CN114023511A - Method for preparing high-temperature electronic paste based on organic phosphorus salt - Google Patents
Method for preparing high-temperature electronic paste based on organic phosphorus salt Download PDFInfo
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- CN114023511A CN114023511A CN202111334245.4A CN202111334245A CN114023511A CN 114023511 A CN114023511 A CN 114023511A CN 202111334245 A CN202111334245 A CN 202111334245A CN 114023511 A CN114023511 A CN 114023511A
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- 238000000034 method Methods 0.000 title claims abstract description 29
- 150000003017 phosphorus Chemical class 0.000 title claims abstract description 21
- 239000000843 powder Substances 0.000 claims abstract description 84
- 239000011521 glass Substances 0.000 claims abstract description 53
- 239000002002 slurry Substances 0.000 claims abstract description 32
- 239000002245 particle Substances 0.000 claims abstract description 25
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 17
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 14
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 9
- 239000011259 mixed solution Substances 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 239000003960 organic solvent Substances 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims description 6
- 239000001856 Ethyl cellulose Substances 0.000 claims description 6
- ZZSNKZQZMQGXPY-UHFFFAOYSA-N Ethyl cellulose Chemical group CCOCC1OC(OC)C(OCC)C(OCC)C1OC1C(O)C(O)C(OC)C(CO)O1 ZZSNKZQZMQGXPY-UHFFFAOYSA-N 0.000 claims description 6
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 6
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 6
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 6
- 238000000498 ball milling Methods 0.000 claims description 6
- 239000003638 chemical reducing agent Substances 0.000 claims description 6
- 239000007822 coupling agent Substances 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 6
- 229910021641 deionized water Inorganic materials 0.000 claims description 6
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-terpineol Natural products CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 6
- 239000002270 dispersing agent Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229920001249 ethyl cellulose Polymers 0.000 claims description 6
- 235000019325 ethyl cellulose Nutrition 0.000 claims description 6
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 6
- 238000010791 quenching Methods 0.000 claims description 6
- 230000000171 quenching effect Effects 0.000 claims description 6
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims description 6
- 229940116411 terpineol Drugs 0.000 claims description 6
- 239000002562 thickening agent Substances 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 claims description 4
- 229910052681 coesite Inorganic materials 0.000 claims description 4
- 229910052906 cristobalite Inorganic materials 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000000377 silicon dioxide Substances 0.000 claims description 4
- 229910052709 silver Inorganic materials 0.000 claims description 4
- 239000004332 silver Substances 0.000 claims description 4
- 229910052682 stishovite Inorganic materials 0.000 claims description 4
- 229910052905 tridymite Inorganic materials 0.000 claims description 4
- 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 2
- 239000011668 ascorbic acid Substances 0.000 claims description 2
- 235000010323 ascorbic acid Nutrition 0.000 claims description 2
- 229960005070 ascorbic acid Drugs 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 239000011347 resin Substances 0.000 claims description 2
- 229920005989 resin Polymers 0.000 claims description 2
- 238000005119 centrifugation Methods 0.000 claims 1
- -1 n-hexyl-3-methylimidazole hexafluorophosphate Chemical compound 0.000 abstract description 12
- 230000004048 modification Effects 0.000 abstract description 7
- 238000012986 modification Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 6
- 239000012071 phase Substances 0.000 description 44
- 238000002360 preparation method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 7
- PSLIMVZEAPALCD-UHFFFAOYSA-N ethanol;ethoxyethane Chemical compound CCO.CCOCC PSLIMVZEAPALCD-UHFFFAOYSA-N 0.000 description 4
- 238000002715 modification method Methods 0.000 description 4
- 238000007639 printing Methods 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- FUJCRWPEOMXPAD-UHFFFAOYSA-N Li2O Inorganic materials [Li+].[Li+].[O-2] FUJCRWPEOMXPAD-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 229910003069 TeO2 Inorganic materials 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- XUCJHNOBJLKZNU-UHFFFAOYSA-M dilithium;hydroxide Chemical compound [Li+].[Li+].[OH-] XUCJHNOBJLKZNU-UHFFFAOYSA-M 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000007650 screen-printing Methods 0.000 description 1
- 238000004513 sizing Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- LAJZODKXOMJMPK-UHFFFAOYSA-N tellurium dioxide Chemical compound O=[Te]=O LAJZODKXOMJMPK-UHFFFAOYSA-N 0.000 description 1
- 125000005147 toluenesulfonyl group Chemical group C=1(C(=CC=CC1)S(=O)(=O)*)C 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
- H01B1/14—Conductive material dispersed in non-conductive inorganic material
- H01B1/16—Conductive material dispersed in non-conductive inorganic material the conductive material comprising metals or alloys
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Dispersion Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Inorganic Chemistry (AREA)
- Conductive Materials (AREA)
Abstract
The invention discloses a method for preparing high-temperature electronic paste based on organic phosphorus salt. According to the invention, the conductive phase powder is subjected to surface modification by using n-hexyl-3-methylimidazole hexafluorophosphate (NHIHP), so that the dispersibility and the bonding strength of the conductive powder are improved; the high-temperature electronic paste comprises the following components in parts by weight: 7-12 parts of a novel slurry carrier, 78-90 parts of conductive powder with different particle sizes and 3-5 parts of a glass phase. According to the invention, the NHIHP is combined with the surface of the conductive phase, so that the slurry particles are uniformly distributed, the bonding strength among the conductive particles can be enhanced, a compact film is formed, the components are environment-friendly, the conductive effect of the slurry can be enhanced, and the performance of the high-temperature electronic slurry can be improved.
Description
Technical Field
The invention relates to a modification method, in particular to a method for preparing high-temperature electronic paste based on organic phosphorus salt.
Background
The high-temperature electronic paste is widely applied to the industrial production of electronic components and integrated circuits, generally comprises a conductive phase, a glass phase and an organic solvent, and can form conductive nanowires by printing; and sintering at high temperature, pyrolyzing and volatilizing the organic phase and the surfactant, and fusing the glass powder on the substrate to be bonded with the silver powder to form the conductive compact film. In the process, the distribution of the conductive particles and the contact resistance among the particles have a far-reaching influence on the performance of the slurry, and the formation of a compact conductive film of the slurry and the conductivity of the compact conductive film of the slurry are influenced. There are many problems to be solved in high temperature electronic paste, such as: the organic solvent contains too many pollutants and is not friendly to the environment; the surface energy of the conductive phase particles is large, the dispersibility is poor, and the particles are easy to agglomerate; the problems of large spacing gap, uneven distribution, more conducting film vacant gaps, untight connection, unnecessary energy consumption and the like caused by the unmodified surface appearance of the conducting phase particles are solved. Various disadvantages have been hindering the industrialization of high temperature electronic paste.
CN108666002A discloses a metal microcrystalline glass powder comprising TeO2：10-50wt％，TiO2：15-70wt％，ZnO：2-10wt％，SiO2: 1-15 wt% and Li2O: 5-20 wt%, the glass phase has high-temperature viscosity, is not easy to flow, has large surface tension, is precise in circuit during printing, but has poor adhesion effect on a conductive phase, conductive powder is easy to agglomerate, a connecting gap is large, and the conductive effect is poor.
CN202011529639.0 discloses that toluene sulfonyl hydrazide is attached to the surface of conductive particles, and hydrolysis generates micro-bubbles to uniformly disperse the conductive particles, the dispersibility of the slurry is improved, but the micro-bubbles improve the contact resistance between the conductive particles, and the performance of the slurry is low.
CN202011253070.X discloses a novel glass comprising Bi2O3：55～75％、B2O3：5～20％、SiO2：5～20％、MgO：1～5％、Al2O3:1 to 5 percent. The glass and the sizing agent have better dispersibility, the dispersibility of the conductive phase is improved, but the environment is seriously polluted by adding auxiliary agents such as toluene and dimethylbenzene.
Therefore, it is an urgent need to solve the problems of the art to provide a novel and environment-friendly modification technique that can make the conductive phase have good dispersibility and the conductive phase powder adhere tightly. According to the preparation method, n-hexyl-3-methylimidazole hexafluorophosphate (NHIHP) is used as a surface modification agent to modify the surface of conductive phase powder, so that the dispersibility and the bonding strength are improved, and the environment-friendly high-performance novel high-temperature electronic paste is prepared.
Disclosure of Invention
In view of the above, the present invention provides a method for preparing high-temperature electronic paste based on organic phosphorus salts, and particularly provides a novel and environment-friendly modification method for achieving good conductive phase dispersibility and tight conductive phase powder adhesion, and an application of the modification method in high-temperature electronic paste.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a surface modification method based on organic phosphorus salt comprises the following steps:
uniformly dispersing the conductive powder in a mixed solution of ethanol and diethyl ether, adding organic phosphate into the solution, uniformly stirring for 30min at a constant temperature of 45 ℃, centrifuging, and drying in vacuum to obtain a pretreated conductive phase.
The organic phosphorus salt is n-hexyl-3-methylimidazolium hexafluorophosphate (NHIHP).
The invention also aims to provide a preparation method of the high-temperature electronic paste.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of high-temperature electronic paste specifically comprises the following steps:
(1) surface pretreatment of the conductive phase powder: uniformly dispersing the conductive phase powder in a mixed solution of ethanol and ether, adding NHIHP into the solution, adding sodium hypophosphite, uniformly stirring at the constant temperature of 45 ℃ for 30min, centrifuging, and drying in vacuum to obtain the pretreated conductive powder.
(2) Preparing novel glass powder: the glass comprises the following components in percentage by mass: bi2O3：67-78wt％；B2O3：5-11wt％；SiO2：0-3wt％；ZnO：8-15wt％；InO: 1-7 wt%; CuO: 0 to 2 weight percent; SnO: 0 to 2 weight percent; proportionally placing the glass components into a sintering furnace, heating to 1100 ℃, firing at a constant temperature for 2h, taking out, pouring into deionized water for cold quenching, and performing ball milling to obtain glass powder with the particle size of 5-40 mu m;
(3) preparing an organic carrier: the novel slurry carrier is prepared by uniformly stirring an organic solvent, a reducing agent, a dispersing agent, a coupling agent, a thickening agent and NHIHP for 15-30min at a rotating speed of 150-250r/min at a temperature of 45-65 ℃ in proportion.
(4) Preparing high-temperature electronic paste: and stirring and mixing the obtained pretreated conductive powder, glass powder and organic carrier uniformly by using a dispersion machine to obtain the high-temperature electronic paste.
Preferably, in the step (1), the conductive phase powder is at least one of silver powder and silver-coated copper powder, and the conductive phase powder and the NHIHP are mixed according to the mass ratio of (28-32): 1.
Further, the proportioned conductive phase powder is silver powder or silver-coated copper powder with the surface pretreated, the small particle size powder is granular powder with the average particle size of 0.5-1 mu m, and the large particle size powder is flaky powder with the average particle size of 7-10 mu m; wherein the average particle diameter of the granular conductive phase powder is 0.5 μm, 0.7 μm, 0.9 μm or 1 μm, and the average particle diameter of the flaky conductive phase powder is 7 μm, 8 μm, 9 μm or 10 μm; the mass ratio of the large-particle-size powder to the small-particle-size powder is MSmall：MBig (a)(0.6-1):2, wherein the mass ratio may be 0.6:2, 0.7:2, 0.8:2, 0.9:2, 1: 2.
Furthermore, the mass ratio of the ethanol to the ether in the mixed solution of the ethanol and the ether is (3-5):1, the centrifugal rotation speed is 6000-10000rpm, and the time is 5-10 min.
Preferably, in the step (2), the glass phase powder is a novel glass powder prepared based on Bi-B-Si.
Preferably, in the step (3), the organic solvent is a high temperature resistant resin or terpineol, the reducing agent is at least one of citric acid, ascorbic acid and formic acid, the dispersing agent is polyvinyl alcohol, the coupling agent is a silane coupling agent, and the thickening agent is ethyl cellulose.
Further, the mass ratio of the organic solvent, the reducing agent, the dispersing agent, the coupling agent, the thickening agent and the NHIHP in the novel slurry carrier is (65-85): 5-15): 1-8): 3-10): 2-10): 0-2.
Preferably, in the step (4), the mass ratio of the novel paste carrier, the conductive phase powder and the glass phase powder in the high-temperature electronic paste is (7-12): (78-90): (3-5).
Further, the rotation speed of the disperser in the stirring step is 9000-.
According to the technical scheme, compared with the prior art, the method for preparing the high-temperature electronic paste based on the organic phosphorus salt has the following excellent effects:
according to the invention, the conductive phase powder is subjected to surface modification by using n-hexyl-3-methylimidazole hexafluorophosphate (NHIHP), so that the dispersibility and the bonding strength of the conductive powder are improved; the high-temperature electronic paste comprises the following components in parts by weight: 7-12 parts of a novel slurry carrier, 78-90 parts of conductive powder with different particle sizes and 3-5 parts of a glass phase. According to the invention, the NHIHP is combined with the surface of the conductive phase, so that the slurry particles are uniformly distributed, the bonding strength among the conductive particles can be enhanced, a compact film is formed, the components are environment-friendly, the conductive effect of the slurry can be enhanced, and the performance of the high-temperature electronic slurry can be improved.
Detailed Description
The technical solutions in the present invention will be described clearly and completely with reference to the following embodiments of the present invention, and it should be understood that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
The embodiment of the invention discloses a method for preparing high-temperature electronic paste based on n-hexyl-3-methylimidazole hexafluorophosphate (NHIHP), and particularly discloses a method for preparing the high-temperature electronic paste.
The present invention will be further specifically illustrated by the following examples for better understanding, but the present invention is not to be construed as being limited thereto, and certain insubstantial modifications and adaptations of the invention by those skilled in the art based on the foregoing disclosure are intended to be included within the scope of the invention.
The technical solution of the present invention will be further described with reference to the following specific examples.
Example 1:
a method for preparing high-temperature electronic paste based on organic phosphorus salt specifically comprises the following steps:
the method comprises the following steps: surface pretreatment of the conductive phase powder: dispersing 85g of proportioned conductive phase powder in 510mL of ethanol ether mixed solution, adding 1g of n-hexyl-3-methylimidazole hexafluorophosphate (NHIHP) into the solution, adding 4g of sodium hypophosphite, uniformly stirring at the constant temperature of 45 ℃ for 30min, centrifuging at 10000rpm for 15min, and drying in vacuum to obtain pretreated conductive phase powder;
step two: preparing novel glass powder: taking out the glass components in proportion, placing the glass components into a sintering heat-preserving furnace for sintering, and performing cold quenching by using deionized water to obtain glass, and performing ball milling on the obtained glass to obtain glass powder;
step three: preparation of organic vehicle: the novel slurry carrier is prepared by uniformly stirring terpineol, citric acid, polyvinyl alcohol, a silane coupling agent, ethyl cellulose and NHIHP at a mass ratio of 76:8:6:5:5:0 at a rotation speed of 150rpm at a temperature of 50 ℃ for 20min to obtain a uniformly mixed novel slurry carrier;
step four: preparation of slurry: dispersing the obtained pretreated conductive powder, glass phase powder and organic carrier for 20min by a dispersion machine at 8000rpm according to the mass ratio of 85:5:10 to obtain uniform and environment-friendly novel high-temperature electronic paste.
Example 2:
a method for preparing high-temperature electronic paste based on organic phosphorus salt specifically comprises the following steps:
the method comprises the following steps: surface pretreatment of the conductive phase powder: dispersing 85g of proportioned conductive phase powder in 510mL of ethanol ether mixed solution, adding 3g of n-hexyl-3-methylimidazole hexafluorophosphate (NHIHP) into the solution, adding 4g of sodium hypophosphite, uniformly stirring at the constant temperature of 45 ℃ for 30min, centrifuging at 10000rpm for 15min, and drying in vacuum to obtain pretreated conductive phase powder;
step two: preparing novel glass powder: taking out the glass components in proportion, placing the glass components into a sintering heat-preserving furnace for sintering, and performing cold quenching by using deionized water to obtain glass, and performing ball milling on the obtained glass to obtain glass powder;
step three: preparation of organic vehicle: the novel slurry carrier is prepared by uniformly stirring terpineol, citric acid, polyvinyl alcohol, a silane coupling agent, ethyl cellulose and NHIHP at a mass ratio of 76:8:6:5:5:0 at a rotation speed of 150rpm at a temperature of 50 ℃ for 20min to obtain a uniformly mixed novel slurry carrier.
Step four: preparation of slurry: dispersing the obtained pretreated conductive powder, glass phase powder and organic carrier for 20min by a dispersion machine at 10000rpm according to the mass ratio of 85:5:10 to obtain the uniform and environment-friendly novel high-temperature electronic paste.
Example 3:
a method for preparing high-temperature electronic paste based on organic phosphorus salt specifically comprises the following steps:
the method comprises the following steps: surface pretreatment of the conductive phase powder: dispersing 85g of proportioned conductive phase powder in 510mL of ethanol ether mixed solution, adding 5g of n-hexyl-3-methylimidazole hexafluorophosphate (NHIHP) into the solution, adding 4g of sodium hypophosphite, uniformly stirring at the constant temperature of 45 ℃ for 30min, centrifuging at 10000rpm for 15min, and drying in vacuum to obtain pretreated conductive phase powder;
step two: preparing novel glass powder: taking out the glass components in proportion, placing the glass components into a sintering heat-preserving furnace for sintering, and performing cold quenching by using deionized water to obtain glass, and performing ball milling on the obtained glass to obtain glass powder;
step three: preparation of organic vehicle: the novel slurry carrier is prepared by uniformly stirring terpineol, citric acid, polyvinyl alcohol, a silane coupling agent, ethyl cellulose and NHIHP at a mass ratio of 76:8:6:5:5:0 at a rotation speed of 150rpm at a temperature of 50 ℃ for 20min to obtain a uniformly mixed novel slurry carrier;
step four: preparation of slurry: dispersing the obtained pretreated conductive powder, glass phase powder and organic carrier for 20min by a dispersion machine at 10000rpm according to the mass ratio of 85:5:10 to obtain the uniform and environment-friendly novel high-temperature electronic paste.
Example 4:
a method for preparing high-temperature electronic paste based on organic phosphorus salt specifically comprises the following steps:
the method comprises the following steps: surface pretreatment of the conductive phase powder: dispersing 85g of proportioned conductive phase powder in 510mL of ethanol ether mixed solution, adding 3g of n-hexyl-3-methylimidazole hexafluorophosphate (NHIHP) into the solution, adding 4g of sodium hypophosphite, uniformly stirring at the constant temperature of 45 ℃ for 30min, centrifuging at 10000rpm for 15min, and drying in vacuum to obtain pretreated conductive phase powder; step two: preparing novel glass powder: taking out the glass components in proportion, placing the glass components into a sintering heat-preserving furnace for sintering, and performing cold quenching by using deionized water to obtain glass, and performing ball milling on the obtained glass to obtain glass powder;
step three: preparation of organic vehicle: the novel slurry carrier is prepared by uniformly stirring terpineol, citric acid, polyvinyl alcohol, a silane coupling agent, ethyl cellulose and NHIHP at a mass ratio of 76:8:6:5:5:2 at a rotation speed of 150rpm at a temperature of 50 ℃ for 20min to obtain a uniformly mixed novel slurry carrier.
Step four: preparation of slurry: dispersing the obtained pretreated conductive powder, glass phase powder and organic carrier for 20min by a dispersion machine at 10000rpm according to the mass ratio of 85:5:10 to obtain the uniform and environment-friendly novel high-temperature electronic paste.
The embodiments in the present description are described in a progressive manner, each embodiment focuses on differences from other embodiments, and the same and similar parts among the embodiments are referred to each other.
The inventive content is not limited to the content of the above-mentioned embodiments, wherein combinations of one or several of the embodiments may also achieve the object of the invention.
To further verify the excellent effects of the present invention, the inventors also conducted the following experiments:
comparative example 1:
this comparative example provides a high temperature electronic paste, consistent with example 2, except that n-hexyl-3-methylimidazolium hexafluorophosphate (NHIHP) was not added in the surface pretreatment of the conductive phase powder of step one.
Comparative example 2:
this comparative example provides a high temperature electronic paste, consistent with example 4, except that n-hexyl-3-methylimidazolium hexafluorophosphate (NHIHP) was not added in the surface pretreatment of the conductive phase powder of step one.
Comparative example 3
High-temperature electronic paste is common in certain markets.
And (3) performance testing:
the conductive pastes provided in examples 1 to 4 and comparative examples 1 to 3 were used for film formation:
a semi-automatic precision printing machine is adopted, a screen printing plate is 325 meshes, the thickness of a glue film is 30um, the glue film is cured for 10min at 400 ℃ after being printed, and then cured for 20min at 700 ℃, and resistance test and adhesion strength test are carried out.
And printing the slurry on a flexible substrate, curing for 10min, starting 200 times of bending, and testing the resistivity after bending.
The results are as follows:
the results show that the product provided by the invention has better conductivity; comparing examples 1 to 4 with comparative examples 1 to 3, it can be seen that the conductive powder is dispersed better and the conductive film is more compact by using the n-hexyl-3-methylimidazolium hexafluorophosphate (NHIHP) surface modification technique, and the gaps in the slurry conductive film are reduced by the reducibility of the conductive film, so that the performance of the slurry is improved.
The previous description of the disclosed embodiments is provided to enable any person skilled in the art to make or use the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.
Claims (10)
1. The method for preparing the high-temperature electronic paste based on the organic phosphorus salt is characterized by comprising the following steps:
(1) surface pretreatment of the conductive phase powder: uniformly dispersing conductive phase powder in a mixed solution of ethanol and ether, adding NHIHP into the solution, adding sodium hypophosphite, uniformly stirring at the constant temperature of 45 ℃ for 30min, centrifuging, and drying in vacuum to obtain pretreated conductive powder;
(2) preparing novel glass powder: proportionally placing the glass components into a sintering furnace for sintering, then performing cold quenching on the glass components by deionized water, and performing ball milling to obtain glass powder;
(3) preparing an organic carrier: the novel slurry carrier is prepared by uniformly stirring an organic solvent, a reducing agent, a dispersing agent, a coupling agent, a thickening agent and NHIHP for 15-30min at a rotating speed of 150-250r/min at a temperature of 45-65 ℃ in proportion to obtain a uniformly mixed novel slurry carrier;
(4) preparing high-temperature electronic paste: and stirring and mixing the obtained pretreated conductive powder, glass powder and organic carrier uniformly by using a dispersion machine to obtain the high-temperature electronic paste.
2. The method for preparing high-temperature electronic paste based on organic phosphorus salt as claimed in claim 1, wherein in step (1), the conductive phase powder is at least one of silver powder and silver-coated copper powder, and the conductive phase powder and NHIHP are mixed according to the mass ratio of (28-32): 1.
3. The method for preparing high-temperature electronic paste based on organic phosphorus salt as claimed in claim 1 or 2, wherein the proportioned conductive phase powder is surfaceThe pretreated silver powder or silver-coated copper powder has the small particle size powder of 0.5-1 μm and the large particle size powder of 7-10 μm; wherein the average particle diameter of the granular conductive phase powder is 0.5 μm, 0.7 μm, 0.9 μm or 1 μm, and the average particle diameter of the flaky conductive phase powder is 7 μm, 8 μm, 9 μm or 10 μm; the mass ratio of the large-particle-size powder to the small-particle-size powder is MSmall：MBig (a)(0.6-1):2, wherein the mass ratio may be 0.6:2, 0.7:2, 0.8:2, 0.9:2, 1: 2.
4. The method as claimed in claim 3, wherein the mass ratio of ethanol to ether in the mixed solution of ethanol and ether is (3-5):1, and the centrifugation speed is 6000-10000rpm, and the time is 5-10 min.
5. The method for preparing high-temperature electronic paste based on organic phosphorus salt as claimed in claim 1, wherein in the step (2), the glass component comprises, by mass percent:
Bi2O3：67-78wt％；B2O3：5-11wt％；SiO2:0 to 3 wt%; ZnO: 8-15 wt%; InO: 1-7 wt%; CuO: 0 to 2 weight percent; SnO: 0 to 2 wt%, and the glass frit is a novel glass frit prepared based on Bi-B-Si.
6. The method for preparing high-temperature electronic paste based on organic phosphorus salt as claimed in claim 1 or 5, wherein the sintering temperature in step (2) is 1100 ℃ and the constant-temperature sintering time is 2 h.
7. The method for preparing high-temperature electronic paste based on organic phosphorus salt as claimed in claim 1, wherein in step (3), the organic solvent is high-temperature resistant resin or terpineol, the reducing agent is at least one of citric acid, ascorbic acid and formic acid, the dispersing agent is polyvinyl alcohol, the coupling agent is silane coupling agent, and the thickening agent is ethyl cellulose.
8. The method for preparing high-temperature electronic paste based on organic phosphorus salt as claimed in claim 6, wherein the mass ratio of the organic solvent, the reducing agent, the dispersing agent, the coupling agent, the thickening agent and the NHIHP in the novel paste carrier is (65-85): 5-15): 1-8: (3-10): 2-10): 0-2.
9. The method for preparing high-temperature electronic paste based on organic phosphorus salt as claimed in claim 1, wherein in step (4), the mass ratio of the novel paste carrier, the conductive phase powder and the glass phase powder in the high-temperature electronic paste is (7-12): (78-90): (3-5).
10. The method for preparing high-temperature electronic paste based on organic phosphorus salt as claimed in claim 1 or 8, wherein the rotation speed of the disperser in the stirring step is 9000-15000rpm, and the treatment time is 15-30 min.
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