CN116532841A - Silver soldering paste and preparation process thereof - Google Patents
Silver soldering paste and preparation process thereof Download PDFInfo
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- CN116532841A CN116532841A CN202310637978.8A CN202310637978A CN116532841A CN 116532841 A CN116532841 A CN 116532841A CN 202310637978 A CN202310637978 A CN 202310637978A CN 116532841 A CN116532841 A CN 116532841A
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- Prior art keywords
- silver
- chip
- paste
- substrate
- soldering paste
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- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 title claims abstract description 167
- 229910052709 silver Inorganic materials 0.000 title claims abstract description 116
- 239000004332 silver Substances 0.000 title claims abstract description 116
- 238000005476 soldering Methods 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title abstract description 29
- 229910052751 metal Inorganic materials 0.000 claims abstract description 81
- 239000002184 metal Substances 0.000 claims abstract description 81
- 239000000758 substrate Substances 0.000 claims abstract description 65
- NDVLTYZPCACLMA-UHFFFAOYSA-N silver oxide Substances [O-2].[Ag+].[Ag+] NDVLTYZPCACLMA-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000002245 particle Substances 0.000 claims abstract description 57
- 229910001923 silver oxide Inorganic materials 0.000 claims abstract description 48
- 238000005245 sintering Methods 0.000 claims abstract description 29
- 229910000679 solder Inorganic materials 0.000 claims description 48
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 39
- -1 silver tetrafluoroborate Chemical compound 0.000 claims description 35
- 238000000034 method Methods 0.000 claims description 33
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 32
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 29
- 238000004806 packaging method and process Methods 0.000 claims description 27
- 230000008569 process Effects 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 26
- 239000003960 organic solvent Substances 0.000 claims description 22
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 21
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 19
- 238000002156 mixing Methods 0.000 claims description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 11
- 239000010949 copper Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- 239000012298 atmosphere Substances 0.000 claims description 10
- 239000011248 coating agent Substances 0.000 claims description 10
- 238000000576 coating method Methods 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 9
- 238000001914 filtration Methods 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- RUJPNZNXGCHGID-UHFFFAOYSA-N (Z)-beta-Terpineol Natural products CC(=C)C1CCC(C)(O)CC1 RUJPNZNXGCHGID-UHFFFAOYSA-N 0.000 claims description 8
- 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 8
- AXINVSXSGNSVLV-UHFFFAOYSA-N 1h-pyrazol-4-amine Chemical compound NC=1C=NNC=1 AXINVSXSGNSVLV-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000009210 therapy by ultrasound Methods 0.000 claims description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 claims description 6
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 6
- QRZMXADUXZADTF-UHFFFAOYSA-N 4-aminoimidazole Chemical compound NC1=CNC=N1 QRZMXADUXZADTF-UHFFFAOYSA-N 0.000 claims description 5
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 5
- 239000003795 chemical substances by application Substances 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- SQIFACVGCPWBQZ-UHFFFAOYSA-N delta-Terpineol Chemical compound CC(C)(O)C1CCC(=C)CC1 SQIFACVGCPWBQZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 5
- 238000007789 sealing Methods 0.000 claims description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- NNRLDGQZIVUQTE-UHFFFAOYSA-N gamma-Terpineol Chemical compound CC(C)=C1CCC(C)(O)CC1 NNRLDGQZIVUQTE-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 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 3
- 235000019253 formic acid Nutrition 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 238000002390 rotary evaporation Methods 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000010931 gold Substances 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 2
- 238000009792 diffusion process Methods 0.000 abstract description 11
- 239000002105 nanoparticle Substances 0.000 abstract description 4
- 238000000280 densification Methods 0.000 abstract description 3
- 230000005012 migration Effects 0.000 abstract description 3
- 238000013508 migration Methods 0.000 abstract description 3
- 238000005324 grain boundary diffusion Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 239000004033 plastic Substances 0.000 abstract description 2
- 239000007787 solid Substances 0.000 abstract description 2
- 238000009713 electroplating Methods 0.000 description 11
- 238000004140 cleaning Methods 0.000 description 9
- 230000000052 comparative effect Effects 0.000 description 7
- 239000000463 material Substances 0.000 description 6
- 238000001878 scanning electron micrograph Methods 0.000 description 6
- 239000004065 semiconductor Substances 0.000 description 6
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 6
- 150000001412 amines Chemical class 0.000 description 5
- 238000000354 decomposition reaction Methods 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- 238000010008 shearing Methods 0.000 description 5
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 4
- 239000000956 alloy Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 230000032683 aging Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000000919 ceramic Substances 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 229910001961 silver nitrate Inorganic materials 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910002601 GaN Inorganic materials 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 125000004429 atom Chemical group 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000006259 organic additive Substances 0.000 description 2
- 238000007747 plating Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004593 Epoxy Substances 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000005456 alcohol based solvent Substances 0.000 description 1
- WUOACPNHFRMFPN-UHFFFAOYSA-N alpha-terpineol Chemical compound CC1=CCC(C(C)(C)O)CC1 WUOACPNHFRMFPN-UHFFFAOYSA-N 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- UFGZSIPAQKLCGR-UHFFFAOYSA-N chromium carbide Chemical compound [Cr]#C[Cr]C#[Cr] UFGZSIPAQKLCGR-UHFFFAOYSA-N 0.000 description 1
- 239000007822 coupling agent Substances 0.000 description 1
- 238000001723 curing Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229960004279 formaldehyde Drugs 0.000 description 1
- 235000019256 formaldehyde Nutrition 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- JVPLOXQKFGYFMN-UHFFFAOYSA-N gold tin Chemical compound [Sn].[Au] JVPLOXQKFGYFMN-UHFFFAOYSA-N 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000017525 heat dissipation Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- LQBJWKCYZGMFEV-UHFFFAOYSA-N lead tin Chemical compound [Sn].[Pb] LQBJWKCYZGMFEV-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 238000000053 physical method Methods 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000010025 steaming Methods 0.000 description 1
- 229940116411 terpineol Drugs 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 238000005382 thermal cycling Methods 0.000 description 1
- 229910003470 tongbaite Inorganic materials 0.000 description 1
- 238000009834 vaporization Methods 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/50—Assembly of semiconductor devices using processes or apparatus not provided for in a single one of the subgroups H01L21/06 - H01L21/326, e.g. sealing of a cap to a base of a container
Abstract
The invention relates to the technical field of silver soldering paste, in particular to silver soldering paste and a preparation process thereof. Wherein the nano silver oxide particles can be decomposed at a lower temperature to generate nano-sized high-energy silver particles in situ. Then, through inter-diffusion sintering, surface diffusion, surface lattice diffusion and gas phase migration occur among atoms, increase occurs in size, and along with the increase of sintering temperature, grain boundary diffusion, grain boundary lattice diffusion and plastic flow occur, so that shrinkage and densification of a sintered structure are facilitated, and micron-sized silver particles of a necked structure are formed. And meanwhile, through solid diffusion, metallurgical bonding is carried out on the chip and the metal layers at the bottom of the chip and the top of the substrate, so that a chip interconnection metal layer which is compact and excellent in interface bonding is obtained.
Description
Technical Field
The invention relates to the technical field of silver soldering paste, in particular to silver soldering paste and a preparation process thereof.
Background
Along with the progress of technology, new energy electric automobile and corresponding quick charging pile thereof, high-speed rail and green electric remote transportation have put forward higher and higher requirements on corresponding power modules, and a high-power device with high temperature resistance, high breakdown voltage and high current density and high switching frequency is needed. However, the conventional silicon-based chip cannot meet the requirements of the above objects due to its inherent physical and chemical properties. Researchers are looking at third generation semiconductors-wide bandgap semiconductors (e.g., siC and GaN) because they can well meet the current demands for high performance chips. However, the high temperature resistance mentioned above generally means that the chip needs to withstand an operating temperature of more than 250 ℃.
Among the current packaging connection materials, solder alloys and conductive adhesives are two commonly used semiconductor device connection materials that are often only capable of service at temperatures below the tolerance level of the semiconductor device. However, unlike most pure metals, solder alloys have relatively low electrical and thermal conductivities. Intermetallic compounds are also prone to fatigue and failure due to their formation and phase separation, which provides a place for crack initiation and growth during thermal cycling. Whereas conventional solders such as tin-lead solders often have melting points below 250 ℃, only a few solder alloys have melting points above 250 ℃, such as gold-tin eutectic solders, but at high cost. On the other hand, cured conductive adhesives have even poorer electrical and thermal conductivity than solder alloys due to higher polymer content. Chips with conventional solders as interconnect layers are typically difficult to apply to the connection of high power and high temperature semiconductor devices because of solder joint melting and failure when operating in this environment. With the commercialization of wide bandgap semiconductor devices such as chromium carbide and gallium nitride, the use of high temperature, high power electronic devices is becoming increasingly widespread. There is a need for a die bonding material that meets this high requirement and achieves stable service at high temperatures and rapid heat dissipation.
Up to now, silver paste is a relatively common material for third generation semiconductor chip package interconnections. The silver soldering layer formed after sintering the silver soldering paste has the advantages of high heat conductivity, high electric conductivity and high temperature resistance. The silver paste is prepared by first undergoing synthesis of nano silver particles, and this is a crucial step in determining the cost of the final silver paste. Generally, the synthesis of nano silver particles includes both physical and chemical methods. Physical methods, while capable of producing nano-silver particles of higher purity, involve higher equipment costs. The chemical method is to utilize oxidation-reduction reaction to reduce silver ions into silver atoms, and then nucleate to form nano silver particles. This method is widely used because of its simplicity, efficiency and low cost. In addition, the preparation of the nano silver soldering paste also comprises the selection of organic reagents such as solvents, dispersing agents, binders and the like; the regulation of the ratio between the nanoparticles and the organic reagent is relatively complex and expensive.
The solder filled with nano silver particles is therefore gradually attracting attention of researchers. The nano silver particles have very small size, the size means that the specific surface area is larger, the surface energy is higher, the melting point of the nano silver particles is not required to be reached in the sintering process, and the diffusion among atoms can be realized by utilizing the driving force caused by the reduction of the surface area, so that the effect of sintering interconnection is realized. However, in order to make the nano silver soldering paste have certain process operability, the preparation of the nano silver soldering paste also comprises the selection of organic reagents such as solvents, dispersing agents, binders and the like; and regulating the ratio of the nano particles to the organic reagent. The organic additives used in the silver paste formulation process are due to their high vaporization and decomposition temperatures. The expression of high surface activity of the nano silver particles is limited during sintering. Therefore, we propose a silver solder paste and a preparation process thereof.
Disclosure of Invention
The invention aims to provide silver soldering paste and a preparation process thereof, which are used for solving the problems in the background technology.
In order to solve the technical problems, the invention provides the following technical scheme: a silver soldering paste is prepared from nano silver oxide particles and organic solvent carrier through mixing.
Further, the mass ratio of the nano silver oxide particles to the organic solvent carrier is (2-10): 1.
Further, the particle size of the nano silver oxide particles is 50 nm-300 nm.
Further, the organic solvent carrier is one or more of ethylene glycol, ammonia water, formic acid, glycerol, diethylene glycol, triethylene glycol, beta-terpineol, gamma-terpineol and delta-terpineol.
Further, the silver soldering paste also contains a silver precursor.
Further, the mass ratio of the nano silver oxide particles to the silver precursor agent is (2-10): 1-2.
Further, the silver precursor is prepared from the following components: silver tetrafluoroborate, amine compounds, and tetramethylammonium hydroxide.
Further, the amine compound is selected from 4-aminopyrazole and 4-aminoimidazole.
Further, the silver precursor is prepared by the following process:
taking silver oxide at the temperature of 21-27 ℃, adding acetonitrile serving as a solvent, stirring, slowly adding fluoboric acid until the solution becomes transparent, and stirring for 30-40 min; filtering to remove impurities, and vacuum drying to obtain silver tetrafluoroborate;
adding methanol into silver tetrafluoroborate and amine compounds, and carrying out ultrasonic treatment for 50-75 s; adding tetramethyl ammonium hydroxide, sealing, and heating at 68-72 deg.c for 20 hr; naturally cooling to room temperature, filtering, and rotary evaporating to obtain silver precursor.
Further, the mass ratio of the silver oxide to the fluoboric acid is 6 (34.1-34.5);
the ratio of silver oxide to acetonitrile was 6 g/100 mL.
Further, the mass ratio of the silver tetrafluoroborate to the amine compound to the tetramethylammonium hydroxide is 10 (14-18) (0.15-0.17);
silver tetrafluoroborate and methanol in a ratio of 1g to 100mL;
further, tetramethylammonium hydroxide was added as a solution, methanol was used as the solvent, and the concentration of the solution was 0.1mol/L.
Further, the silver solder paste is applied to a chip packaging interconnection structure;
the chip packaging interconnection structure sequentially comprises the following components from top to bottom: chip, chip interconnection metal layer and substrate;
the substrate is a copper-clad ceramic plate;
the chip interconnection metal layer is formed by sintering silver solder paste.
Further, the sintering process conditions are as follows: the heating temperature is 150-300 ℃, the pressing pressure is 0.1-20 MPa, and the sintering time is 30-3600 s.
Further, the bottom of the chip and the top of the substrate are both provided with metal layers; sequentially named as a chip metal layer and a base metal layer.
Further, the metal layer is prepared by adopting an electroplating or sputtering process.
Further, the metal layer is one of copper, silver, gold, nickel, cobalt, indium, palladium, platinum and aluminum.
Further, the thickness of the metal layer is 0.1-500 μm.
Further, the bottom of the chip and the top of the substrate are both electroplated with a metallic silver layer.
Further, the chip and the substrate are subjected to ultrasonic cleaning before use, so that surface impurities are removed.
In the technical scheme, the silver paste is prepared by mutually mixing nano silver oxide particles and an organic solvent carrier. Wherein the nano silver oxide particles can be decomposed at a lower temperature to generate nano-sized high-energy silver particles in situ. Then, through inter-diffusion sintering, surface diffusion, surface lattice diffusion and gas phase migration occur among atoms, increase occurs in size, and along with the increase of sintering temperature, grain boundary diffusion, grain boundary lattice diffusion and plastic flow occur, so that shrinkage and densification of a sintered structure are facilitated, and micron-sized silver particles of a necked structure are formed. And meanwhile, through solid diffusion, metallurgical bonding is carried out on the chip and the metal layers at the bottom of the chip and the top of the substrate, so that a chip interconnection metal layer (hereinafter referred to as an interconnection layer) which is compact and excellent in interface bonding is obtained.
The organic solvent carrier is selected to contain an alcohol solvent with certain reducibility, so that the reduction process of the nano silver oxide particles can be accelerated under the action of reducing the nano silver oxide particles, the strength of the prepared interconnection layer is promoted, and the interface performance among the interconnection layer, the chip and the substrate is improved. The optional components in the organic solvent carrier also comprise ammonia water and formic acid, so that the nano silver oxide particles can be dissolved, the dispersion and the miniaturization of the nano silver oxide particles in the organic solvent carrier are improved, the reduction rate of the nano silver oxide particles in the sintering process is promoted, the strength of the prepared interconnection layer is further improved, and the interface performance among the interconnection layer, the chip and the substrate is improved.
Through the technical scheme for generating the high-energy nano silver by utilizing silver oxide decomposition, the oxidation of the substrate can be inhibited, the negative influence of the organic additive in the prior art is eliminated, the sintering activity of the silver soldering paste is improved, the production cost of a chip can be effectively reduced, and the packaging efficiency is improved.
The invention provides a method for generating high-activity nano silver by utilizing silver oxide decomposition and further realizing stable interconnection by using the nano silver as a chip interconnection material. Firstly, electroplating or sputtering a metal layer with a certain thickness on the back of a chip and the top layer of a substrate (taking a direct copper-clad plate DBC as an example); and then, silver paste is coated on the prepared metal layer, and sintering is carried out at a certain temperature and pressure, so that stable connection of the chip and the substrate is realized.
In the technical scheme, the silver soldering paste also contains a silver precursor and a reducing agent, wherein the silver precursor is prepared from silver tetrafluoroborate and amine compounds, the tetramethylammonium hydroxide is used for regulating the pH of a system, silver ions are combined and coordinated with amine, tetrafluoroborate and nitrogen atoms are connected to form bonds, so that coulombic attraction exists between silver precursor containing silver ligand ions (positive electricity) and tetrafluoroborate ions (negative electricity) and nano silver oxide particles, the surface energy of the nano silver oxide particles is reduced before the silver soldering paste is used, the agglomeration phenomenon is relieved, the lubricity of the nano silver oxide particles is utilized to promote the dispersion of the nano silver oxide particles in an organic solvent carrier, and the component uniformity of the silver soldering paste is ensured.
The adsorption of the silver precursor on the surfaces of the nano silver oxide particles can reduce the electron cloud density of the silver precursor, weaken the bond strength of the silver precursor, promote the dispersion of the silver precursor at the initial stage of the sintering process of the silver soldering paste, ensure the uniformity of the components of the silver soldering paste and the reduction of the nano silver oxide particles, promote the migration of silver atoms at the interface of the interconnection layer and the metal layer, improve the sintering density of the silver soldering paste, enhance the bonding capability between the silver precursor and the metal layer on the surfaces of the chip and the substrate, improve the high-temperature resistance of the prepared interconnection layer and improve the comprehensive performance of the interconnection layer.
Alcohol solvents in the organic solvent carrier are oxidized to form aldehyde in the sintering process of the silver soldering paste, meanwhile, the generated nano silver can catalyze the aldehyde forming reaction, the reduction of silver ions in the silver precursor is promoted, nano silver particles are formed, the sintered pores of the nano silver oxide particles are filled, the densification growth of the nano silver particles can be promoted, and the comprehensive performance of the interconnection layer is further improved.
The silver precursor is selected to prepare components silver tetrafluoroborate and amine compounds, and the amine compounds are selected from 4-aminopyrazole and 4-aminoimidazole and contain a cyclic structure, so that the prepared silver precursor has higher stability, the initial degradation of the silver precursor can be avoided, and the influence of degradation products overflow on nano silver oxide particles is prevented; has alkalinity, and is helpful for the reduction of silver ions; the energy barrier of the preliminary decomposition is lower, the silver solder paste can be heated to decompose and open the ring in the sintering process of the silver solder paste, and the final decomposition product (triamine structure) is released; the introduced tetrafluoroboric acid can be decomposed and released in the sintering process, so that silver is reduced, and the influence of organic matters in the silver soldering paste is reduced.
Drawings
The accompanying drawings are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate the invention and together with the embodiments of the invention, serve to explain the invention. In the drawings:
FIG. 1 is a schematic diagram of a chip package interconnect structure of the present invention;
FIG. 2 is an SEM image of a broken surface of a metal layer for chip interconnection of example 1 according to the present invention;
FIG. 3 is a SEM image of a fracture surface of a metal layer of an example 2 chip interconnect according to the present invention;
FIG. 4 is a SEM image of the fracture surface of a metal layer for chip interconnection of example 3 of the present invention;
FIG. 5 is a SEM image of a fracture surface of a metal layer for chip interconnection of example 4 of the present invention;
fig. 6 is a SEM image of the fracture surface of the metal layer of the chip interconnection of example 5 in the present invention.
Detailed Description
The following description of the technical solutions in the embodiments of the present invention will be clear and complete, and it is obvious that the described embodiments are only some embodiments of the present invention, but not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
In the following examples, nano silver oxide particles: the particle size is 50 nm-300 nm, the purity is 99.9%, and the product is obtained from Shanghai Bo Hanhua technology limited company.
The substrate was a copper-clad ceramic plate with dimensions of 5X 5mm and 3X 3mm, a copper layer with a thickness of 0.3mm and a ceramic with a thickness of 0.635mm, which were obtained from Shanghai Shen and Thermomagnetic electronics Inc.
The specific process of electroplating the silver layer in the metal layer comprises the following steps: the substrate or the chip is a working electrode, the saturated calomel is a reference electrode, the platinum is a counter electrode, and the current density is 1.5+/-0.2 A.dm -2 The temperature is 28+/-2 ℃;
the plating solution is cyanide-free silver plating solution (50 g/L silver nitrate, pH 8.0) and is derived from Shenzhen Tianyuanzhi new material science and technology Co.
Example 1: a preparation process of a chip packaging interconnection structure comprises the following steps:
(1) Preparation of silver solder paste:
mixing nano silver oxide particles and ethylene glycol serving as an organic solvent carrier according to a mass ratio of 5:1 to obtain silver soldering paste;
(2) Application of silver solder paste:
placing a substrate and a chip into an ultrasonic cleaner for cleaning, wherein the bottom of the chip and the top of the substrate are respectively provided with a metal layer, the metal layers are electroplated silver layers, the copper layers at the top of the substrate and the bottom of the chip are used as seed layers for electroplating, and the thickness of the metal layers is 10 mu m;
silver solder paste is coated on the metal layers of the chip and the substrate, and the coating thickness is 100 mu m; then the chip is turned over, one surface coated with silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is sintered in an air atmosphere, wherein the sintering process conditions are as follows: the pressure is 10MPa, the temperature is 300 ℃, the pressure holding time is 600s, and the chip interconnection metal layer is formed, so that the chip packaging interconnection structure is obtained.
Example 2: a preparation process of a chip packaging interconnection structure comprises the following steps:
(1) Preparation of silver solder paste:
mixing nano silver oxide particles, ethylene glycol serving as an organic solvent carrier and beta-terpineol according to the mass ratio of the nano silver oxide particles to the organic solvent carrier of 4:1 to obtain silver soldering paste; wherein the mass ratio of the ethylene glycol to the beta-terpineol is 2:1;
(2) Application of silver solder paste:
placing a substrate and a chip into an ultrasonic cleaner for cleaning, wherein the bottom of the chip and the top of the substrate are respectively provided with a metal layer, the metal layers are electroplated silver layers, the copper layers at the top of the substrate and the bottom of the chip are used as seed layers for electroplating, and the thickness of the metal layers is 10 mu m;
silver solder paste is coated on the metal layers of the chip and the substrate, and the coating thickness is 100 mu m; then the chip is turned over, one surface coated with silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is sintered in an air atmosphere, wherein the sintering process conditions are as follows: the pressure is 1MPa, the temperature is 250 ℃, the pressure holding time is 1800s, and the chip interconnection metal layer is formed, so that the chip packaging interconnection structure is obtained.
Example 3: a preparation process of a chip packaging interconnection structure comprises the following steps:
(1) Preparation of silver solder paste:
mixing nano silver oxide particles, organic solvent carrier ammonia water and beta-terpineol according to the mass ratio of the nano silver oxide particles to the organic solvent carrier of 8:1 to obtain silver soldering paste; wherein the mass ratio of the ammonia water to the beta-terpineol is 1:6;
(2) Application of silver solder paste:
placing a substrate and a chip into an ultrasonic cleaner for cleaning, wherein the bottom of the chip and the top of the substrate are respectively provided with a metal layer, the metal layers are electroplated silver layers, the copper layers at the top of the substrate and the bottom of the chip are used as seed layers for electroplating, and the thickness of the metal layers is 10 mu m;
silver solder paste is coated on the metal layers of the chip and the substrate, and the coating thickness is 100 mu m; then the chip is turned over, one surface coated with silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is sintered in an air atmosphere, wherein the sintering process conditions are as follows: the pressure is 20MPa, the temperature is 160 ℃, the pressure holding time is 3600s, and the chip interconnection metal layer is formed, so that the chip packaging interconnection structure is obtained.
Example 4: a preparation process of a chip packaging interconnection structure comprises the following steps:
(1) Preparation of silver solder paste:
taking silver oxide at 21 ℃, adding acetonitrile serving as a solvent, stirring, slowly adding fluoboric acid until the solution becomes transparent, and stirring for 30min; filtering to remove impurities, and vacuum drying to obtain silver tetrafluoroborate; the mass ratio of the silver oxide to the fluoboric acid is 6:34.1; the proportion of silver oxide to acetonitrile is 6g to 100mL;
taking silver tetrafluoroborate and an amine compound 4-aminopyrazole, adding methanol, and carrying out ultrasonic treatment for 50s; adding tetramethylammonium hydroxide (the tetramethylammonium hydroxide is added in the form of a solution, the solvent is methanol, the concentration of the solution is 0.1 mol/L), sealing, and heating at the constant temperature of 68 ℃ for 20h; naturally cooling to room temperature, filtering, and performing rotary evaporation to obtain a silver precursor; silver tetrafluoroborate, amine compound 4-aminopyrazole and tetramethylammonium hydroxide in a mass ratio of 10:14:0.15; silver tetrafluoroborate and methanol in a ratio of 1g to 100mL;
mixing nano silver oxide particles, an organic solvent carrier ethylene glycol and a silver precursor agent according to the mass ratio of 5:1:1, and carrying out ultrasonic treatment for 20min to obtain silver soldering paste;
(2) Application of silver solder paste:
placing a substrate and a chip into an ultrasonic cleaner for cleaning, wherein the bottom of the chip and the top of the substrate are both provided with metal layers, and the metal layers are electroplated silver layers;
silver solder paste is coated on the metal layers of the chip and the substrate, and the coating thickness is 100 mu m; then the chip is turned over, one surface coated with silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is sintered in an air atmosphere, wherein the sintering process conditions are as follows: the pressure is 10MPa, the temperature is 300 ℃, the pressure holding time is 600s, and the chip interconnection metal layer is formed, so that the chip packaging interconnection structure is obtained.
Example 5: a preparation process of a chip packaging interconnection structure comprises the following steps:
(1) Preparation of silver solder paste:
taking silver oxide at the temperature of 27 ℃, adding acetonitrile serving as a solvent, stirring, slowly adding fluoboric acid until the solution becomes transparent, and stirring for 40min; filtering to remove impurities, and vacuum drying to obtain silver tetrafluoroborate; the mass ratio of the silver oxide to the fluoboric acid is 6:34.5; the proportion of silver oxide to acetonitrile is 6g to 100mL;
taking silver tetrafluoroborate and amine compound 4-aminoimidazole, adding methanol, and carrying out ultrasonic treatment for 75s; adding tetramethylammonium hydroxide (the tetramethylammonium hydroxide is added in the form of solution, the solvent is methanol, the concentration of the solution is 0.1 mol/L), sealing, and heating at the constant temperature of 72 ℃ for 20h; naturally cooling to room temperature, filtering, and performing rotary evaporation to obtain a silver precursor; silver tetrafluoroborate, amine compound 4-aminoimidazole and tetramethyl ammonium hydroxide in the mass ratio of 10:18:0.17; silver tetrafluoroborate and methanol in a ratio of 1g to 100mL;
mixing nano silver oxide particles, ethylene glycol serving as an organic solvent carrier and beta-terpineol according to the mass ratio of the nano silver oxide particles to the organic solvent carrier of 8:2:1 to obtain silver soldering paste; wherein the mass ratio of the ethylene glycol to the beta-terpineol is 2:1;
(2) Application of silver solder paste:
placing a substrate and a chip into an ultrasonic cleaner for cleaning, wherein the bottom of the chip and the top of the substrate are respectively provided with a metal layer, the metal layers are electroplated silver layers, the copper layers at the top of the substrate and the bottom of the chip are used as seed layers for electroplating, and the thickness of the metal layers is 10 mu m;
silver solder paste is coated on the metal layers of the chip and the substrate, and the coating thickness is 100 mu m; then the chip is turned over, one surface coated with silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is sintered in an air atmosphere, wherein the sintering process conditions are as follows: the pressure is 1MPa, the temperature is 250 ℃, the pressure holding time is 1800s, and the chip interconnection metal layer is formed, so that the chip packaging interconnection structure is obtained.
Comparative example 1: a preparation process of a chip packaging interconnection structure comprises the following steps:
(1) Preparation of silver solder paste:
mixing micrometer silver oxide particles (average particle diameter 10 μm, purity 99.9% and originating from Shanghai Bo Hanhua science and technology Co., ltd.), dispersant dodecyl amine and organic solvent carrier glycol according to the mass ratio of 5:0.05:1 to obtain silver soldering paste;
(2) Application of silver solder paste:
placing a substrate and a chip into an ultrasonic cleaner for cleaning, wherein the bottom of the chip and the top of the substrate are respectively provided with a metal layer, the metal layers are electroplated silver layers, the copper layers at the top of the substrate and the bottom of the chip are used as seed layers for electroplating, and the thickness of the metal layers is 10 mu m;
silver solder paste is coated on the metal layers of the chip and the substrate, and the coating thickness is 100 mu m; then the chip is turned over, one surface coated with silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is sintered in an air atmosphere, wherein the sintering process conditions are as follows: the pressure is 10MPa, the temperature is 300 ℃, the pressure holding time is 600s, and the chip interconnection metal layer is formed, so that the chip packaging interconnection structure is obtained.
Comparative example 2: a preparation process of a chip packaging interconnection structure comprises the following steps:
(1) Preparation of silver solder paste:
mixing nano silver particles (particle size of 20-80 nm, purity of 99.9% from Whan Ke Mike biomedical technology Co., ltd.), tin powder (average particle size of 50nm, purity of 99.9% from Ning Porro nano technology Co., ltd.) and terpineol according to a mass ratio of 10:0.5:2 to obtain silver soldering paste;
(2) Application of silver solder paste:
placing a substrate and a chip into an ultrasonic cleaner for cleaning, wherein the bottom of the chip and the top of the substrate are respectively provided with a metal layer, the metal layers are electroplated silver layers, the copper layers at the top of the substrate and the bottom of the chip are used as seed layers for electroplating, and the thickness of the metal layers is 10 mu m;
silver solder paste is coated on the metal layers of the chip and the substrate, and the coating thickness is 100 mu m; then the chip is turned over, one surface coated with silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is sintered in an air atmosphere, wherein the sintering process conditions are as follows: the pressure is 10MPa, the temperature is 300 ℃, the pressure holding time is 600s, and the chip interconnection metal layer is formed, so that the chip packaging interconnection structure is obtained.
Comparative example 3: a preparation process of a chip packaging interconnection structure comprises the following steps:
(1) Preparation of silver solder paste:
taking 18.0wt% of epoxy resin (E-44, epoxy equivalent 196g/eq, from Baling petrochemical Co., ltd.), 0.9wt% of dicyandiamide curing agent (SH-300, from Guangzhou New Metallurgical chemical Co., ltd.), stirring for 20min, adding 75.0wt% of nano silver particles, 2.5wt% of coupling agent (KH-902) and 3.6wt% of diluting agent (acetone), mixing and grinding for 60min to obtain silver soldering paste;
(2) Application of silver solder paste:
placing a substrate and a chip into an ultrasonic cleaner for cleaning, wherein the bottom of the chip and the top of the substrate are respectively provided with a metal layer, the metal layers are electroplated silver layers, the copper layers at the top of the substrate and the bottom of the chip are used as seed layers for electroplating, and the thickness of the metal layers is 10 mu m;
silver solder paste is coated on the metal layers of the chip and the substrate, and the coating thickness is 100 mu m; then the chip is turned over, one surface coated with silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is placed in an air atmosphere for thermal curing under the following process conditions: and forming a chip interconnection metal layer at the temperature of 150 ℃ for 60min to obtain a chip packaging interconnection structure.
Comparative example 4: a preparation process of a chip packaging interconnection structure comprises the following steps:
(1) Preparation of silver solder paste:
taking silver tetrafluoroborate and 4-aminopyrazole, adding methanol, and carrying out ultrasonic treatment for 50s; adding tetramethylammonium hydroxide (the tetramethylammonium hydroxide is added in the form of a solution, the solvent is methanol, the concentration of the solution is 0.1 mol/L), sealing, and heating at the constant temperature of 68 ℃ for 20h; naturally cooling to room temperature, filtering, and steaming; adding acetaldehyde to obtain silver precursor; the mass ratio of the silver nitrate to the 4-aminopyrazole to the tetramethylammonium hydroxide to the acetaldehyde is 8.7:14:0.15:2.1; the proportion of the silver nitrate to the methanol is 1g to 100mL;
mixing nano silver oxide particles, an organic solvent carrier ethylene glycol and a silver precursor agent according to the mass ratio of 5:1:1, and carrying out ultrasonic treatment for 20min to obtain silver soldering paste;
(2) Application of silver solder paste:
placing a substrate and a chip into an ultrasonic cleaner for cleaning, wherein the bottom of the chip and the top of the substrate are respectively provided with a metal layer, the metal layers are electroplated silver layers, the copper layers at the top of the substrate and the bottom of the chip are used as seed layers for electroplating, and the thickness of the metal layers is 10 mu m;
silver solder paste is coated on the metal layers of the chip and the substrate, and the coating thickness is 100 mu m; then the chip is turned over, one surface coated with silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is sintered in an air atmosphere, wherein the sintering process conditions are as follows: the pressure is 10MPa, the temperature is 300 ℃, the pressure holding time is 600s, and the chip interconnection metal layer is formed, so that the chip packaging interconnection structure is obtained.
Experiment
Taking chip package interconnection structure samples obtained in examples 1-5 and comparative examples 1-4, respectively detecting the performances of the chip package interconnection structure samples and recording detection results:
shear fracture test: carrying out shearing fracture test on the sample by utilizing a multifunctional micro-welding spot strength tester, wherein a shearing head is parallel to the edge of the chip, the shearing height is 20 mu m, and the shearing speed is 100 mu m/s;
high temperature resistance test: placing the sample at 300 ℃, preserving heat for 2000 hours, and carrying out shearing fracture test again;
from the data in the above table, the following conclusions can be clearly drawn:
the chip interconnection metal layers obtained in examples 1-5 are more excellent in shear strength before and after high-temperature aging, and a shear section SEM image of a packaging interconnection structure of the chip interconnection metal layers shows that the chip interconnection metal layers obtained in examples 1-5 are uniform and compact, have obvious breaking points, and form stable connection between metal layers of a sintered chip and a substrate.
The chip interconnection metal layers obtained in comparative examples 1 to 3 were subjected to a silver paste preparation process which is technically different from that of example 1; and the chip interconnect metal layer obtained in example 1 has higher shear strength before and after high temperature aging. The chip interconnect metal layers obtained in examples 4 to 5, which were different in the preparation of silver paste from examples 1 to 3, were in turn compared with examples 1 and 2; the chip interconnection metal layer obtained in comparative example 4, the preparation of which silver solder paste is technically different from that of example 4; and the chip interconnect metal layer obtained in example 4 has higher shear strength before and after high temperature aging. From the above, the silver soldering paste composition and the process thereof can promote the improvement of the strength and the high temperature resistance of the manufactured chip interconnection metal layer.
It is noted that relational terms such as first and second, and the like are used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process method article or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process method article or apparatus.
Finally, it should be noted that: the foregoing description is only a preferred embodiment of the present invention, and the present invention is not limited thereto, but it is to be understood that modifications and equivalents of some of the technical features described in the foregoing embodiments may be made by those skilled in the art, although the present invention has been described in detail with reference to the foregoing embodiments. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A silver solder paste, characterized in that: is prepared by mixing nano silver oxide particles and an organic solvent carrier.
2. A silver paste as claimed in claim 1, wherein: the mass ratio of the nano silver oxide particles to the organic solvent carrier is (2-10): 1.
3. A silver paste as claimed in claim 1, wherein: the particle size of the nano silver oxide particles is 50 nm-300 nm.
4. A silver paste as claimed in claim 1, wherein: the organic solvent carrier is one or more of ethylene glycol, ammonia water, formic acid, glycerol, diethylene glycol, triethylene glycol, beta-terpineol, gamma-terpineol and delta-terpineol.
5. A silver paste as claimed in claim 1, wherein: the silver soldering paste also contains a silver precursor; the mass ratio of the nano silver oxide particles to the silver precursor agent is (2-10) to (1-2).
6. A silver paste as claimed in claim 5, wherein: the silver precursor is prepared by the following process:
taking silver oxide at the temperature of 21-27 ℃, adding acetonitrile serving as a solvent, stirring, slowly adding fluoboric acid until the solution becomes transparent, and stirring for 30-40 min; filtering to remove impurities, and vacuum drying to obtain silver tetrafluoroborate;
adding methanol into silver tetrafluoroborate and amine compounds, and carrying out ultrasonic treatment for 50-75 s; adding tetramethyl ammonium hydroxide, sealing, and heating at 68-72 deg.c for 20 hr; naturally cooling to room temperature, filtering, and performing rotary evaporation to obtain a silver precursor;
the amine compound is 4-aminopyrazole or 4-aminoimidazole.
7. A silver paste as claimed in claim 6, wherein: the mass ratio of the silver oxide to the fluoboric acid is 6 (34.1-34.5); the mass ratio of the silver tetrafluoroborate to the amine compound to the tetramethylammonium hydroxide is 10 (14-18) (0.15-0.17).
8. Use of a silver paste according to any of claims 1-7, characterized in that: the silver solder paste is applied to a chip packaging interconnection structure; the chip packaging interconnection structure sequentially comprises the following components from top to bottom: chip, chip interconnection metal layer and substrate;
the chip packaging interconnection structure is prepared by the following process:
the bottom of the chip and the top of the substrate are both provided with metal layers; taking a substrate and a chip for ultrasonic cleaning;
coating silver solder paste on the metal layers of the chip and the substrate; and then the chip is turned over, one surface of the chip coated with the silver soldering paste is attached to the silver soldering paste on the surface of the substrate, and the chip is sintered in an air atmosphere to form a chip interconnection metal layer, so that a chip packaging interconnection structure is obtained.
9. The use of a silver solder paste according to claim 8, wherein: the sintering process conditions are as follows: the heating temperature is 150-300 ℃, the pressing pressure is 0.1-20 MPa, and the sintering time is 30-3600 s.
10. The use of a silver solder paste according to claim 8, wherein: the metal layer is one of copper, silver, gold, nickel, cobalt, indium, palladium, platinum and aluminum.
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