CN114799615A - Silver powder surface modification method, silver solder paste, and preparation method and application of silver solder paste - Google Patents
Silver powder surface modification method, silver solder paste, and preparation method and application of silver solder paste Download PDFInfo
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- CN114799615A CN114799615A CN202210356303.1A CN202210356303A CN114799615A CN 114799615 A CN114799615 A CN 114799615A CN 202210356303 A CN202210356303 A CN 202210356303A CN 114799615 A CN114799615 A CN 114799615A
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- silver powder
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- dispersing
- ether
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 276
- 238000002715 modification method Methods 0.000 title claims abstract description 19
- 229910000679 solder Inorganic materials 0.000 title claims description 57
- 238000002360 preparation method Methods 0.000 title abstract description 13
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- 229910052709 silver Inorganic materials 0.000 claims abstract description 44
- 239000004332 silver Substances 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims abstract description 41
- 238000005245 sintering Methods 0.000 claims abstract description 35
- 238000002156 mixing Methods 0.000 claims abstract description 33
- 238000005476 soldering Methods 0.000 claims abstract description 32
- 238000001035 drying Methods 0.000 claims abstract description 17
- 238000007710 freezing Methods 0.000 claims abstract description 17
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- 239000003960 organic solvent Substances 0.000 claims description 39
- 238000000034 method Methods 0.000 claims description 36
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
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- 238000010438 heat treatment Methods 0.000 claims description 17
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- NUMQCACRALPSHD-UHFFFAOYSA-N tert-butyl ethyl ether Chemical compound CCOC(C)(C)C NUMQCACRALPSHD-UHFFFAOYSA-N 0.000 claims description 6
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 5
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- JLGLQAWTXXGVEM-UHFFFAOYSA-N triethylene glycol monomethyl ether Chemical compound COCCOCCOCCO JLGLQAWTXXGVEM-UHFFFAOYSA-N 0.000 claims description 5
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- YAJYJWXEWKRTPO-UHFFFAOYSA-N 2,3,3,4,4,5-hexamethylhexane-2-thiol Chemical compound CC(C)C(C)(C)C(C)(C)C(C)(C)S YAJYJWXEWKRTPO-UHFFFAOYSA-N 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 4
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- 238000003756 stirring Methods 0.000 claims description 4
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 4
- WUOACPNHFRMFPN-SECBINFHSA-N (S)-(-)-alpha-terpineol Chemical compound CC1=CC[C@@H](C(C)(C)O)CC1 WUOACPNHFRMFPN-SECBINFHSA-N 0.000 claims description 3
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- GDXHBFHOEYVPED-UHFFFAOYSA-N 1-(2-butoxyethoxy)butane Chemical compound CCCCOCCOCCCC GDXHBFHOEYVPED-UHFFFAOYSA-N 0.000 claims description 3
- IBLKWZIFZMJLFL-UHFFFAOYSA-N 1-phenoxypropan-2-ol Chemical compound CC(O)COC1=CC=CC=C1 IBLKWZIFZMJLFL-UHFFFAOYSA-N 0.000 claims description 3
- OAYXUHPQHDHDDZ-UHFFFAOYSA-N 2-(2-butoxyethoxy)ethanol Chemical compound CCCCOCCOCCO OAYXUHPQHDHDDZ-UHFFFAOYSA-N 0.000 claims description 3
- GZMAAYIALGURDQ-UHFFFAOYSA-N 2-(2-hexoxyethoxy)ethanol Chemical compound CCCCCCOCCOCCO GZMAAYIALGURDQ-UHFFFAOYSA-N 0.000 claims description 3
- ULIKDJVNUXNQHS-UHFFFAOYSA-N 2-Propene-1-thiol Chemical compound SCC=C ULIKDJVNUXNQHS-UHFFFAOYSA-N 0.000 claims description 3
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 claims description 3
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 claims description 3
- WVDYBOADDMMFIY-UHFFFAOYSA-N Cyclopentanethiol Chemical compound SC1CCCC1 WVDYBOADDMMFIY-UHFFFAOYSA-N 0.000 claims description 3
- ZAFNJMIOTHYJRJ-UHFFFAOYSA-N Diisopropyl ether Chemical compound CC(C)OC(C)C ZAFNJMIOTHYJRJ-UHFFFAOYSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- 230000001476 alcoholic effect Effects 0.000 claims description 3
- OVKDFILSBMEKLT-UHFFFAOYSA-N alpha-Terpineol Natural products CC(=C)C1(O)CCC(C)=CC1 OVKDFILSBMEKLT-UHFFFAOYSA-N 0.000 claims description 3
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 claims description 3
- 229940088601 alpha-terpineol Drugs 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- WQAQPCDUOCURKW-UHFFFAOYSA-N butanethiol Chemical compound CCCCS WQAQPCDUOCURKW-UHFFFAOYSA-N 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- VTXVGVNLYGSIAR-UHFFFAOYSA-N decane-1-thiol Chemical compound CCCCCCCCCCS VTXVGVNLYGSIAR-UHFFFAOYSA-N 0.000 claims description 3
- KZCOBXFFBQJQHH-UHFFFAOYSA-N octane-1-thiol Chemical compound CCCCCCCCS KZCOBXFFBQJQHH-UHFFFAOYSA-N 0.000 claims description 3
- QJVXKWHHAMZTBY-GCPOEHJPSA-N syringin Chemical compound COC1=CC(\C=C\CO)=CC(OC)=C1O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 QJVXKWHHAMZTBY-GCPOEHJPSA-N 0.000 claims description 3
- 229940116411 terpineol Drugs 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- IKWYUCWHODZHMH-UHFFFAOYSA-N 1-hydroxysulfanylhexane Chemical compound CCCCCCSO IKWYUCWHODZHMH-UHFFFAOYSA-N 0.000 claims 1
- GMEYGUADINVWFH-UHFFFAOYSA-N 1-hydroxysulfanylundecane Chemical compound CCCCCCCCCCCSO GMEYGUADINVWFH-UHFFFAOYSA-N 0.000 claims 1
- AIZDPURTKBBYEA-UHFFFAOYSA-N hydroxysulfanylcyclohexane Chemical compound OSC1CCCCC1 AIZDPURTKBBYEA-UHFFFAOYSA-N 0.000 claims 1
- PWRKXLBZLTYQGN-UHFFFAOYSA-N hydroxysulfanylmethylbenzene Chemical compound OSCC1=CC=CC=C1 PWRKXLBZLTYQGN-UHFFFAOYSA-N 0.000 claims 1
- 238000004806 packaging method and process Methods 0.000 abstract description 11
- 239000000843 powder Substances 0.000 abstract description 6
- 125000003396 thiol group Chemical group [H]S* 0.000 abstract 2
- 239000000758 substrate Substances 0.000 description 26
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- 239000004065 semiconductor Substances 0.000 description 6
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 4
- 239000000919 ceramic Substances 0.000 description 4
- 238000009792 diffusion process Methods 0.000 description 4
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- 239000010703 silicon Substances 0.000 description 4
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- QZLAEIZEPJAELS-UHFFFAOYSA-N 2,4,4-trimethylpentane-2-thiol Chemical compound CC(C)(C)CC(C)(C)S QZLAEIZEPJAELS-UHFFFAOYSA-N 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 229910052802 copper Inorganic materials 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 238000004100 electronic packaging Methods 0.000 description 3
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- 238000003466 welding Methods 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- PMBXCGGQNSVESQ-UHFFFAOYSA-N 1-Hexanethiol Chemical compound CCCCCCS PMBXCGGQNSVESQ-UHFFFAOYSA-N 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical class SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- QCEUXSAXTBNJGO-UHFFFAOYSA-N [Ag].[Sn] Chemical compound [Ag].[Sn] QCEUXSAXTBNJGO-UHFFFAOYSA-N 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- UENWRTRMUIOCKN-UHFFFAOYSA-N benzyl thiol Chemical compound SCC1=CC=CC=C1 UENWRTRMUIOCKN-UHFFFAOYSA-N 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- CMKBCTPCXZNQKX-UHFFFAOYSA-N cyclohexanethiol Chemical compound SC1CCCCC1 CMKBCTPCXZNQKX-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
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- 230000008020 evaporation Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- ORTRWBYBJVGVQC-UHFFFAOYSA-N hexadecane-1-thiol Chemical compound CCCCCCCCCCCCCCCCS ORTRWBYBJVGVQC-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
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- 239000011148 porous material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- GEKDEMKPCKTKEC-UHFFFAOYSA-N tetradecane-1-thiol Chemical compound CCCCCCCCCCCCCCS GEKDEMKPCKTKEC-UHFFFAOYSA-N 0.000 description 1
- GZCWPZJOEIAXRU-UHFFFAOYSA-N tin zinc Chemical compound [Zn].[Sn] GZCWPZJOEIAXRU-UHFFFAOYSA-N 0.000 description 1
- CCIDWXHLGNEQSL-UHFFFAOYSA-N undecane-1-thiol Chemical compound CCCCCCCCCCCS CCIDWXHLGNEQSL-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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Images
Classifications
-
- 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
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/30—Selection of soldering or welding materials proper with the principal constituent melting at less than 1550 degrees C
- B23K35/3006—Ag as the principal constituent
-
- 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
- B23K35/40—Making wire or rods for soldering or welding
Abstract
The invention provides a silver powder surface modification method, silver soldering paste, a preparation method and application thereof, wherein the silver powder surface modification method comprises the following steps: dispersing the silver powder in a first solvent, and separating to obtain wet silver powder; mixing and dispersing the coating agent, the first solvent and the wet silver powder, and separating to obtain the surface-coated wet silver powder; mixing the surface-coated wet silver powder with a second solvent, dispersing, freezing and drying to obtain surface-modified silver powder, and finishing surface modification of the silver powder; wherein the coating agent is a thiol organic coating agent. According to the invention, the thiol organic coating agent is used for carrying out surface modification on the silver powder, so that the nano silver powder is prevented from easily agglomerating and the bonding strength is improved. The connection interface of the connection layer formed by sintering the silver soldering paste is good in combination degree, uniform and compact, the shear strength of the connection layer can reach more than 10MPa after the connection layer is sintered at 300 ℃, and the connection layer can be well applied to packaging and interconnection of electronic devices.
Description
Technical Field
The invention relates to the technical field of electronic packaging, in particular to a silver powder surface modification method, silver solder paste, a preparation method and application thereof.
Background
With the rapid development of new electronic fields, such as aerospace, new energy vehicles, high speed railways, displays, radio frequency electronics, etc., the demands for efficient energy utilization, miniaturized packaging and high temperature device application are increasing, and silicon-based devices have not been able to meet the working requirements. Compared with the traditional silicon-based semiconductor, wide band gap semiconductor devices such as silicon carbide (SiC) and gallium nitride (GaN) have the advantages of higher operating temperature and breakdown voltage, lower switching loss, higher current density and the like, and are receiving wide attention. Compared with the instability of the traditional silicon-based semiconductor under high-temperature application, the wide-band-gap semiconductor can realize high reliability of work under high temperature (more than 250 ℃), and can meet the high-temperature application requirements of power devices. Chip package interconnection technology is a key technology in power electronic device packaging, and directly influences the thermal performance, electrical performance and reliability of power electronic devices. At present, lead-free soft solders such as tin-silver, tin-zinc and tin-copper are common packaging interconnection materials in the electronic industry, but the materials used as the interconnection layer are easy to fail due to melting of solder joints under a high-temperature working environment. Therefore, there is a strong need in the electronics industry to develop interconnect materials suitable for wide bandgap semiconductor device packages to address issues related to heat dissipation, reliability, etc. of high temperature operating devices.
In the field of wide bandgap semiconductor packaging, sintered silver has received much attention from researchers due to its excellent thermal and electrical conductivity and good high temperature stability. Unlike conventional soldering processes, sintered silver bonding techniques are formed by solvent wetting, evaporation and solid diffusion processes, and exhibit a nano-or micron-scale pore structure after sintering. There is a review paper that the sintering temperature, pressure and holding time during sintering all have an effect on the microstructure of the sintered silver particles, and the bonding quality of the sintered silver depends to a large extent on the size and shape of the silver powder. The surface energy of micron silver is low, satisfactory sintering quality cannot be obtained under low-temperature and pressureless conditions, and sintering under the pressureless condition is required to achieve the satisfactory sintering quality, so that the probability of causing damage to a chip during bonding is increased. Therefore, the realization of high-quality pressureless sintering by using nano silver powder is widely researched. When the silver powder reaches the nano scale, the small size effect can occur, and the melting point and the sintering temperature of the silver powder can be obviously reduced. The small size means larger specific surface area, and the driving force of the surface area reduction can be used for realizing the inter-atomic diffusion without reaching the melting point in the sintering process, thereby realizing the effect of low-temperature sintering interconnection.
The metallic bulk silver has a high melting point of 961.8 ℃, and once the nano silver is sintered, the melting point of the nano silver is close to that of the bulk silver, so that the nano silver has a very good high-temperature stability. There are a number of problems that still need to be solved in the application of nanosilver to sintered solder pastes. For example, when the size is less than a certain value, the surface energy becomes very high, and the high surface energy causes the nano silver to spontaneously agglomerate at room temperature and cause non-uniform dispersion. The agglomerated nano silver may form micron-sized agglomerates, so that the surface energy is reduced, the sintering driving force of the nano silver is reduced, and the sintering assisting effect of the nano silver serving as nano particles is lost. Therefore, it is an urgent problem to prevent the spontaneous aggregation of the silver nanopowder at room temperature and modify the surface thereof to prevent the aggregation.
In addition to the influence of nanosilver on the sintering properties of solder pastes, the solvent of solder pastes is also a very important influencing factor. Most current solder paste formulations are single solvent systems. However, a single-solvent system is easy to decompose and volatilize rapidly at a certain temperature point, and the condition can cause too many internal cavities of the sintered silver and even cracking, thereby causing the sintering quality to be reduced.
Based on the defects of the current nano silver applied to the sintering solder paste, the improvement is needed.
Disclosure of Invention
In view of the above, the present invention provides a silver powder surface modification method, a silver solder paste, and a preparation method and an application thereof, so as to solve or partially solve the problems in the prior art.
In a first aspect, the present invention provides a method for modifying the surface of silver powder, comprising the steps of:
dispersing the silver powder in a first solvent, and separating to obtain wet silver powder;
mixing and dispersing the coating agent, the first solvent and the wet silver powder, and separating to obtain the surface-coated wet silver powder;
mixing the surface-coated wet silver powder with a second solvent, dispersing, freezing and drying to obtain surface-modified silver powder, and finishing surface modification of the silver powder;
wherein the coating agent is a thiol organic coating agent.
Preferably, in the silver powder surface modification method, the thiol organic coating agent includes at least one of n-butylthiol, cyclopentylthiol, allylthiol, pentylthiol, octylthiol, tert-octylthiol, n-dodecylthiol, tert-dodecylthiol, tetradecylthiol, n-pentadecylthiol, hexadecylthiol, n-octadecylthiol, 1-decylthiol, 1-undecylthiol, 2-phenethylthiol, benzylthiol, cyclohexylthiol, and 1-hexylthiol;
and/or, the first solvent comprises ethanol and/or water;
and/or the second solvent comprises a mixed solution of ethanol and tert-butyl alcohol.
Preferably, in the silver powder surface modification method, the mass ratio of the first solvent to the silver powder in the step of placing the silver powder in the first solvent for dispersion is (4-20): 1;
the mass ratio of the coating agent to the first solvent to the silver powder in the step of mixing the coating agent, the first solvent and the wet silver powder is (0.01-0.2): 4-20): 1;
the mass ratio of the silver powder to the second solvent is 1 (1-10).
Preferably, in the method for surface modification of silver powder, the silver powder includes a plate-like silver powder and/or a spherical silver powder;
placing the silver powder in a first solvent for dispersion, wherein the dispersion specifically comprises the following steps: dispersing for 3-60 min under ultrasound;
in the step of mixing and dispersing the coating agent, the first solvent and the wet silver powder, the dispersion specifically comprises the following steps: dispersing for 3-60 min under ultrasound;
mixing the surface-coated wet silver powder with a second solvent, and then dispersing, wherein in the steps of freezing and drying, the dispersion specifically comprises the following steps: dispersing for 3-60 min under ultrasound; the freezing method specifically comprises the following steps: freezing in a refrigerator for 1-12 h; the drying specifically comprises the following steps: drying in a freeze dryer for 5-48 h;
if the second solvent comprises a mixed solution of ethanol and tert-butyl alcohol, the volume ratio of the ethanol to the tert-butyl alcohol is (0.02-0.4): 1.
In a second aspect, the invention also provides a silver solder paste, which comprises the surface modified silver powder obtained by the modification method and a multi-component organic solvent.
Preferably, the silver solder paste comprises two or more of the polyhydric organic solvents including alcohol solvents, ether solvents and acid solvents;
the alcoholic solvent comprises one or more of ethanol, ethylene glycol, tert-butanol, diethylene glycol, terpineol, triethylene glycol, alpha-terpineol, beta-terpineol, gamma-terpineol and delta-terpineol;
the ether solvent comprises one or more of isopropyl ether, ethyl tert-butyl ether, diethylene glycol butyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, diethylene glycol monohexyl ether, ethylene glycol dibutyl ether, ethylene glycol phenyl ether, ethylene glycol butyl ether and propylene glycol phenyl ether;
the acid solvent comprises one or more of succinic acid, citric acid, n-octanoic acid, n-decanoic acid, oleic acid, sebacic acid, dodecanedioic acid and suberic acid.
Preferably, the mass ratio of the surface modified silver powder to the multi-element organic solvent in the silver solder paste is (2-10): 1;
if the surface modified silver powder comprises flaky surface modified silver powder, the particle size of the flaky surface modified silver powder is 100 nm-800 nm, and the thickness of the flaky surface modified silver powder is 20-50 nm;
if the surface-modified silver powder comprises spherical surface-modified silver powder, the particle size of the spherical surface-modified silver powder is 10 nm-200 nm;
if the surface modified silver powder comprises flaky surface modified silver powder and spherical surface modified silver powder, the mass ratio of the flaky surface modified silver powder to the spherical surface modified silver powder is (5-10) to (5-1).
In a third aspect, the invention further provides a preparation method of the silver solder paste, which comprises the following steps: and mixing and stirring the surface modified silver powder and the multi-element organic solvent to obtain the silver soldering paste.
In a fourth aspect, the invention also provides an application of the silver solder paste in chip packaging interconnection.
Preferably, in the above application, the chip package interconnection includes a first mother sheet, a second mother sheet, and a connection layer for connecting the first mother sheet and the second mother sheet, and the connection layer is formed by sintering the silver solder paste through a pressureless sintering process;
the pressureless sintering process comprises the following specific steps: the heating rate is 1-25 ℃/min, the heating peak temperature is 150-300 ℃, and the heat preservation time is 10-120 min.
Compared with the prior art, the silver powder surface modification method, the silver soldering paste and the preparation method and application thereof have the following beneficial effects:
1. according to the silver powder surface modification method, the thiol organic coating agent is used for carrying out surface modification on the silver powder, so that the nano silver powder is prevented from easily agglomerating, the bonding strength is improved, and the problems that the existing nano silver powder is easily agglomerated and the shearing strength is low after a soldering paste is sintered to form a connecting layer are solved;
2. the silver soldering paste comprises surface modification and a multi-component organic solvent, wherein the multi-component organic solvent enables the sintering and diffusion of the surface modified silver powder to be more sufficient so as to realize a more compact interconnected structure;
3. the silver solder paste is applied to chip packaging interconnection, bonding is realized within 150-300 ℃, the sintering temperature is far lower than the melting point (961.8 ℃) of bulk silver, and the silver solder paste can be well applied to the field of non-pressure low-temperature welding and high-temperature service electronic packaging. The connection interface of the connection layer formed by sintering the soldering paste has good combination degree, is uniform and compact, can achieve the shear strength of more than 10MPa when being sintered at 300 ℃, and can be well applied to the packaging interconnection of electronic devices.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below. It is obvious that the drawings in the following description are only some embodiments of the invention, and that for a person skilled in the art, other drawings can be derived from them without inventive effort.
FIG. 1 is a schematic structural view of a DBC substrate used in the present invention;
FIG. 2 is a schematic structural diagram of a package interconnect structure according to the present invention;
FIG. 3 is an SEM photograph of a commercial spherical silver powder used in example 1 of the present invention;
fig. 4 is an SEM image of a shear fracture surface of the connection layer formed using the silver solder paste of example 2.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention. It is to be understood that the embodiments described are only a few embodiments of the present invention, and not all embodiments. The components of embodiments of the present invention generally described and illustrated in the figures herein may be arranged and designed in a wide variety of different configurations.
The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is obvious 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 obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
The embodiment of the application provides a silver powder surface modification method, which comprises the following steps:
s1, placing the silver powder in a first solvent for dispersion, and separating to obtain wet silver powder;
s2, mixing and dispersing the coating agent, the first solvent and the wet silver powder, and separating to obtain the surface-coated wet silver powder;
s3, mixing the surface-coated wet silver powder with a second solvent, dispersing, freezing and drying to obtain surface-modified silver powder, and finishing surface modification of the silver powder;
wherein the coating agent is a thiol organic coating agent.
In the silver powder surface modification method of the present application, the dispersion in steps S1 to S3 may be physical dispersion, such as mechanical dispersion or ultrasonic dispersion, and the purpose of dispersion is achieved by breaking the agglomerates mainly by using mechanical forces such as impact, shear and stretching generated by strong stirring, extrusion and impact. According to the method, the surface of the silver powder is modified by the thiol organic coating agent, so that the nano silver powder is prevented from easily agglomerating and the bonding strength is improved, and the problems that the existing nano silver powder is easily agglomerated and the shearing strength is low after a soldering paste is sintered to form a connecting layer are solved.
It is pointed out that commercial nano silver particles leave the factory, and because some unknown organic coating impurities exist on the surfaces of the silver particles, the sintering and diffusion of the silver particles are hindered, and the shear strength is low; adopt first solvent to wash silver powder in order to get rid of silver powder surface impurity in this application, adopt the organic cladding agent of mercaptan class to carry out surface modification to silver powder simultaneously, reach the effect that prevents silver particle reunion, can be when the sintering again, the decomposition of volatilizing that organic coating can be complete finally promotes bonding shear strength.
In some embodiments, the thiol-based organic capping agent comprises at least one of n-butylthiol, cyclopentylthiol, allylthiol, pentylmercaptan, octylthiol, tert-octylthiol, n-dodecylthiol, tert-dodecylthiol, tetradecylthiol, n-pentadecylthiol, hexadecylthio, n-octadecylthiol, 1-decylthiol, 1-undecylthio-thiol, 2-phenethyl-thiol, benzylthio, cyclohexylthio, and 1-hexylthio-thiol;
and/or, the first solvent comprises ethanol and/or water;
and/or the second solvent comprises a mixed solution of ethanol and tertiary butanol.
In some embodiments, the mass ratio of the first solvent to the silver powder in the step of dispersing the silver powder in the first solvent is (4-20): 1;
the mass ratio of the coating agent to the first solvent to the silver powder in the step of mixing the coating agent, the first solvent and the wet silver powder is (0.01-0.2): 4-20): 1;
the mass ratio of the silver powder to the second solvent is 1 (1-10).
In some embodiments, the silver powder includes a plate-like silver powder and/or a spherical silver powder;
placing the silver powder in a first solvent for dispersion, wherein the dispersion specifically comprises the following steps: dispersing for 3-60 min under ultrasound;
in the step of mixing and dispersing the coating agent, the first solvent and the wet silver powder, the dispersion specifically comprises the following steps: dispersing for 3-60 min under ultrasound;
mixing the surface-coated wet silver powder with a second solvent, and then dispersing, wherein in the steps of freezing and drying, the dispersion specifically comprises the following steps: dispersing for 3-60 min under ultrasound; the freezing method specifically comprises the following steps: freezing in a refrigerator for 1-12 h; the drying specifically comprises the following steps: drying in a freeze dryer for 5-48 h;
if the second solvent comprises a mixed solution of ethanol and tert-butyl alcohol, the volume ratio of the ethanol to the tert-butyl alcohol is (0.02-0.4): 1.
In some embodiments, after the silver powder is placed in the first solvent for ultrasonic dispersion, the wet silver powder is obtained after solid-liquid separation, and in practice, the above steps may be repeated for a plurality of times, for example, 1 to 5 times, according to circumstances, that is, the obtained wet silver powder is placed in the first solvent again for ultrasonic dispersion, and the operation is repeated for a plurality of times.
Specifically, if the silver powder is flake silver powder, the surface-modified flake silver powder is finally prepared; if the silver powder is spherical silver powder, the spherical silver powder with the modified surface is finally prepared.
Based on the same inventive concept, the embodiment of the application also provides the silver soldering paste which comprises the surface modified silver powder obtained by modification by the modification method and the multi-element organic solvent.
Specifically, the polybasic organic solvent means that at least two organic solvents are contained; the silver solder paste comprises the multi-component organic solvent, and the surface modified silver powder is more fully sintered and diffused due to the multi-component organic solvent, so that a more compact interconnection structure is realized.
In some embodiments, the polyhydric organic solvent includes two or more of an alcohol solvent, an ether solvent, an acid solvent;
the alcoholic solvent comprises one or more of ethanol, ethylene glycol, tert-butyl alcohol, diethylene glycol, terpineol, triethylene glycol, alpha-terpineol, beta-terpineol, gamma-terpineol and delta-terpineol;
the ether solvent comprises one or more of isopropyl ether, ethyl tert-butyl ether, diethylene glycol butyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, diethylene glycol monohexyl ether, ethylene glycol dibutyl ether, ethylene glycol phenyl ether, ethylene glycol butyl ether and propylene glycol phenyl ether;
the acid solvent comprises one or more of succinic acid, citric acid, n-octanoic acid, n-decanoic acid, oleic acid, sebacic acid, dodecanedioic acid and suberic acid.
In some embodiments, the mass ratio of the surface-modified silver powder to the multi-component organic solvent is (2-10): 1;
if the surface modified silver powder comprises the flaky surface modified silver powder, the particle size of the flaky surface modified silver powder is 100 nm-800 nm, and the thickness of the flaky surface modified silver powder is 20-50 nm;
if the surface-modified silver powder comprises spherical surface-modified silver powder, the particle size of the spherical surface-modified silver powder is 10 nm-200 nm;
if the surface modified silver powder comprises the flaky surface modified silver powder and the spherical surface modified silver powder, the mass ratio of the flaky surface modified silver powder to the spherical surface modified silver powder is (5-10): 5-1.
In some embodiments, if the polyhydric organic solvent is a mixture of three solvents, namely an alcohol solvent, an ether solvent and an acid solvent, the mass ratio of the alcohol solvent to the ether solvent to the acid solvent is (1-10): 1-3).
Based on the same inventive concept, the embodiment of the present application further provides a preparation method of the silver solder paste, which includes the following steps: and mixing and stirring the surface modified silver powder and the multi-element organic solvent to obtain the silver soldering paste.
Based on the same inventive concept, the embodiment of the application also provides an application of the silver solder paste in chip package interconnection.
In some embodiments, the chip package interconnect comprises a first master, a second master, and a connection layer for connecting the first master and the second master, the connection layer being formed by sintering using the silver solder paste described above by a pressureless sintering process.
Specifically, the first master slice and the second master slice can adopt copper sheets, gold sheets, silver sheets and the like; or, the first mother sheet and the second mother sheet can be respectively coated with copper, gold or silver ceramic sheets, silicon sheets, functional devices and the like. When the non-pressure sintering silver solder paste is applied, the silver solder paste can be coated on a first mother sheet, then a second mother sheet is stacked, and then the non-pressure sintering process is carried out, so that a connecting layer can be formed between the first mother sheet and the second mother sheet. The pressureless sintering process specifically comprises the following steps: the heating rate is 1-25 ℃/min, the heating peak temperature is 150-300 ℃, and the heat preservation time is 10-120 min.
The sintering process is pressureless sintering, so that the process complexity is reduced, and compared with pressureless sintering, the probability of damage caused by the pressure applied to the chip can be well prevented; according to the silver soldering paste containing the surface modified silver powder and the sintering process, bonding is realized within 150-300 ℃, the sintering temperature is far lower than the melting point (961.8 ℃) of the block silver, and the silver soldering paste can be well applied to the field of non-pressure low-temperature welding and high-temperature service electronic packaging. The connection interface of the connection layer formed by sintering the soldering paste has good combination degree, is uniform and compact, can achieve the shear strength of more than 10MPa when being sintered at 300 ℃, and can be well applied to the packaging interconnection of electronic devices.
The method for modifying the surface of silver powder, the silver solder paste, the method for producing the same and the use thereof are described below with reference to specific examples.
Example 1
The embodiment of the application provides a silver powder surface modification method, which comprises the following steps:
s1, putting 10g of commercial silver powder (spherical silver powder with the particle size of 60nm) into 120ml of ethanol, oscillating and dispersing in an ultrasonic cleaning machine for 20min, centrifuging, and performing solid-liquid separation to obtain wet silver powder; repeating the steps for 3 times;
s2, mixing 0.1g of n-dodecyl mercaptan, 120ml of ethanol and the wet silver powder obtained in the step S1, oscillating and dispersing in an ultrasonic cleaning machine for 30min, centrifuging, and performing solid-liquid separation to obtain surface-coated wet silver powder;
s3, mixing the surface-coated wet silver powder in the step S2, 6ml of ethanol and 30ml of tert-butyl alcohol, oscillating and dispersing in an ultrasonic cleaning machine for 60min, and then placing in a refrigerator for freezing for 10h to obtain frozen surface-coated silver powder; and drying the frozen surface-coated silver powder in a freeze dryer for 10 hours to obtain the surface modified silver powder.
The embodiment of the application also provides a silver soldering paste which comprises the surface modified silver powder prepared in the embodiment 1 and a multi-component organic solvent, wherein the mass ratio of the surface modified silver powder to the multi-component organic solvent is 8.5:1.5, and the multi-component organic solvent is formed by mixing ethylene glycol, triethylene glycol dimethyl ether and n-caprylic acid in a mass ratio of 3:3: 1.
The preparation method of the silver soldering paste comprises the following steps: and (3) placing the surface modified silver powder and the multi-element organic solvent into a mixer to mix for 20min to obtain the silver soldering paste.
Example 2
The embodiment of the application provides a silver powder surface modification method, which comprises the following steps:
s1, placing 2g of commercial silver powder (spherical silver powder with the particle size of 50 nm) in 30ml of ethanol, oscillating and dispersing in an ultrasonic cleaning machine for 30min, centrifuging, and performing solid-liquid separation to obtain wet silver powder; repeating the steps for 3 times;
s2, mixing 0.02g of tert-dodecyl mercaptan, 30ml of ethanol and the wet silver powder obtained in the step S1, oscillating and dispersing the mixture in an ultrasonic cleaner for 40min, centrifuging the mixture, and performing solid-liquid separation to obtain the surface-coated wet silver powder;
s3, mixing the surface-coated wet silver powder in the step S2, 3ml of ethanol and 15ml of tert-butyl alcohol, oscillating and dispersing in an ultrasonic cleaning machine for 40min, and then placing in a refrigerator for freezing for 12h to obtain frozen surface-coated silver powder; and drying the frozen surface-coated silver powder in a freeze dryer for 12h to obtain the surface-modified silver powder.
The embodiment of the application also provides silver solder paste which comprises the surface modified silver powder prepared in the embodiment 2 and a multi-component organic solvent, wherein the mass ratio of the surface modified silver powder to the multi-component organic solvent is 4:1, and the multi-component organic solvent is formed by mixing ethylene glycol, triethylene glycol monomethyl ether and n-decanoic acid in a mass ratio of 2:3: 1.
The preparation method of the silver soldering paste comprises the following steps: and (3) placing the surface modified silver powder and the multi-element organic solvent into a mixer to mix for 30min to obtain the silver soldering paste.
Example 3
The embodiment of the application provides a silver powder surface modification method, which comprises the following steps:
s1, placing 2g of commercial silver powder (spherical silver powder with the particle size of 20nm and flaky silver powder with the particle size of 150nm and the thickness of 20nm, wherein the mass ratio of the two types of silver powder is 1:1) in 30ml of ethanol, oscillating and dispersing in an ultrasonic cleaning machine for 30min, centrifuging, and carrying out solid-liquid separation to obtain wet silver powder; repeating the above steps for 5 times;
s2, mixing 0.02g of tert-octyl mercaptan, 30ml of ethanol and the wet silver powder obtained in the step S1, oscillating and dispersing for 50min in an ultrasonic cleaner, centrifuging, and performing solid-liquid separation to obtain the surface-coated wet silver powder;
s3, mixing the surface-coated wet silver powder in the step S2, 4ml of ethanol and 15ml of tert-butyl alcohol, oscillating and dispersing in an ultrasonic cleaning machine for 50min, and then placing in a refrigerator for freezing for 8h to obtain frozen surface-coated silver powder; and drying the frozen surface-coated silver powder in a freeze dryer for 12h to obtain the surface-modified silver powder.
The embodiment of the application also provides a silver soldering paste, which comprises the surface modified silver powder prepared in the embodiment 3 and a multi-component organic solvent, wherein the mass ratio of the surface modified silver powder to the multi-component organic solvent is 8.7:1.3, and the multi-component organic solvent is formed by mixing triethylene glycol, triethylene glycol dimethyl ether and oleic acid in a mass ratio of 2:3: 1.
The preparation method of the silver soldering paste comprises the following steps: and (3) placing the surface modified silver powder and the multi-element organic solvent into a mixer to mix for 30min to obtain the silver soldering paste.
Example 4
The embodiment of the application provides a silver powder surface modification method, which comprises the following steps:
s1, placing 2g of commercial silver powder (flaky silver powder with the particle size of 500nm and the thickness of 50 nm) in 30ml of ethanol, oscillating and dispersing in an ultrasonic cleaning machine for 50min, centrifuging, and performing solid-liquid separation to obtain wet silver powder; repeating the above steps for 4 times;
s2, mixing 0.02g of tetradecanethiol, 30ml of ethanol and the wet silver powder obtained in the step S1, oscillating and dispersing in an ultrasonic cleaning machine for 50min, centrifuging, and performing solid-liquid separation to obtain the surface-coated wet silver powder;
s3, mixing the surface-coated wet silver powder in the step S2, 4ml of ethanol and 10ml of tert-butyl alcohol, oscillating and dispersing in an ultrasonic cleaning machine for 60min, and then placing in a refrigerator for freezing for 11h to obtain frozen surface-coated silver powder; and drying the frozen surface-coated silver powder in a freeze dryer for 9 hours to obtain the surface modified silver powder.
The embodiment of the application also provides silver solder paste which comprises the surface modified silver powder prepared in the embodiment 4 and a multi-component organic solvent, wherein the mass ratio of the surface modified silver powder to the multi-component organic solvent is 9:1, and the multi-component organic solvent is formed by mixing ethylene glycol and oleic acid in the mass ratio of 1: 1.
The preparation method of the silver soldering paste comprises the following steps: and (3) placing the surface modified silver powder and the multi-element organic solvent into a mixer to mix for 30min to obtain the silver soldering paste.
Comparative example 1
This comparative example provides a silver solder paste comprising an original commercial silver powder (the same as the commercial silver powder used in example 2, the silver powder being a spherical silver powder having a particle size of 50 nm) and a polyvalent organic solvent, wherein the mass ratio of the commercial silver powder to the polyvalent organic solvent is 4:1, and the polyvalent organic solvent is formed by mixing ethylene glycol, triethylene glycol monomethyl ether, and n-decanoic acid in a mass ratio of 2:3: 1.
The preparation method of the silver soldering paste comprises the following steps: and (3) placing the surface modified silver powder and the multi-element organic solvent into a mixer to mix for 20min to obtain the silver soldering paste.
Performance testing
The silver solder pastes prepared in the above examples 1 to 4 and comparative example 1 were applied to a package interconnection structure of an electronic device. Fig. 2 shows a schematic structural diagram of a package interconnection structure, a first mother substrate and a second mother substrate in the package interconnection structure are both selected to be DBC substrates (i.e., copper-clad ceramic substrates), and a schematic structural diagram of the DBC substrates is shown in fig. 1. Specifically, the DBC substrate includes a ceramic substrate 2 and a copper plating layer 1 on the ceramic substrate 2. In fig. 2, the package interconnection structure includes a first mother sheet 3, a second mother sheet 4 and a connection layer 5, wherein the connection layer 5 is formed by performing a pressureless sintering process on the silver solder paste according to the present application.
Specifically, the application of the silver solder paste to the packaging interconnection structure of the electronic device comprises the following specific steps:
first, the master is processed: ultrasonically washing the DBC substrate (a first master slice and a second master slice) in ethanol for 3min to remove impurities on the surface of the DBC substrate, and airing;
then, uniformly coating the silver solder pastes prepared in the embodiments 1-4 and the comparative example 1 on the connecting surface of the DBC substrate, and then stacking the silver solder pastes to obtain a sandwich structure of the DBC substrate/the silver solder paste coating/the DBC substrate; then, the above DBC substrate/silver solder paste coating/DBC substrate stacked structure is placed on a heating stage, and low-temperature sintering soldering is performed, and the silver solder paste coating is sintered to form a connection layer. After cooling, the package interconnect structure as shown in fig. 2 is obtained.
And carrying out a shear fracture test on the formed connecting layer, specifically: fixing the sample on a fixing clamp of a shear force tester, controlling the tester to push and compress the sample at the speed of 100 mu m/s to carry out shear fracture test, and reading from the shear force tester to obtain the corresponding shear force when the sample is fractured.
The DBC substrate/silver solder paste coating/DBC substrate stack structure of example 1 was placed on a heating table according to the above method, and the temperature was raised from room temperature to 200 ℃, the heating rate was 5 ℃/min, and the holding time was 60min for low temperature sintering soldering, and the nano silver solder paste coating was sintered to form a connection layer.
After testing, the shear force of the connection layer formed by sintering the silver paste of example 1 was measured to be 12.1Mpa after cooling (wherein, 5 test samples were prepared according to the method, and the test data was the average value of the 5 test samples).
The DBC substrate/silver solder paste coating/DBC substrate stack structure of example 2 was placed on a heating table according to the above method, and the temperature was raised from room temperature to 250 ℃, the heating rate was 15 ℃/min, and the holding time was 20min for low temperature sintering soldering, and the nano silver solder paste coating was sintered to form the connection layer.
After testing, the shear force of the bonding layer formed by sintering the silver paste of example 2 was measured to be 37.8Mpa after cooling (wherein, 5 test samples were prepared according to the method, and the test data was the average of the 5 test samples).
The DBC substrate/silver solder paste coating/DBC substrate stack structure of example 3 was placed on a heating table according to the above method, and the temperature was raised from room temperature to 300 ℃, the heating rate was 18 ℃/min, and the holding time was 90min for low temperature sintering soldering, and the nano silver solder paste coating was sintered to form the connection layer.
After testing, the shear force of the bonding layer formed by sintering the silver paste of example 3 was measured to be 20.8Mpa after cooling (wherein, 5 test samples were prepared according to the method, and the test data was the average of the 5 test samples).
The DBC substrate/example 4 silver solder paste coating/DBC substrate stack was placed on a heating table according to the above method, and the temperature was raised from room temperature to 280 ℃, the heating rate was 20 ℃/min, and the holding time was 120min for low temperature sintering soldering, and the nano silver solder paste coating was sintered to form the connection layer.
After testing, the shear force of the bonding layer formed by sintering the silver paste of example 4 was measured to be 17.8Mpa after cooling (wherein, 5 test samples were prepared according to the method, and the test data was the average of the 5 test samples).
The DBC substrate/silver solder paste coating/DBC substrate stacking structure of comparative example 1 is placed on a heating table according to the method, the temperature is increased to 250 ℃ from room temperature, the heating rate is 15 ℃/min, the heat preservation time is 20min, low-temperature sintering welding is carried out, and the nano-silver solder paste coating is sintered to form the connecting layer.
After testing, the shear force of the connection layer formed by sintering the silver solder paste of comparative example 1 was measured to be 9.8Mpa after cooling (wherein, 5 test samples were prepared according to the method, and the test data was the average of the 5 test samples).
It can be seen from comparison between example 2 and comparative example 1 that the connection layer formed by sintering the silver solder paste in example 2 after modifying the silver powder reaches 37.8Mpa, which is much higher than 9.8Mpa in comparative example 1, which indicates that the connection layer formed by sintering the silver solder paste prepared by modifying the silver nano powder has extremely high shear strength and can be well applied to the packaging and interconnection of electronic devices.
An SEM photograph of a commercial spherical silver powder (particle size: 60nm) used in example 1 is shown in FIG. 3.
SEM image of the shear fracture surface of the connection layer formed using the silver solder paste of example 2 is shown in fig. 4.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (10)
1. The method for modifying the surface of the silver powder is characterized by comprising the following steps of:
dispersing the silver powder in a first solvent, and separating to obtain wet silver powder;
mixing and dispersing the coating agent, the first solvent and the wet silver powder, and separating to obtain the surface-coated wet silver powder;
mixing the surface-coated wet silver powder with a second solvent, dispersing, freezing and drying to obtain surface-modified silver powder, and finishing surface modification of the silver powder;
wherein the coating agent is a thiol organic coating agent.
2. The method for surface modification of silver powder according to claim 1, wherein the thiol-based organic capping agent comprises at least one of n-butylthiol, cyclopentylthiol, allylthiol, pentylmercaptan, octylthiol, t-octylthiol, n-dodecylthiol, t-dodecylthiol, tetradecylthiol, n-pentadecylthiol, hexadecylthio-octadecaylthiol, 1-decylthiol, 1-undecylthio-alcohol, 2-phenethyl-thiol, benzylthio-alcohol, cyclohexylthio-alcohol, and 1-hexylthio-alcohol;
and/or, the first solvent comprises ethanol and/or water;
and/or the second solvent comprises a mixed solution of ethanol and tert-butyl alcohol.
3. The method for surface modification of silver powder according to claim 1, wherein the step of dispersing the silver powder in the first solvent has a mass ratio of the first solvent to the silver powder of (4 to 20): 1;
the mass ratio of the coating agent to the first solvent to the silver powder in the step of mixing the coating agent, the first solvent and the wet silver powder is (0.01-0.2): 4-20): 1;
the mass ratio of the silver powder to the second solvent is 1 (1-10).
4. The method for surface modification of silver powder according to any one of claims 1 to 3, wherein the silver powder comprises a plate-like silver powder and/or a spherical silver powder;
placing the silver powder in a first solvent for dispersion, wherein the dispersion specifically comprises the following steps: dispersing for 3-60 min under ultrasound;
in the step of mixing and dispersing the coating agent, the first solvent and the wet silver powder, the dispersion specifically comprises the following steps: dispersing for 3-60 min under ultrasound;
mixing the surface-coated wet silver powder with a second solvent, and then dispersing, wherein in the steps of freezing and drying, the dispersion specifically comprises the following steps: dispersing for 3-60 min under ultrasound; the freezing method specifically comprises the following steps: freezing in a refrigerator for 1-12 h; the drying specifically comprises the following steps: drying for 5-48 h in a freeze dryer;
if the second solvent comprises a mixed solution of ethanol and tert-butyl alcohol, the volume ratio of the ethanol to the tert-butyl alcohol is (0.02-0.4): 1.
5. A silver solder paste comprising the surface-modified silver powder obtained by the modification method according to any one of claims 1 to 4 and a polyvalent organic solvent.
6. The silver solder paste according to claim 5, wherein the polyhydric organic solvent comprises two or more of an alcohol solvent, an ether solvent, and an acid solvent;
the alcoholic solvent comprises one or more of ethanol, ethylene glycol, tert-butanol, diethylene glycol, terpineol, triethylene glycol, alpha-terpineol, beta-terpineol, gamma-terpineol and delta-terpineol;
the ether solvent comprises one or more of isopropyl ether, ethyl tert-butyl ether, diethylene glycol butyl ether, triethylene glycol monomethyl ether, triethylene glycol dimethyl ether, diethylene glycol monohexyl ether, ethylene glycol dibutyl ether, ethylene glycol phenyl ether, ethylene glycol butyl ether and propylene glycol phenyl ether;
the acid solvent comprises one or more of succinic acid, citric acid, n-octanoic acid, n-decanoic acid, oleic acid, sebacic acid, dodecanedioic acid and suberic acid.
7. The silver paste according to claim 5, wherein the mass ratio of the surface-modified silver powder to the polyvalent organic solvent is (2-10): 1;
if the surface modified silver powder comprises flaky surface modified silver powder, the particle size of the flaky surface modified silver powder is 100 nm-800 nm, and the thickness of the flaky surface modified silver powder is 20-50 nm;
if the surface-modified silver powder comprises spherical surface-modified silver powder, the particle size of the spherical surface-modified silver powder is 10 nm-200 nm;
if the surface modified silver powder comprises the flaky surface modified silver powder and the spherical surface modified silver powder, the mass ratio of the flaky surface modified silver powder to the spherical surface modified silver powder is (5-10): (5-1).
8. A method for preparing a silver paste according to any one of claims 5 to 7, comprising the steps of: and mixing and stirring the surface modified silver powder and the multi-element organic solvent to obtain the silver soldering paste.
9. Use of the silver solder paste according to any one of claims 5 to 7 in chip package interconnections.
10. The use of claim 9, wherein said chip package interconnect comprises a first master, a second master and a connection layer for connecting said first and second masters, said connection layer being formed by sintering using said silver paste by a pressureless sintering process;
the pressureless sintering process comprises the following specific steps: the heating rate is 1-25 ℃/min, the heating peak temperature is 150-300 ℃, and the heat preservation time is 10-120 min.
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