CN113284645B - 一种纳米银膏及其制备方法 - Google Patents
一种纳米银膏及其制备方法 Download PDFInfo
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- CN113284645B CN113284645B CN202110447478.9A CN202110447478A CN113284645B CN 113284645 B CN113284645 B CN 113284645B CN 202110447478 A CN202110447478 A CN 202110447478A CN 113284645 B CN113284645 B CN 113284645B
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 202
- 238000002360 preparation method Methods 0.000 title abstract description 12
- 239000000843 powder Substances 0.000 claims abstract description 133
- 239000002245 particle Substances 0.000 claims abstract description 121
- 229910000679 solder Inorganic materials 0.000 claims abstract description 43
- 239000002270 dispersing agent Substances 0.000 claims abstract description 31
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 28
- 239000003085 diluting agent Substances 0.000 claims abstract description 27
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 23
- 229910045601 alloy Inorganic materials 0.000 claims description 61
- 239000000956 alloy Substances 0.000 claims description 61
- 238000000034 method Methods 0.000 claims description 15
- 238000002844 melting Methods 0.000 claims description 12
- 230000008018 melting Effects 0.000 claims description 12
- VUFGUVLLDPOSBC-XRZFDKQNSA-M cephalothin sodium Chemical compound [Na+].N([C@H]1[C@@H]2N(C1=O)C(=C(CS2)COC(=O)C)C([O-])=O)C(=O)CC1=CC=CS1 VUFGUVLLDPOSBC-XRZFDKQNSA-M 0.000 claims description 8
- 150000001408 amides Chemical class 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 150000001298 alcohols Chemical class 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 150000002148 esters Chemical class 0.000 claims description 2
- 229930195733 hydrocarbon Natural products 0.000 claims description 2
- 150000002430 hydrocarbons Chemical class 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 235000005985 organic acids Nutrition 0.000 claims description 2
- 238000003466 welding Methods 0.000 abstract description 59
- 238000002156 mixing Methods 0.000 abstract description 3
- 229910052709 silver Inorganic materials 0.000 description 23
- 239000004332 silver Substances 0.000 description 23
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 21
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 14
- 238000012360 testing method Methods 0.000 description 11
- 230000015556 catabolic process Effects 0.000 description 10
- 238000006731 degradation reaction Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 8
- 238000005476 soldering Methods 0.000 description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 6
- 230000008021 deposition Effects 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 239000002923 metal particle Substances 0.000 description 6
- MUBZPKHOEPUJKR-UHFFFAOYSA-N oxalic acid group Chemical group C(C(=O)O)(=O)O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 6
- 239000012266 salt solution Substances 0.000 description 6
- GGCZERPQGJTIQP-UHFFFAOYSA-N sodium;9,10-dioxoanthracene-2-sulfonic acid Chemical compound [Na+].C1=CC=C2C(=O)C3=CC(S(=O)(=O)O)=CC=C3C(=O)C2=C1 GGCZERPQGJTIQP-UHFFFAOYSA-N 0.000 description 6
- BTXXTMOWISPQSJ-UHFFFAOYSA-N 4,4,4-trifluorobutan-2-one Chemical group CC(=O)CC(F)(F)F BTXXTMOWISPQSJ-UHFFFAOYSA-N 0.000 description 5
- BQACOLQNOUYJCE-FYZZASKESA-N Abietic acid Natural products CC(C)C1=CC2=CC[C@]3(C)[C@](C)(CCC[C@@]3(C)C(=O)O)[C@H]2CC1 BQACOLQNOUYJCE-FYZZASKESA-N 0.000 description 5
- RSWGJHLUYNHPMX-UHFFFAOYSA-N Abietic-Saeure Natural products C12CCC(C(C)C)=CC2=CCC2C1(C)CCCC2(C)C(O)=O RSWGJHLUYNHPMX-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000000227 grinding Methods 0.000 description 5
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 4
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000010949 copper Substances 0.000 description 4
- 230000006866 deterioration Effects 0.000 description 4
- JFCQEDHGNNZCLN-UHFFFAOYSA-N glutaric acid group Chemical group C(CCCC(=O)O)(=O)O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 description 4
- 229920002401 polyacrylamide Polymers 0.000 description 4
- 229920005614 potassium polyacrylate Polymers 0.000 description 4
- 229920002554 vinyl polymer Polymers 0.000 description 4
- 238000001514 detection method Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000004806 packaging method and process Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N 2-Oxohexane Chemical compound CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 2
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 2
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 2
- 235000006408 oxalic acid Nutrition 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 229920001495 poly(sodium acrylate) polymer Polymers 0.000 description 2
- 229920001083 polybutene Polymers 0.000 description 2
- ONQDVAFWWYYXHM-UHFFFAOYSA-M potassium lauryl sulfate Chemical compound [K+].CCCCCCCCCCCCOS([O-])(=O)=O ONQDVAFWWYYXHM-UHFFFAOYSA-M 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- NNMHYFLPFNGQFZ-UHFFFAOYSA-M sodium polyacrylate Chemical compound [Na+].[O-]C(=O)C=C NNMHYFLPFNGQFZ-UHFFFAOYSA-M 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910002601 GaN Inorganic materials 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- NEIHULKJZQTQKJ-UHFFFAOYSA-N [Cu].[Ag] Chemical compound [Cu].[Ag] NEIHULKJZQTQKJ-UHFFFAOYSA-N 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 238000004021 metal welding Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
Classifications
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- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/052—Metallic powder characterised by the size or surface area of the particles characterised by a mixture of particles of different sizes or by the particle size distribution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/103—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing an organic binding agent comprising a mixture of, or obtained by reaction of, two or more components other than a solvent or a lubricating agent
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/10—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material
- B22F1/107—Metallic powder containing lubricating or binding agents; Metallic powder containing organic material containing organic material comprising solvents, e.g. for slip casting
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/14—Treatment of metallic powder
- B22F1/145—Chemical treatment, e.g. passivation or decarburisation
- B22F1/147—Making a dispersion
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
- B23K35/0244—Powders, particles or spheres; Preforms made therefrom
- B23K35/025—Pastes, creams, slurries
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B13/00—Apparatus or processes specially adapted for manufacturing conductors or cables
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/02—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers
- B22F7/04—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal
- B22F2007/042—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method
- B22F2007/047—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite layers with one or more layers not made from powder, e.g. made from solid metal characterised by the layer forming method non-pressurised baking of the paste or slurry containing metal powder
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- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/25—Noble metals, i.e. Ag Au, Ir, Os, Pd, Pt, Rh, Ru
- B22F2301/255—Silver or gold
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F2301/00—Metallic composition of the powder or its coating
- B22F2301/30—Low melting point metals, i.e. Zn, Pb, Sn, Cd, In, Ga
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- B22—CASTING; POWDER METALLURGY
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- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/054—Particle size between 1 and 100 nm
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- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/056—Particle size above 100 nm up to 300 nm
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F2304/00—Physical aspects of the powder
- B22F2304/05—Submicron size particles
- B22F2304/058—Particle size above 300 nm up to 1 micrometer
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F2304/00—Physical aspects of the powder
- B22F2304/10—Micron size particles, i.e. above 1 micrometer up to 500 micrometer
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- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
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Abstract
本发明公开了一种纳米银膏及其制备方法。本发明的纳米银膏包括纳米银粉、微米锡基焊料粉粒、还原剂、分散剂、稀释剂。本发明的纳米银膏是将纳米银粉、微米锡基焊料粉粒与还原剂、分散剂、稀释剂混合均匀得到。本发明的纳米银膏解决了现有技术中的纳米银膏在无压焊接时堆垛密度低、孔隙率高、体积收缩剧烈、易出现裂纹、界面焊合率低的问题,从而提高了焊接部位的力学性能与可靠性。
Description
技术领域
本发明涉及电子元器件焊接技术领域,特别是涉及一种纳米银膏及其制备方法。
背景技术
随着电子元器件日趋精密、微型化和集成化,势必导致封装密度与功率密度更高,因而会对封装的散热和可靠性要求越来越高。以碳化硅、氮化镓为代表的新一代功率半导体,具有禁带宽度宽、击穿电压高、热稳定强、开关特性稳定等特点,被广泛应用于轨道交通、航空航天、新能源汽车、深海深井探测等领域。
在服役过程中,功率器件的互连材料会受到来自机械振动、热应力、高密度电流和功率循环等严苛考验,传统的锡基焊料势必会无法满足日益苛刻的可靠性要求,因此亟需开发新的耐高温焊接材料和相应的焊接工艺。
由于纳米金属颗粒具有高表面能、低熔点特性,近年来国内外提出使用纳米金属焊接封装器件。纳米银膏因具有良好的导电导热、低温焊接、高可靠性,具有高温服役性能,是目前最具潜力的低温焊接互连材料。然而,纳米银膏原始堆垛密度较低,封装焊接时,特别是焊接器件的结构导致无法给予压力,或者为了防止压力对焊接器件造成损伤而需要无压焊接时,会产生大量不可控制的孔隙结构,焊接层致密度低,体积收缩明显,在无压焊接时焊接层易出现裂纹,导致界面焊合率降低、机械强度低,导电导热性能相比于块体银大幅下降。而且,焊接银膏因具有较大的热膨胀系数,在服役过程中也会产生较大的热机械应力,造成焊接部位的失效。
发明内容
本发明的首要目的在于克服现有技术的缺点与不足,提供了一种纳米银膏,以解决现有纳米银膏在无压焊接时焊接层堆垛密度低、体积收缩剧烈、易出现裂纹、界面焊合率低的问题,进而提高焊接部位的力学性能与可靠性。
本发明的另一目的在于提供上述纳米银膏的制备方法。
本发明的目的通过下述技术方案实现:一种纳米银膏,包括纳米银粉、微米锡基焊料粉粒、还原剂、分散剂、稀释剂。
所述微米锡基焊料粉粒的材质为熔点在120-250℃范围内的锡基合金;优选为SnBi系列合金、SnBiAg系列合金、SnAg系列合金、SnCu系列合金、SnAgCu系列合金、SnSb系列合金、SnSbCu系列合金、SnSbAg系列合金、SnAgCuBi系列合金、SnAgCuSb系列合金中的至少一种。
所述纳米银粉的平均粒径为5-3000nm。
优选的,所述纳米银粉的平均粒径为10-1500nm。
所述纳米银粉为一种平均粒径的纳米银粉或两种以上不同平均粒径的纳米银粉混合体。
所述微米锡基焊料粉粒的平均粒径为0.1-100μm。
优选的,所述微米锡基焊料粉粒的平均粒径为0.5-50μm。
所述纳米银粉与所述微米锡基焊料粉粒的质量之比为20-500:1。
优选的,所述纳米银粉与所述微米锡基焊料粉粒的质量之比为30-200:1。
所述稀释剂为醇类、烃类、酮类、酯类等中的至少一种。
所述稀释剂在体系中的质量百分比为2-8%。
所述分散剂为聚烃类酰胺、聚烃类酸盐、烷基酸盐等中的至少一种。
所述分散剂在体系中的质量百分比为0.1-3%。
所述还原剂为有机酸中的至少一种。
所述还原剂在体系中的质量百分比为0.1-1.5%。
上述纳米银膏的制备方法:将所述纳米银粉、所述微米锡基焊料粉粒与所述还原剂、分散剂、稀释剂混合均匀,得到纳米银膏。
所述纳米银粉是通过化学还原银盐溶液,并将银沉积层在100Pa以下的负压环境中干燥的方法得到。
所述微米锡基焊料粉粒是将锡基焊料通过真空研磨机研磨得到。
所述混合均匀优选为采用机械搅拌或者磁力搅拌的方式。
纳米银膏中低熔点的微米锡基焊料粉粒,如果加入量太少,则不足以起到填充未完全熔化的纳米银颗粒间的孔隙的效果;如果加入量太多,焊后焊层中存在太多的低熔点相,反而会降低焊接后焊层的可靠性。所以控制纳米银膏中低熔点微米锡基焊料粉粒的用量是本发明的关键之一。
低熔点的微米锡基焊料粉粒,如果粒径太小,一方面由于粒径越小,比表面积越大,粉粒越容易氧化;另一方面,粒径小,制造粉粒的成本高。但是如果粒径太大,与纳米银膏中的纳米银粉的接触几率会降低,不利于微米锡基焊料粉粒在纳米银膏中充分混合。
与现有技术相比,本发明具有以下有益效果:
1、本发明的纳米银膏中均匀混有低熔点微米锡基焊料粉粒,焊接过程中完全熔化的微米锡基焊料粉粒填充了未完全熔化的纳米银颗粒间的孔隙,从而解决了现有纳米银膏在无压焊接时堆垛密度低、孔隙率高、体积收缩剧烈、易出现裂纹、界面焊合率低的问题,进而提高了焊接部位的力学性能与可靠性。
2、本发明的纳米银膏的制备方法以可规模化生产为出发点,工艺简单,成本低,可操作性强,可批量生产,经济效益显著。
具体实施方式
下面结合实施例,对本发明的具体实施方式作进一步详细描述。以下实施例用于说明本发明,但不用来限制本发明的范围。
实施例一
本实施例提供了一种纳米银膏,该纳米银膏中含有平均粒径为30nm的纳米银粉、平均粒径为5μm的Sn42Bi58合金粉粒(熔点为139℃)、将上述粉粒形成膏状的稀释剂、防止银膏中粉末发生团聚的分散剂、焊接过程用于还原被焊面氧化层和银膏中金属颗粒氧化层的还原剂。所述纳米银粉与微米Sn42Bi58合金粉粒的质量之比为200:1。所述稀释剂为质量百分比为1:2的乙二醇和正丁烷,所述稀释剂在整个纳米银膏体系中的质量百分比为2%。所述分散剂为质量百分比为3:1的十二烷基硫酸钾和聚丁烯酸钠,所述分散剂在整个纳米银膏体系中的质量百分比为1.2%。所述还原剂为质量百分比为1:4的松香酸和乙酸,所述还原剂在整个纳米银膏体系中的质量百分比为0.5%。
纳米银膏的制备方法,包括如下步骤:
S1、通过化学还原银盐溶液,并采用将银沉积层在100Pa以下的负压环境中干燥的方法得到平均粒径为30nm的纳米银粉;
S2、按照锡基焊料的合金成分(Sn和Bi的质量百分比(42:58))配置好Sn42Bi58合金,将Sn42Bi58合金通过真空研磨机研磨,得到平均粒径为5μm的Sn42Bi58合金粉粒;
S3、按照质量百分比为1:2的乙二醇和正丁烷,在整个纳米银膏体系中的总质量百分比为2%的配比,配好稀释剂。按照质量百分比为3:1的十二烷基硫酸钾和聚丁烯酸钠,在整个纳米银膏体系中的总质量百分比为1.2%的配比,配好分散剂。按照质量百分比为1:4的松香酸和乙酸,在整个纳米银膏体系中的总质量百分比为0.5%的配比,配好还原剂。
S4、将步骤S1制成的纳米银粉与步骤S2制成的微米Sn42Bi58粉粒按照200:1的质量比,加入到步骤S3配好的含有还原剂、分散剂、稀释剂的混合溶剂中,采用机械搅拌均匀混合,得到混有微米锡基焊料粉粒的纳米银膏。
实施例二
本实施例提供了一种纳米银膏,该纳米银膏中含有平均粒径为20nm的纳米银粉、平均粒径为100nm的纳米银粉所组成的混合纳米银粉,其质量比为5:3;平均粒径为10μm的Sn96.5Ag3.5合金粉粒(熔点为221℃),混合纳米银粉与微米Sn96.5Ag3.5合金粉粒的质量之比为160:1;并含有将上述粉粒形成膏状的稀释剂、防止银膏中粉末发生团聚的分散剂、焊接过程用于还原被焊面氧化层和银膏中金属颗粒氧化层的还原剂。所述稀释剂为质量百分比为3:2的己酮和正戊烷,所述稀释剂在整个纳米银膏体系中的质量百分比为3.5%。所述分散剂为质量百分比为4:3的聚乙烯酰胺和聚丙烯酸钾,所述分散剂在整个纳米银膏体系中的质量百分比为1.9%。所述还原剂为质量百分比为2:1的草酸和己二酸,所述还原剂在整个纳米银膏体系中的质量百分比为0.8%。
纳米银膏的制备方法,包括如下步骤:
S1、通过化学还原银盐溶液,并采用将银沉积层在100Pa以下的负压环境中干燥的方法分别得到平均粒径为20nm和100nm的纳米银粉;
S2、按照锡基焊料的合金成分配置好所述的Sn96.5Ag3.5合金,将Sn96.5Ag3.5合金通过真空研磨机研磨,得到平均粒径为10μm的Sn96.5Ag3.5合金粉粒;
S3、按照质量百分比为3:2的己酮和正戊烷,在整个纳米银膏体系中的总质量百分比为3.5%的配比,配好稀释剂。按照质量百分比为4:3的聚乙烯酰胺和聚丙烯酸钾,在整个纳米银膏体系中的总质量百分比为1.9%的配比,配好分散剂。按照质量百分比为2:1的草酸和己二酸,在整个纳米银膏体系中的总质量百分比为0.8%的配比,配好还原剂。
S4、将步骤S1制成的纳米银粉(平均粒径为20nm的纳米银粉、平均粒径为100nm的纳米银粉的质量百分比为5:3)与步骤S2制成的微米Sn96.5Ag3.5合金粉粒按照160:1的质量比,加入到步骤S3配好的含有还原剂、分散剂、稀释剂的混合溶剂中,采用磁力搅拌均匀混合,得到混有微米锡基焊料粉粒的纳米银膏。
实施例三
本实施例提供了一种纳米银膏,该纳米银膏中含有平均粒径为10nm的纳米银粉、平均粒径为120nm的纳米银粉、平均粒径为800nm的纳米银粉所组成的混合纳米银粉,其质量比为7:4:1;含有平均粒径为15μm的Sn99.3Cu0.7合金粉粒(熔点为227℃),混合纳米银粉与微米Sn99.3Cu0.7合金粉粒的质量之比为120:1;并含有将上述粉粒形成膏状的稀释剂、防止银膏中粉末发生团聚的分散剂、焊接过程用于还原被焊面氧化层和银膏中金属颗粒氧化层的还原剂。所述稀释剂为质量百分比为2:5的正戊烷和醋酸乙酯,所述稀释剂在整个纳米银膏体系中的质量百分比为5%。所述分散剂为质量百分比为1:3的聚丙烯酰胺和十二烷基硫酸钠,所述分散剂在整个纳米银膏体系中的质量百分比为2.2%。所述还原剂为质量百分比为3:1的戊二酸和松香酸,所述还原剂在整个纳米银膏体系中的质量百分比为1%。
纳米银膏的制备方法,包括如下步骤:
S1、通过化学还原银盐溶液,并采用将银沉积层在100Pa以下的负压环境中干燥的方法分别得到平均粒径为10nm、120nm、800nm的纳米银粉;
S2、按照锡基焊料的合金成分配置好所述的Sn99.3Cu0.7合金,将Sn99.3Cu0.7合金通过真空研磨机研磨,得到平均粒径为15μm的Sn99.3Cu0.7合金粉粒;
S3、按照质量百分比为2:5的正戊烷和醋酸乙酯,在整个纳米银膏体系中的总质量百分比为5%的配比,配好稀释剂。按照质量百分比为1:3的聚丙烯酰胺和十二烷基硫酸钠,在整个纳米银膏体系中的总质量百分比为2.2%的配比,配好分散剂。按照质量百分比为3:1的戊二酸和松香酸,在整个纳米银膏体系中的总质量百分比为1%的配比,配好还原剂。
S4、将步骤S1制成的纳米银粉(平均粒径为10nm的纳米银粉、平均粒径为120nm的纳米银粉、平均粒径为800nm的纳米银粉的质量比为7:4:1)与步骤S2制成的微米Sn99.3Cu0.7合金粉粒按照120:1的质量比,加入到步骤S3配好的含有还原剂、分散剂、稀释剂的混合溶剂中,采用机械搅拌均匀混合,得到混有微米锡基焊料粉粒的纳米银膏。
实施例四
本实施例提供了一种纳米银膏,该纳米银膏中含有平均粒径为25nm的纳米银粉、平均粒径为70nm的纳米银粉、平均粒径为1200nm的纳米银粉所组成的混合纳米银粉,其质量比为9:5:1;含有平均粒径为20μm的Sn42Bi57Ag1合金粉粒(熔点为139℃)和Sn96.5Ag3Cu0.5合金粉粒(熔点为217℃)所组成的混合低熔点微米合金粉粒(其质量比为4:1),上述混合纳米银粉与混合低熔点微米合金粉粒的质量之比为30:1;并含有将上述粉粒形成膏状的稀释剂、防止银膏中粉末发生团聚的分散剂、焊接过程用于还原被焊面氧化层和银膏中金属颗粒氧化层的还原剂。所述稀释剂为质量百分比为1:3:4的正戊烷、丙二醇和醋酸乙酯,所述稀释剂在整个纳米银膏体系中的质量百分比为8%。所述分散剂为质量百分比为1:2:4的聚乙烯酰胺、聚丙烯酸钠和十二烷基硫酸钠,所述分散剂在整个纳米银膏体系中的质量百分比为2.5%。所述还原剂为质量百分比为1:4的草酸和松香酸,所述还原剂在整个纳米银膏体系中的质量百分比为1.2%。
纳米银膏的制备方法,包括如下步骤:
S1、通过化学还原银盐溶液,并采用将银沉积层在100Pa以下的负压环境中干燥的方法分别得到平均粒径为25nm、70nm、1200nm的纳米银粉;
S2、按照锡基焊料的合金成分分别配置好所述的Sn96.5Ag3Cu0.5合金和Sn42Bi57Ag1合金,并将Sn42Bi57Ag1合金和Sn96.5Ag3Cu0.5合金分别通过真空研磨机研磨,得到平均粒径均为20μm的Sn42Bi57Ag1合金粉粒和Sn96.5Ag3Cu0.5合金粉粒;
S3、按照质量百分比为1:3:4的正戊烷、丙二醇和醋酸乙酯,在整个纳米银膏体系中的总质量百分比为8%的配比,配好稀释剂。按照质量百分比为1:2:4的聚乙烯酰胺、聚丙烯酸钠和十二烷基硫酸钠,在整个纳米银膏体系中的总质量百分比为2.5%的配比,配好分散剂。按照质量百分比为1:4的草酸和松香酸,在整个纳米银膏体系中的总质量百分比为1.2%的配比,配好还原剂。
S4、将步骤S1制成的纳米银粉(平均粒径为25nm的纳米银粉、平均粒径为70nm的纳米银粉、平均粒径为1200nm的纳米银粉的质量比为9:5:1)与步骤S2制成的微米合金粉粒(Sn42Bi57Ag1合金粉粒和Sn96.5Ag3Cu0.5合金粉粒的质量比为4:1)按照质量比30:1,加入到步骤S3配好的含有还原剂、分散剂、稀释剂的混合溶剂中,采用磁力搅拌均匀混合,得到混有微米锡基焊料粉粒的纳米银膏。
实施例五
本实施例提供了一种纳米银膏,该纳米银膏中含有平均粒径为15nm的纳米银粉、平均粒径为60nm的纳米银粉、平均粒径为900nm的纳米银粉、平均粒径为1500nm的纳米银粉所组成的混合纳米银粉,其质量比为12:9:5:1;含有平均粒径为50μm的Sn64Bi35Ag1合金粉粒(熔点范围约为139-180℃)、平均粒径为10μm的Sn96Ag2.5Bi1Cu0.5合金粉粒(熔点约为215℃)、平均粒径为2μm的SnSb5合金粉粒(熔点约为240℃)所组成的混合低熔点微米合金粉粒,其质量比为11:5:2;上述混合纳米银粉与混合低熔点微米合金粉粒的质量之比为80:1;并含有将上述粉粒形成膏状的稀释剂、防止银膏中粉末发生团聚的分散剂、焊接过程用于还原被焊面氧化层和银膏中金属颗粒氧化层的还原剂。所述稀释剂为质量百分比为1:2:5的正庚烷、丁醇和醋酸乙酯,所述稀释剂在整个纳米银膏体系中的质量百分比为6%。所述分散剂为质量百分比为1:1:2的聚丙烯酸钾、聚丙烯酰胺和十二烷基硫酸钠,所述分散剂在整个纳米银膏体系中的质量百分比为3%。所述还原剂为质量百分比为1:3:4的乙酸、戊二酸和松香酸,所述还原剂在整个纳米银膏体系中的质量百分比为1.5%。
纳米银膏的制备方法,包括如下步骤:
S1、通过化学还原银盐溶液,并采用将银沉积层在100Pa以下的负压环境中干燥的方法分别得到平均粒径为15nm、60nm、900nm和1500nm的纳米银粉;
S2、按照锡基焊料的合金成分分别配置好所述的Sn64Bi35Ag1合金、Sn96Ag2.5Bi1Cu0.5合金和SnSb5合金,并将其分别通过真空研磨机研磨得到平均粒径为50μm的Sn64Bi35Ag1合金粉粒、平均粒径为10μm的Sn96Ag2.5Bi1Cu0.5合金粉粒、平均粒径为2μm的SnSb5合金粉粒;
S3、按照质量百分比为1:2:5的正庚烷、丁醇和醋酸乙酯,在整个纳米银膏体系中的总质量百分比为6%的配比,配好稀释剂。按照质量百分比为1:1:2的聚丙烯酸钾、聚丙烯酰胺和十二烷基硫酸钠,在整个纳米银膏体系中的总质量百分比为3%的配比,配好分散剂。按照质量百分比为1:3:4的乙酸、戊二酸和松香酸,在整个纳米银膏体系中的总质量百分比为1.5%的配比,配好还原剂。
S4、将步骤S1制成的纳米银粉(平均粒径为15nm的纳米银粉、平均粒径为60nm的纳米银粉、平均粒径为900nm的纳米银粉、平均粒径为1500nm的纳米银粉的质量百分比为12:9:5:1)与步骤S2制成的微米合金粉粒(Sn64Bi35Ag1合金粉粒、Sn96Ag2.5Bi1Cu0.5合金粉粒和SnSb5合金粉粒的质量比为11:5:2)按照80:1的质量比,加入到步骤S3配好的含有还原剂、分散剂、稀释剂的混合溶剂中,采用机械搅拌均匀混合,得到混有微米锡基焊料粉粒的纳米银膏。
为了进一步验证本发明的技术效果,以下对本发明的纳米银膏进行焊接试验。其中,焊接试验所需用到的检测样品和被焊接材料具体为:
检测样品:
本发明实施例五:混有微米锡基焊料粉粒的纳米银膏
对比例一:未加有微米锡基焊料粉粒(其它条件与本发明实施例五相同)的纳米银膏
被焊接材料:厚度为1.5mm,焊接面积为10mm*8mm的无氧铜板。
焊接方式:通过在两块无氧铜板中间分别夹设0.1mm厚的对比例一的纳米银膏或者本发明实施例五的纳米银膏,且对对比例一的纳米银膏和本发明实施例五的纳米银膏同时进行无额外施加压力的常压回流焊接。
以下对焊接后的焊层进行性能测试,焊层的性能测试包括焊层孔隙率、剪切强度、热导率,以及焊层进行温度循环冲击后的孔隙率。焊层孔隙率通过超声波扫描仪或X-Ray检测仪来检测,剪切强度通过电子万能试验机来测试,热导率通过激光闪色法导热分析仪来测试。
焊层的孔隙率越小,表明纳米银膏焊接后的焊层质量越好,以及焊层进行温度循环冲击后的孔隙率变化越小,表明焊层的退化程度越低,即焊层抗温度冲击的能力越强。焊层的剪切强度越大,表明焊层抗机械冲击的能力越强。焊层的热导率越大,表明焊层将功率器件工作时产生的热量传导出去的能力越强。
(1)实验一:焊层孔隙率和热导率测试
表1焊接后的焊层孔隙率和热导率
从表1可以看出,焊接后,本发明实施例五的纳米银膏比对比例一的纳米银膏的焊层孔隙率平均降低约53.2%((19.74-9.24)/19.74×100%=53.2%),热导率提高约35.5%((248-183)/183×100%=35.5%)。
(2)实验二:焊层剪切强度测试
对实验一中的对比例一的纳米银膏和本发明实施例五的纳米银膏焊接后相互对应的五组焊层分别进行剪切强度测试,测试结果如表2所示。
表2焊接后的焊层剪切强度
从表2可以看出,焊接后,本发明实施例五的纳米银膏比对比例一的纳米银膏的焊层剪切强度提高约29.2%((35.0-27.1)/27.1×100%=29.2%)。
(3)实验三:焊层经过温度循环冲击后的孔隙率(退化程度)
对实验一中的对比例一的纳米银膏和本发明实施例五的纳米银膏焊接后相互对应的五组焊层分别经过1000次,-40℃-125℃的温度循环冲击后,检测其焊层孔隙率(温度循环冲击后的焊层孔隙率相较于温度循环冲击前的焊层孔隙率变化较大时,说明退化程度较严重,其中,退化程度=温度循环冲击后的孔隙率-温度循环冲击前的孔隙率),测试结果如表3所示。
表3焊接后的焊层经温度循环冲击后的退化程度
从表3可以看出,采用对比例一的纳米银膏和本发明实施例五的纳米银膏焊接后的焊层在经过1000次,-40℃-125℃的温度循环冲击后,本发明实施例五的纳米银膏的焊层退化程度明显低于对比例一的纳米银膏的焊层退化程度,本发明实施例五的纳米银膏的焊层退化程度比对比例一的纳米银膏的焊层退化程度要降低约46.7%((3.45-1.84)/3.45×100%=46.7%)。
为了更进一步验证本发明的技术效果,以下对本发明实施例一的加有不同粒径和不同加入量的微米锡基焊料粉粒的纳米银膏,作为对比例进行焊接试验。其中,焊接试验所需用到的检测样品和被焊接材料具体为:
检测样品:本发明实施例一的加有不同粒径和不同加入量的微米锡基焊料粉粒的纳米银膏
本发明实施例一:按照纳米银粉与平均粒径为5μm的微米Sn42Bi58粉粒的质量之比为200:1,制成的纳米银膏
对比例二:按照纳米银粉与平均粒径为5μm的微米Sn42Bi58粉粒的质量之比为10:1(其它条件与本发明实施例一相同),制成的纳米银膏
对比例三:按照纳米银粉与平均粒径为5μm的微米Sn42Bi58粉粒的质量之比为800:1(其它条件与本发明实施例一相同),制成的纳米银膏
对比例四:按照纳米银粉与平均粒径为250μm的微米Sn42Bi58粉粒的质量之比为200:1(其它条件与本发明实施例一相同),制成的纳米银膏
被焊接材料:厚度为1.5mm,焊接面积为10mm*8mm的无氧铜板。
焊接方式:通过在两块无氧铜板中间分别夹设0.1mm厚的本发明实施例一、对比例二、对比例三、对比例四的纳米银膏,且对本发明实施例一、对比例二、对比例三、对比例四的纳米银膏同时进行无额外施加压力的常压回流焊接。
对焊接后的焊层,经过1000次,-40℃-125℃的温度循环冲击后的退化程度进行测试,测试结果如表4所示。
表4焊接后的焊层经温度循环冲击后的退化程度
从表4可以看出,采用本发明实施例一、对比例二、对比例三、对比例四的纳米银膏焊接后的焊层在经过1000次,-40℃-125℃的温度循环冲击后,本发明实施例一的纳米银膏的焊层退化程度明显低于对比例二、对比例三、对比例四的纳米银膏的焊层退化程度,本发明实施例一的纳米银膏的焊层退化程度比对比例二的纳米银膏的焊层退化程度要降低约59.3%((5.77-2.35)/5.77×100%=59.3%),比对比例三的纳米银膏的焊层退化程度要降低约31.1%((3.41-2.35)/3.41×100%=31.1%),比对比例四的纳米银膏的焊层退化程度要降低约46.6%((4.40-2.35)/4.40×100%=46.6%)。
以上所述仅是本发明的优选实施方式,应当指出,对于本技术领域的普通技术人员来说,在不脱离本发明技术原理的前提下,还可以做出若干改进和替换,这些改进和替换也应视为本发明的保护范围。
Claims (9)
1.一种纳米银膏,其特征在于,包括纳米银粉、微米锡基焊料粉粒、还原剂、分散剂、稀释剂;
所述纳米银粉与所述微米锡基焊料粉粒的质量之比为20-500:1。
2.根据权利要求1所述的纳米银膏,其特征在于,所述微米锡基焊料粉粒的材质为熔点在120-250℃范围内的锡基合金。
3.根据权利要求2所述的纳米银膏,其特征在于,所述微米锡基焊料粉粒的材质为SnBi系列合金、SnBiAg系列合金、SnAg系列合金、SnCu系列合金、SnAgCu系列合金、SnSb系列合金、SnSbCu系列合金、SnSbAg系列合金、SnAgCuBi系列合金、SnAgCuSb系列合金中的至少一种。
4.根据权利要求1所述的纳米银膏,其特征在于,
所述纳米银粉的平均粒径为5-3000nm;
所述微米锡基焊料粉粒的平均粒径为0.1-100μm。
5.根据权利要求4所述的纳米银膏,其特征在于,
所述纳米银粉的平均粒径为10-1500nm;
所述微米锡基焊料粉粒的平均粒径为0.5-50μm。
6.根据权利要求1所述的纳米银膏,其特征在于,所述纳米银粉为一种平均粒径的纳米银粉或两种以上不同平均粒径的纳米银粉混合体。
7.根据权利要求1所述的纳米银膏,其特征在于,所述纳米银粉与所述微米锡基焊料粉粒的质量之比为30-200:1。
8.根据权利要求1所述的纳米银膏,其特征在于,
所述稀释剂为醇类、烃类、酮类、酯类等中的至少一种;
所述稀释剂在体系中的质量百分比为2-8%;
所述分散剂为聚烃类酰胺、聚烃类酸盐、烷基酸盐等中的至少一种;
所述分散剂在体系中的质量百分比为0.1-3%;
所述还原剂为有机酸中的至少一种;
所述还原剂在体系中的质量百分比为0.1-1.5%。
9.权利要求1-8任一项所述的纳米银膏的制备方法,其特征在于,是将所述纳米银粉、所述微米锡基焊料粉粒与所述还原剂、分散剂、稀释剂混合均匀,得到纳米银膏。
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