm) to prepare a copper ion ink solution. The metal salt in this comparative example contains a reducing formic acid group, so no additional reducing agent is required;
(3) And uniformly forming a film on the soda-lime glass substrate by adopting a spin coating mode, and performing pre-baking, wherein the spin coating speed is 3000rpm, the time is 30s, and the pre-baking temperature is 80 ℃ and the time is 10min.
(4) Selectively metallizing the near infrared femtosecond laser induced ink film with 1030nm, 100fs pulse width and 80MHz repetition frequency at the scanning speed of 1mm/s with 70mW laser power; after the processing is finished, the substrate is placed in absolute ethyl alcohol to be developed for 30min, then deionized water is used for washing for 5s, and argon is used for drying; and (3) putting the obtained product into a mixed gas of 95% and 5% of argon and hydrogen to perform a subsequent heat treatment at 400 ℃ for 30min, so as to obtain a patterned selective copper metallization product.
Comparative example 2
The comparative example provides copper oxide nanoparticle ink and a process method, and the specific operation steps are as follows:
(1) Copper oxide spherical nano particles (50 wt%) (average particle diameter is 20-30 nm), polyvinylpyrrolidone (16 wt%) is used as a dispersing agent, ethylene glycol (34 wt%) is used as a solvent and a reducing agent, and the copper oxide spherical nano particles are dispersed in a water bath for 30min by ultrasonic treatment to obtain copper oxide nano particle ink;
(2) And uniformly forming a film on the soda-lime glass substrate by adopting a spin coating mode, and performing pre-baking, wherein the spin coating speed is 1500rpm, the time is 30s, and the pre-baking temperature is 80 ℃ and the time is 10min.
(3) The ink film is selectively metallized by adopting 1030nm, the pulse width is 100fs, the repetition frequency is 80MHz femtosecond laser to induce the ink film, the laser power is 50mW, and the scanning speed is 1mm/s. After the processing is completed, the substrate is placed in absolute ethyl alcohol for development for 30min, then is rinsed for 5s by deionized water, and is dried by argon. And (3) putting the obtained product into a mixed gas of 95% and 5% of argon and hydrogen to perform a subsequent heat treatment at 400 ℃ for 30min, so as to obtain a patterned selective copper metallization product.
Comparative example 3
The comparative example provides a composite ink for laser-induced selective copper metallization and a process method, and the specific preparation method is the same as that of example 3, and the difference is that: and (3) a composite ink system using ethylene glycol to replace isopropanol as a solvent in the step (2).
Performance detection
1. Line height test
The line heights of the copper metallization products prepared in examples 1-12 and comparative examples 1-3 were measured using a DektakXT probe type surface profiler.
2. Conductivity function detection
The resistances of the copper metallization products prepared in examples 1 to 12 and comparative examples 1 to 3 were measured by a four-probe analysis method using a semiconductor analyzer B1500A, and sample geometric information was obtained by a microscope and DektakXT probe type surface profiler, and the sample resistivity was calculated.
3. Porosity measurement
The surfaces of the copper metallization products prepared in examples 1 to 12 and comparative examples 1 to 3 were imaged using a Nova NanoSEM 450FP2053/45 thermal field emission scanning electron microscope, and the test pictures were analyzed for porosity based on ImageJ software.
4. Absorption rate test
The ink films of examples 1 to 12 and comparative examples 1 to 3 were obtained by spin-coating a film on a JGS2 quartz substrate of 20 mm. Times.20 mm. Times.1 mm by a spin-coating method, and then subjecting to pre-baking. Film thickness was measured based on a contact step-meter DektakXT, and film absorbance was measured with a SolidSpec-3700 ultraviolet-visible near infrared spectrophotometer. Absorbance was normalized to a thickness of 10 microns according to film thickness and converted to absorbance according to a defined formula.
The detection results are shown in Table 1.
TABLE 1
As shown in Table 1, the copper metal structure wire heights of examples 3-8 prepared by using the copper ion and copper nanoparticle composite ink are significantly improved compared with the copper ion ink of comparative example 1, and the porosity of the copper ion ink is significantly reduced compared with the copper oxide nanoparticle ink of comparative example 2. Comparative example 3 compared with example 3, the use of a volatile solvent instead of ethylene glycol is advantageous in reducing the porosity and improving the resistivity. Examples 3 to 8 have significantly improved optical absorptance at 1064nm as compared with comparative example 1. Examples 1-3 compare that the chain length of the primary amine and the particle size of the copper oxide have a significant impact on the product resistivity and pore size, with long alkyl chains and nanoscale particle sizes being more conducive to achieving highly conductive and highly dense products. Comparison of examples 8 and 9 with example 3 shows that the morphology of the copper oxide particles also has a significant effect on the conductivity of the product, and comparison of examples 10 and 11 with example 3 shows that the addition of copper oxide particles has a significant effect on the line height, resistivity, porosity and light absorptivity of the product; example 12 compares with example 3 and shows that the ratio of self-reducing copper salt and complexing agent of the present application is more advantageous for highly conductive and highly dense products.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.
Claims (10)
1. A preparation method of a composite ink for laser-induced selective copper metallization is characterized by comprising the following steps: the method comprises the following steps:
S1, mixing self-reducing copper salt, primary amine and volatile organic solvent to prepare copper ion ink, wherein the primary amine comprises one or more of long alkyl organic primary amines with the alkyl chain length of more than or equal to 5, and the volatile organic solvent is a solvent with the boiling point of less than or equal to 85 ℃;
S2, mixing the copper ion ink, copper oxide particles and polyvinylpyrrolidone to prepare the composite ink.
2. A method of preparing a composite ink for laser induced selective copper metallization as defined in claim 1, wherein: the self-reducing copper salt comprises copper formate or copper glyoxylate, and the long alkyl primary amine comprises one or more of octylamine, nonylamine, heptylamine, hexylamine and dipentylamine; the organic solvent includes one of methanol, ethanol and isopropanol.
3. A method of preparing a composite ink for laser induced selective copper metallization as defined in claim 1, wherein: the mol ratio of the self-reducing copper salt to the long alkyl primary amine is 1:1.5-2.5, and the copper ion concentration in the copper ion ink is 1-5mol/L.
4. A method of preparing a composite ink for laser induced selective copper metallization as defined in claim 1, wherein: the preparation method of the self-reducing copper salt comprises the following steps: mixing copper metal salt solution and reducing carboxylic acid solution, reacting for 6-12h at 24-28 ℃, and removing solvent to obtain self-reducing copper salt, wherein the pH value of the reducing carboxylic acid solution is 6-8.
5. The method for preparing the composite ink for laser-induced selective copper metallization according to claim 4, wherein the method comprises the following steps: the concentration of the copper metal salt solution is 0.5-1mol/L, and the copper metal salt solution comprises one or more of a copper sulfate solution, a copper nitrate solution and a copper chloride solution; the concentration of the reducing carboxylic acid solution is 1-2mol/L, and the reducing carboxylic acid solution comprises formic acid solution and/or glyoxylic acid solution.
6. A method of preparing a composite ink for laser induced selective copper metallization as defined in claim 1, wherein: the copper oxide particles are spherical and/or flaky, and the particle size of the copper oxide particles is 20 nm-2 mu m.
7. A method of preparing a composite ink for laser induced selective copper metallization as defined in claim 1, wherein: in the step S2, in the composite ink, the copper ion ink accounts for 20-70%, the copper oxide particles account for 20-60% and the polyvinylpyrrolidone accounts for 10-20% in percentage by mass.
8. A composite ink, characterized in that: a composite ink for laser induced selective copper metallization according to any one of claims 1 to 7.
9. Use of a composite ink according to claim 8, wherein: the composite ink is used for preparing a selective copper metallization product, and the preparation method comprises the following steps of:
A1, uniformly forming a film on a target substrate by adopting a solution forming technology, and performing pre-baking to remove an organic solvent, wherein the parameters of the pre-baking are 60-80 ℃ for 5-15 min;
And A2, performing patterning direct writing on the ink film by adopting a laser induction method to induce the decomposition, reduction and sintering of the ink, and then performing cleaning development and subsequent heat treatment to obtain a patterned selective copper metallization product.
10. Use of a composite ink according to claim 9, wherein: in step A2, the parameters of the laser induction method specifically include: the laser center wavelength is the near infrared band of 1000 nm-1100 nm, the laser pulse width is more than or equal to 100fs, the repetition frequency is more than or equal to 500KHz, the laser power is more than or equal to 50mW, and the scanning speed is more than or equal to 1mm/s.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013466A (en) * | 2006-07-04 | 2008-01-24 | Seiko Epson Corp | Copper formate complex, method for producing copper particle and method for producing circuit board |
| CN104185880A (en) * | 2012-03-28 | 2014-12-03 | 富士胶片株式会社 | Liquid composition, copper metal film, conductive wiring line, and method for producing copper metal film |
| US20180103546A1 (en) * | 2007-05-24 | 2018-04-12 | Ncc Nano, Llc | Method for Reducing Thin Films on Low Temperature Substrates |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2008013466A (en) * | 2006-07-04 | 2008-01-24 | Seiko Epson Corp | Copper formate complex, method for producing copper particle and method for producing circuit board |
| US20180103546A1 (en) * | 2007-05-24 | 2018-04-12 | Ncc Nano, Llc | Method for Reducing Thin Films on Low Temperature Substrates |
| CN104185880A (en) * | 2012-03-28 | 2014-12-03 | 富士胶片株式会社 | Liquid composition, copper metal film, conductive wiring line, and method for producing copper metal film |
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