CN101569965A - Quaternary Pb-free solder composition incorporating Sn-Ag-Cu-In - Google Patents
Quaternary Pb-free solder composition incorporating Sn-Ag-Cu-In Download PDFInfo
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- CN101569965A CN101569965A CNA2008100938399A CN200810093839A CN101569965A CN 101569965 A CN101569965 A CN 101569965A CN A2008100938399 A CNA2008100938399 A CN A2008100938399A CN 200810093839 A CN200810093839 A CN 200810093839A CN 101569965 A CN101569965 A CN 101569965A
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- 239000000203 mixture Substances 0.000 title claims abstract description 167
- 229910000679 solder Inorganic materials 0.000 title claims abstract description 59
- 239000010949 copper Substances 0.000 claims abstract description 16
- 229910052738 indium Inorganic materials 0.000 claims abstract description 9
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims abstract description 9
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims abstract description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229910052802 copper Inorganic materials 0.000 claims abstract description 6
- 229910052709 silver Inorganic materials 0.000 claims abstract description 6
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000004332 silver Substances 0.000 claims abstract description 5
- 230000004907 flux Effects 0.000 claims description 39
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 9
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 9
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 9
- 239000011651 chromium Substances 0.000 claims description 6
- 239000010931 gold Substances 0.000 claims description 6
- 239000011777 magnesium Substances 0.000 claims description 6
- 239000011572 manganese Substances 0.000 claims description 6
- 239000010955 niobium Substances 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- SQIBVKXUIBVITQ-UHFFFAOYSA-N [Ag].[Sn].[In].[Cu] Chemical compound [Ag].[Sn].[In].[Cu] SQIBVKXUIBVITQ-UHFFFAOYSA-N 0.000 claims description 5
- 238000010406 interfacial reaction Methods 0.000 claims description 5
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 3
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- 239000004411 aluminium Substances 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052733 gallium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 229910052748 manganese Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 3
- 150000002910 rare earth metals Chemical class 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- 229910052715 tantalum Inorganic materials 0.000 claims description 3
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims description 3
- JBQYATWDVHIOAR-UHFFFAOYSA-N tellanylidenegermanium Chemical compound [Te]=[Ge] JBQYATWDVHIOAR-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 6
- 238000005382 thermal cycling Methods 0.000 abstract description 2
- 238000009736 wetting Methods 0.000 description 31
- 238000003466 welding Methods 0.000 description 19
- 238000012360 testing method Methods 0.000 description 11
- 229910045601 alloy Inorganic materials 0.000 description 10
- 239000000956 alloy Substances 0.000 description 10
- 235000011837 pasties Nutrition 0.000 description 9
- 239000002002 slurry Substances 0.000 description 7
- 230000004927 fusion Effects 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 238000004781 supercooling Methods 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910017944 Ag—Cu Inorganic materials 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 238000009955 starching Methods 0.000 description 2
- 101100256637 Drosophila melanogaster senju gene Proteins 0.000 description 1
- 244000287680 Garcinia dulcis Species 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000006071 cream Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
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- 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
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn 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
- B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
- B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
-
- 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
- B23K35/22—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
- B23K35/302—Cu 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
- B23K35/22—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
- B23K35/3033—Ni 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
- B23K35/22—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
- B23K35/3046—Co as the principal constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
- C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
Provided is a quaternary Pb-free solder composition incorporating Sn-Ag-Cu-In, which can prevent a cost increase and sufficiently ensure proccessability and mechanical property as a solder material. To this end, indium (In) with appropriate amount is added into the Pb-free solder composition, and the addition amount of Ag is optimized, thus preventing a decrease in wettability caused by a decrease in the amount of Ag and improving resistance to a thermal cycling and a mechanical impact. The quaternary Pb-free solder composition includes silver (Ag) of about 0.3 wt. % or more, and less than about 2.5 wt. %, copper (Cu) of about 0.2 wt. % or more, and less than about 2.0 wt. %, indium (In) of about 0.2 wt. % or more, and less than about 1.0 wt. % or less, and a balance of tin (Sn).
Description
The cross reference of related application
The present invention requires the priority of the korean patent application No.10-2007-0050905 of submission on May 25th, 2007, incorporates its full content into this paper at this in the introducing mode.
Technical field
The present invention relates to a kind of unleaded (Pb) flux composition, more specifically, the present invention relates to a kind of tin-silver-copper-indium (Sn-Ag-Cu-In) quaternary unleaded solder composition, this flux composition can reduce the amount of silver by using indium.
Background technology
At present, as the unleaded solder composition, its representative composition can be expressed as Sn-3.0Ag-0.5Cu to the Sn-Ag-Cu system: compositions the most at large.In order to improve the non-oxidizability of this unleaded solder composition, can be phosphorus (P), germanium (Ge), gallium (Ga), aluminium (Al) or the silicon (Si) etc. of tens of ppm to wherein adding concentration to thousands of ppm.In addition, in order to improve mechanical performance and interfacial reaction performance, can in lead-free composition, add each concentration and be nickel (Ni), cobalt (Co), iron (Fe), bismuth (Bi), gold (Au), platinum (Pt), plumbous (Pb), manganese (Mn), vanadium (V), titanium (Ti), chromium (Cr), niobium (Nb), palladium (Pd), antimony (Sb), magnesium (Mg), tantalum (Ta), cadmium (Cd) or the rare earth metal etc. of tens of ppm to thousands of ppm.
Yet, along with people require and manufacturing cost when being devoted to reduce electronic device package, because Ag is the most expensive in the element that is added, so people attempt reducing the consumption of silver (Ag).For example, Sn-2.5Ag-0.5Cu or Sn-1.0Ag-0.5Cu composition are as unleaded solder.In addition, the someone proposes the Sn-0.3Ag-0.5Cu composition recently, and analyzes its performance and whether be applicable to unleaded solder.
According to the variation of the amount of Ag, Sn-Ag-Cu is that the metallurgical performance of solder flux and variation that mechanical performance takes place are summarized as follows.
1) addition along with Ag reduces, and the difference of liquidus temperature and solid-state temperature increases, thereby causes starching the increase in attitude scope or pasty state zone.
2) addition along with Ag reduces, because slurry attitude scope or the increase of pasty state zone, so wetability reduces.
3) addition along with Ag reduces, and the intensity of alloy and creep resistance reduce.
4) amount along with Ag reduces, because the intensity of alloy and creep resistance reduction, so the crack velocity of solder joint is accelerated in the thermal cycling test.
5) amount along with Ag reduces, and the percentage elongation of alloy increases, and the crack velocity of solder joint is slack-off in the mechanical shock test.
Herein, situation 1) variation that produces along with the difference of the amount of Ag in the solder flux of expression metallurgical performance.Therefore, even in the situation of the amount that reduces Ag, also should determine the suitable addition of Ag.And, although the amount of Ag has reduced, the scolder that has low manufacturing cost for this composition be can be used as, the wetability of this flux composition should be similar to the wetability of typical Sn-3.0Ag-0.5Cu composition.
Situation 4) and 5) expression is because the opposite characteristic that the reduction of the amount of Ag in the unleaded solder causes.Therefore consider the characteristic that these are opposite, should determine the suitable addition of Ag.Except the amount that should have proper A g, for example also should improve the mechanical performance of unleaded solder composition, thereby make flux composition have heat-resisting cyclicity and anti-mechanical impact property by adding alloying metal.Therefore, by reducing the addition of Ag, can obtain the high desirable flux composition of reliability, and can further reduce manufacturing cost.
Yet, the still untapped so far unleaded solder composition that goes out to satisfy above-mentioned condition of people.
Summary of the invention
Embodiment of the present invention relate to provides a kind of tin-silver-copper-indium (Sn-Ag-Cu-In) quaternary unleaded (Pb) flux composition, and this flux composition can prevent the increase of cost, and processability and mechanical performance can fully guarantee it as scolder the time.In order to reach this purpose, in this unleaded solder composition, add the indium (In) of appropriate amount, and the addition of Ag is optimized, thereby the amount owing to Ag of can preventing reduces the wetability that causes and reduces, and can improve heat-resisting cyclicity and anti-mechanical impact property.
According to an aspect of the present invention, a kind of tin-silver-copper-indium quaternary unleaded solder composition is provided, and it comprises: more than or equal to about 0.3 weight % and less than the silver (Ag) of about 2.5 weight %, more than or equal to about 0.2 weight % and less than the copper (Cu) of about 2.0 weight %, more than or equal to about 0.2 weight % and less than the indium (In) of about 1.0 weight % and the tin (Sn) of surplus.
In unleaded solder composition of the present invention, the amount that reduces Ag is to save manufacturing cost.Therefore, in order to improve heat-resisting cyclicity and anti-mechanical impact property, and cause that in order to prevent that reliably addition owing to Ag from reducing wetability reduces, and adds indium (In) in the unleaded solder composition.Therefore, can provide a kind of low-cost, high-quality unleaded solder composition.
Description of drawings
Fig. 1 is the figure that the conventional endothermic peak of flux composition in heated condition is shown.
Fig. 2 is the figure that the endothermic peak of flux composition of the present invention in heated condition is shown.
Fig. 3 illustrates the conventional flux composition fusion figure of the exothermic peak in the state of cooling afterwards.
Fig. 4 is the figure that the exothermic peak in the state of cooling after the flux composition fusion of the present invention is shown.
Fig. 5 illustrates the figure of (the zero cross time) value of zero friendship time of conventional flux composition with respect to welding temperature.
Fig. 6 illustrates zero of flux composition of the present invention to hand over the figure of time value with respect to welding temperature.
Fig. 7 illustrates the figure of the conventional wetting power of flux composition in the time of 2 seconds with respect to welding temperature.
Fig. 8 illustrates the figure of the wetting power of flux composition of the present invention in the time of 2 seconds with respect to welding temperature.
Fig. 9 illustrates the figure of the final wetting power of conventional flux composition with respect to welding temperature.
Figure 10 illustrates the figure of the final wetting power of flux composition of the present invention with respect to welding temperature.
Figure 11 is the figure that the result of the test that is obtained by the stretching sample is shown, and this stretching sample has conventional flux composition Sn-3.0Ag-0.5Cu, Sn-1.0Ag-0.5Cu and Sn-1.2Ag-0.5Cu-0.05Ni respectively.
Figure 12 is the figure that the result of the test that is obtained by the stretching sample is shown, and this stretching sample has flux composition Sn-1.2Ag-0.5Cu-0.4In of the present invention, Sn-1.2Ag-0.5Cu-0.2In, Sn-1.2Ag-0.5Cu-0.6In, Sn-1.2Ag-0.5Cu-0.8In and Sn-1.0Ag-0.5Cu-1.0In respectively.
Figure 13 illustrates zero to hand over the figure of time value with respect to welding temperature, and this figure compares composition Sn-0.3Ag-0.7Cu-0.2In of the present invention and composition Sn-3.0Ag-0.5Cu, Sn-1.0Ag-0.5Cu and the Sn-0.3Ag-0.7Cu of routine.
Figure 14 be wetting power when being illustrated in 2 seconds with respect to the figure of welding temperature, this figure compares composition Sn-0.3Ag-0.7Cu-0.2In of the present invention and conventional composition Sn-3.0Ag-0.5Cu, Sn-1.0Ag-0.5Cu and Sn-0.3Ag-0.7Cu.
Figure 15 illustrates the figure of final wetting power with respect to welding temperature, and this figure compares composition Sn-0.3Ag-0.7Cu-0.2In of the present invention and composition Sn-3.0Ag-0.5Cu, Sn-1.0Ag-0.5Cu and the Sn-0.3Ag-0.7Cu of routine.
The specific embodiment
Explain tin-silver-copper-indium of the present invention (Sn-Ag-Cu-In) quaternary unleaded (Pb) flux composition below with reference to accompanying drawings.Hereinafter, relevant known function or structure are carried out specific description when main idea of the present invention is unnecessarily thickened, will omit these specific descriptions when thinking.
In unleaded solder composition of the present invention, the percentage by weight of Ag is less than about 2.5 weight % but be not less than about 0.3 weight %.If the percentage by weight of Ag is less than 0.3 weight %, liquidus temperature is difficult to reduce so, thereby causes the fusing point and the encapsulation process increase in temperature of solder flux.On the contrary, if the percentage by weight of Ag is 2.5 weight % or higher, manufacturing cost can increase unfriendly so.So the percentage by weight of Ag should be less than about 2.5 weight % but is not less than about 0.3 weight %, is preferably about 1.2 weight %.
Unleaded solder composition of the present invention comprises Cu, and the percentage by weight of Cu is less than about 2.0 weight % but is not less than about 0.2 weight %.If the percentage by weight of Cu is less than 0.2 weight %, the liquidus temperature reduction is very little so, and Cu
6Sn
5Mutually shared part is very little, and this makes the intensity of solder alloy excessively reduce.On the contrary, if the percentage by weight of Cu is 2.0 weight % or higher, the difference of liquidus temperature and solid-state temperature increases so, and therefore starching attitude scope or pasty state zone increases, and this causes Cu
6Sn
5Mutually shared part increases, and therefore makes the mechanical performance of solder alloy excessively strengthen, and the speed of growth of interfacial reaction layer is increased.Therefore, the percentage by weight of Cu should be less than about 2.0 weight % but is not less than about 0.2 weight %, is preferably about 0.5 weight %.
Unleaded solder composition of the present invention further comprises In, and the percentage by weight of In still is not less than about 0.2 weight % less than about 1.0 weight %.If the percentage by weight of In can't improve wetability and mechanical performance so basically less than 0.2 weight %.If the percentage by weight of In is 1.0 weight % or higher, wetability and mechanical performance do not improve pro rata with the addition of In so, and the price of solder alloy is significantly increased.Therefore, the percentage by weight of In should still be not less than about 0.2 weight % less than about 1.0 weight %, is preferably about 0.4 weight %.
According to each proper proportion of adding element, most preferred unleaded solder composition is Sn-1.2Ag-0.5Cu-0.4In.This most preferred composition Sn-1.2Ag-0.5Cu-0.4In is tested under identical condition respectively with composition Sn-3.0Ag-0.5Cu, Sn-1.0Ag-0.5Cu and the Sn-1.2Ag-0.5Cu-0.05Ni of other research with composition and routine, estimate then, its result such as Fig. 1 are to shown in Figure 11.
Fig. 1 and Fig. 2 are the figure that the endothermic peak of flux composition in heated condition is shown.Specifically, Fig. 1 and Fig. 2 show when being that 10 ℃/min, nitrogen flow rate are when heating under the condition of 50ml/min with flux composition (about 8mg) in firing rate, the observed endothermic peak by using differential scanning calorimeter (DSC).As shown in Figure 1, the Sn-3.0Ag-0.5Cu composition locates to have endothermic peak at about 217 ℃ to about 218 ℃, and this temperature melting temperature with this alloy basically is identical.And the Sn-1.0Ag-0.5Cu composition locates to have first endothermic peak at about 218 ℃ to about 219 ℃, and locates to have second endothermic peak at about 226 ℃, and these two temperature can be regarded liquidus temperature and solid-state temperature respectively as.Therefore, can observe slurry attitude scope or pasty state zone significantly increases.The Sn-1.2Ag-0.5Cu-0.05Ni composition locates to have first endothermic peak at about 219 ℃ to about 220 ℃, and locates to have second endothermic peak at about 225 ℃ to about 226 ℃, and these two temperature can be regarded liquidus temperature and solid-state temperature respectively as.Therefore, also can observe slurry attitude scope or pasty state zone significantly increases.
As shown in Figure 2, the Sn-1.0Ag-0.5Cu-1.0In composition locates to have first endothermic peak at about 216 ℃, and locates to have second endothermic peak at about 224 ℃ to about 225 ℃, and these two temperature can be regarded liquidus temperature and solid-state temperature respectively as.In this case, though also can observe slurry attitude scope or the sizable increase of pasty state zone generation, liquidus temperature and solid-state temperature have all reduced comparatively speaking generally.This liquidus curve and solidus can be given the effect that solder flux has excellent wetting capacity at low temperatures to the phenomenon of low temperature shift.The Sn-1.0Ag-0.5Cu-0.5In composition locates to have first endothermic peak at about 217 ℃, and locates to have second endothermic peak at about 225 ℃, and these two temperature can be regarded liquidus temperature and solid-state temperature respectively as.In this case, though also can observe slurry attitude scope or the sizable increase of pasty state zone generation, liquidus temperature and solid-state temperature have all reduced comparatively speaking generally.
Sn-1.2Ag-0.5Cu-0.8～0.4In composition locates to have first endothermic peak at about 217 ℃ to about 218 ℃, and locates to have second endothermic peak at about 224 ℃ to about 225 ℃, and these two temperature can be regarded liquidus temperature and solid-state temperature respectively as.In this case, though also can observe slurry attitude scope or the sizable increase of pasty state zone generation, liquidus temperature and solid-state temperature have all reduced comparatively speaking generally.The Sn-1.2Ag-0.5Cu-0.2In composition locates to have first endothermic peak at about 219 ℃ to about 220 ℃, and locates to have second endothermic peak at about 226 ℃, and this two places temperature can be regarded liquidus temperature and solid-state temperature respectively as.In this case, though can observe slurry attitude scope or pasty state zone generation increase considerably, compare with solid-state temperature with the liquidus temperature of Sn-1.0Ag-0.5Cu composition, the liquidus temperature of said composition and solid-state temperature do not reduce yet.By this result as can be known, with respect to Sn-1.0Ag-0.5Cu composition wetability at low temperatures, Sn-1.2Ag-0.5Cu-0.2In composition solder flux wetability does not at low temperatures improve too much.
Fig. 3 and Fig. 4 are the figure that first exothermic peak in the state of cooling after the flux composition fusion is shown.Specifically, Fig. 3 and Fig. 4 show when being when cooling off after 10 ℃/min, nitrogen flow rate are to be heated to 250 ℃ under the condition of 50ml/min with flux composition (about 8mg) in firing rate again, the observed exothermic peak by using DSC.As shown in Figure 3, the Sn-3.0Ag-0.5Cu composition locates to have first exothermic peak at about 194 ℃, and this temperature is represented the actual setting temperature of this alloy.On metallurgy, poor (that is, in this case, about 23 ℃ to 24 ℃ temperature difference) of the melt temperature of alloy and actual setting temperature is called degree of supercooling.Degree of supercooling increases along with the minimizing of the amount of Ag in the alloy.For example, the Sn-1.0Ag-0.5Cu composition locates to have first exothermic peak at about 188 ℃, and this proof degree of supercooling increases.In contrast, the Sn-1.2Ag-0.5Cu-0.05Ni composition locates to have first exothermic peak at about 206 ℃ to about 207 ℃.By this result as can be known, add minor N i and can reduce degree of supercooling significantly.
By in composition, adding result that In obtains as shown in Figure 4.As shown in Figure 4, the Sn-1.0Ag-0.5Cu-1.0In composition locates to have first exothermic peak at about 200 ℃, and the Sn-1.0Ag-0.5Cu-0.5In composition locates to have first exothermic peak at about 190 ℃ to about 191 ℃, therefore, adds In and also can greatly reduce degree of supercooling.What can find in addition is, the Sn-1.2Ag-0.5Cu-0.8In composition locates to have first exothermic peak at about 192 ℃ to about 193 ℃, the Sn-1.2Ag-0.5Cu-0.6In composition locates to have first exothermic peak at about 197 ℃ to about 198 ℃, the Sn-1.2Ag-0.5Cu-0.4In composition locates to have first exothermic peak at about 200 ℃ to about 201 ℃, and the Sn-1.2Ag-0.5Cu-0.2In composition locates to have first exothermic peak at about 202 ℃ to about 203 ℃.
Fig. 5 and Fig. 6 illustrate zero to hand over the figure of time value with respect to welding temperature.In the single wettability test, measure zero and hand over time value, the wetting power in the time of 2 seconds and final wetting power, following result is a resulting mean value from 10 times or more times result of the test.Used sample is that width is that 3mm, length are the copper sheet of 10mm in the wettability test.The water soluble flux that SENJU company is produced is coated on the surface of copper sheet, is inserted into then in the solder flux of fusion, and wherein the degree of depth of Cha Ruing is 2mm.The insertion speed of copper sheet and take-off speed are 5mm/ second.As shown in Figure 5, zero of Sn-1.2Ag-0.5Cu-0.05Ni composition and Sn-1.0Ag-0.5Cu composition hand over time value to hand over time value much larger than zero of Sn-3.0Ag-0.5Cu composition.Particularly, can observe zero of in about 230 ℃ to 240 ℃ low temperature range composition hands over the time value increase bigger.On the contrary, as shown in Figure 6, if in composition, add In, can observe zero of composition and hand over time value obviously to reduce, and in about 230 ℃ to 240 ℃ low temperature range, make zero of composition hand over time value more effectively to reduce.Particularly, zero friendship time value of representative compositions of the present invention (being the Sn-1.2Ag-0.5Cu-0.4In composition) is similar to or is lower than zero of Sn-3.0Ag-0.5Cu composition and hands over time value.Therefore, can confirm that Sn-1.2Ag-0.5Cu-0.4In composition of the present invention has excellent wetting capacity as scolder.
Fig. 7 and Fig. 8 are that wetting power when being illustrated in 2 seconds is with respect to the figure of welding temperature.As shown in Figure 7, Sn-1.0Ag-0.5Cu composition and the Sn-1.2Ag-0.5Cu-0.05Ni composition wetting power in the time of 2 seconds is less than the wetting power of Sn-3.0Ag-0.5Cu composition 2 seconds the time.Particularly, Sn-1.0Ag-0.5Cu composition and the Sn-1.2Ag-0.5Cu-0.05Ni composition wetting power in the time of 2 seconds obviously reduces in about 230 ℃ to 240 ℃ low temperature range.In contrast, as shown in Figure 8, if add In in composition, the wetting power of composition in the time of 2 seconds significantly increases, and makes at the wetting power of the composition under 230 ℃ to 240 ℃ the low temperature during at 2 seconds and more effectively increase.Particularly, can confirm that the wetting power of representative compositions of the present invention (being the Sn-1.2Ag-0.5Cu-0.4In composition) in the time of 2 seconds is similar to or greater than the wetting power of Sn-3.0Ag-0.5Cu composition 2 seconds the time.
By The above results as can be known,, have excellent wetting capacity, therefore be suitable for welding material although the price of the present composition is very cheap.Therefore, unleaded solder composition of the present invention can be used for making tin cream, tin ball, tin bar, solder, solder bump, weldering paper tinsel, welding powder and preformed tin material.Herein, described preformed tin material can comprise solder balls, solder flux grain, solder flux band, solder flux packing ring, solder flux ring and solder flux dish.
Fig. 9 and Figure 10 illustrate the figure of final wetting power with respect to welding temperature.As shown in Figure 9, the final wetting power of Sn-1.0Ag-0.5Cu composition and Sn-1.2Ag-0.5Cu-0.05Ni composition is less than the final wetting power of Sn-3.0Ag-0.5Cu composition.Particularly, the final wetting power of Sn-1.0Ag-0.5Cu composition and Sn-1.2Ag-0.5Cu-0.05Ni composition significantly reduces in 230 ℃ to 240 ℃ low temperature range.In contrast, as shown in figure 10, produce interesting result behind the interpolation In.That is, when the addition height (for example 0.8 weight %) of In in the Sn-1.2Ag-0.5Cu-xIn composition, because the indium of fusion has low surface tension, so the final wetting power increase of composition seldom; And when the addition of In low (for example 0.2 weight %),, make final wetting power not improve because wetability improves seldom.On the contrary, can confirm that the final wetting power of representative compositions of the present invention (being the Sn-1.2Ag-0.5Cu-0.4In composition) is similar to or is slightly less than the final wetting power of Sn-3.0Ag-0.5Cu composition.Particularly, can observe the final wetting power of other compositions in 230 ℃ to 240 ℃ low temperature range that the final wetting power of Sn-1.2Ag-0.5Cu-0.4In composition in 230 ℃ to 240 ℃ low temperature range more is better than having Ag in a small amount.
Figure 11 is the figure that the result of the test that is obtained by the stretching sample is shown, and this stretching sample has conventional flux composition Sn-3.0Ag-0.5Cu, Sn-1.0Ag-0.5Cu and Sn-1.2Ag-0.5Cu-0.05Ni respectively.The proportional sample of stretching sample for making based on Korea S's standard (KS) 13A, its thickness is that 2mm, length are 27mm.Tension test is that room temperature, extension test speed are to carry out under the condition of 7.8mm/min in temperature.As shown in figure 11, the Sn-3.0Ag-0.5Cu composition has high intensity, but percentage elongation is low.This shows that when the Sn-3.0Ag-0.5Cu composition was used as welding material, though estimate that said composition has good heat-resisting cyclicity, anti-mechanical impact property was poor.On the contrary, the percentage elongation of Sn-1.0Ag-0.5Cu composition increases a little to some extent, but its intensity is too little.Therefore, be better than the anti-mechanical impact property of Sn-3.0Ag-0.5Cu composition though estimate the anti-mechanical impact property of Sn-1.0Ag-0.5Cu composition, its heat-resisting cyclicity is inferior to the heat-resisting cyclicity of Sn-3.0Ag-0.5Cu composition.The Sn-1.2Ag-0.5Cu-0.05Ni compositions table reveals the medium characteristic between Sn-3.0Ag-0.5Cu composition and Sn-1.0Ag-0.5Cu composition.
Figure 12 is the figure that the result of the test that is obtained by the stretching sample is shown, and this stretching sample has flux composition Sn-1.2Ag-0.5Cu-0.4In of the present invention, Sn-1.2Ag-0.5Cu-0.2In, Sn-1.2Ag-0.5Cu-0.6In, Sn-1.2Ag-0.5Cu-0.8In and Sn-1.0Ag-0.5Cu-1.0In respectively.As seen from Figure 12, the intensity of Sn-1.2Ag-0.5Cu-0.4In composition and percentage elongation all are higher than the intensity and the percentage elongation of similar compositions (for example Sn-1.0Ag-0.5Cu composition).That is, compare with the toughness of Sn-1.0Ag-0.5Cu composition, the toughness of Sn-1.2Ag-0.5Cu-0.4In composition improves.Can estimate that by this result the Sn-1.2Ag-0.5Cu-0.4In composition has the best anti-mechanical impact property, also have good heat-resisting cyclicity.Therefore, the Sn-1.2Ag-0.5Cu-0.4In composition is suitable as the welding material of the electronic device in the automobile that stands mechanical impact or vibration and the mobile product.In the Sn-1.2Ag-0.5Cu-0.2In composition, owing to add In, cause the reinforcing degree of metal to reduce, thereby make the intensity of metal reduce.In Sn-1.2Ag-0.5Cu-0.6In composition and Sn-1.2Ag-0.5Cu-0.8In composition, along with the increase of the addition of In, its percentage elongation reduces gradually.Though added a large amount of In in the Sn-1.0Ag-0.5Cu-1.0In composition, it does not show good intensity.
Adopt as above-mentioned identical experimental procedure, Sn-3.0Ag-0.5Cu composition, Sn-1.0Ag-0.5Cu composition and the Sn-0.3Ag-0.7Cu composition of another kind of quaternary unleaded solder composition of the present invention (being the Sn-0.3Ag-0.7Cu-0.2In composition) with routine compared.The results are shown among Figure 13 to Figure 15 of their wetability.
Figure 13 illustrates zero to hand over the figure of time value with respect to welding temperature, Figure 14 be wetting power when being illustrated in 2 seconds with respect to the figure of welding temperature, Figure 15 illustrates the figure of final wetting power with respect to welding temperature., compare with the Sn-0.3Ag-0.7Cu composition to shown in Figure 15 as Figure 13, the Sn-0.3Ag-0.7Cu-0.2In composition with a small amount of In has good above-mentioned wetability being higher than under 240 ℃ the temperature.That is, the wetability of Sn-0.3Ag-0.7Cu-0.2In composition is similar to the wetability of Sn-1.0Ag-0.5Cu composition.Can confirm also that by this result the unleaded solder composition with indium of appropriate amount of the present invention can make cost increase degree minimize and also can prevent to reduce the wetability reduction that causes owing to the content of Ag.
In order to improve the non-oxidizability of Sn-Ag-Cu-In quaternary unleaded solder composition, can in this quaternary unleaded solder composition, add percentage by weight and be about 0.001 weight % one or more elements in phosphorus (P), germanium (Ge), gallium (Ga), aluminium (Al) and the silicon (Si) of being selected to about 1 weight %.
In addition, for the interfacial reaction performance that improves Sn-Ag-Cu-In quaternary unleaded solder composition and reduce its fusing point, can in this quaternary unleaded solder composition, add percentage by weight and be about 0.001 weight % one or both elements in zinc (Zn) and the bismuth (Bi) of being selected to about 2 weight %.
In addition, in order to improve the mechanical performance and the interfacial reaction performance of Sn-Ag-Cu-In quaternary unleaded solder composition, can in this quaternary unleaded solder composition, add percentage by weight and be about 0.001 weight % one or more elements in nickel (Ni), cobalt (Co), gold (Au), platinum (Pt), plumbous (Pb), manganese (Mn), vanadium (V), titanium (Ti), chromium (Cr), niobium (Nb), palladium (Pd), antimony (Sb), magnesium (Mg), tantalum (Ta), cadmium (Cd) and the rare earth metal of being selected to about 1 weight %.
The reason of making above-mentioned additional description is in order to illustrate the following fact: be intended to get around patent of the present invention and the Sn-Ag-Cu-In quaternary unleaded solder composition that is added with other element in quaternary unleaded solder composition in fact also drops within the technological thought of the present invention.
As mentioned above, according to the present invention, the amount by reducing Ag is also added In, can be so that because the reduction of the wetability that the reduction of the amount of Ag causes is compensated, and can improve heat-resisting cyclicity and anti-mechanical impact property.Therefore the present invention can provide a kind of low-cost, high-quality unleaded solder composition.
Although invention has been described with reference to specific embodiment, but it is evident that to one skilled in the art, under the condition that does not break away from the spirit and scope of the present invention that limit as claims, can make various changes and modification.
Claims (4)
1. tin-silver-copper-indium quaternary unleaded (Pb) flux composition, it comprises:
More than or equal to about 0.3 weight % and less than the silver (Ag) of about 2.5 weight %;
More than or equal to about 0.2 weight % and less than the copper (Cu) of about 2.0 weight %;
More than or equal to about 0.2 weight % and less than the indium (In) of about 1.0 weight %; And
The tin of surplus (Sn).
2. composition as claimed in claim 1, wherein in order to improve the non-oxidizability of unleaded solder composition, also be added with percentage by weight in the described quaternary unleaded solder composition and be about 0.001 weight % one or more elements in phosphorus (P), germanium (Ge), gallium (Ga), aluminium (Al) and the silicon (Si) of being selected to about 1 weight %.
3. composition as claimed in claim 1, wherein for the interfacial reaction performance that improves the unleaded solder composition and reduce its fusing point, also be added with percentage by weight in the described quaternary unleaded solder composition and be about 0.001 weight % one or both elements in zinc (Zn) and the bismuth (Bi) of being selected to about 2 weight %.
4. composition as claimed in claim 1 also is added with percentage by weight and is about 0.001 weight % one or more elements in nickel (Ni), cobalt (Co), gold (Au), platinum (Pt), plumbous (Pb), manganese (Mn), vanadium (V), titanium (Ti), chromium (Cr), niobium (Nb), palladium (Pd), antimony (Sb), magnesium (Mg), tantalum (Ta), cadmium (Cd) and the rare earth metal of being selected to about 1 weight % in the wherein said quaternary unleaded solder composition.
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| KR1020070050905A KR100797161B1 (en) | 2007-05-25 | 2007-05-25 | Quaternary pb-free solder composition incorporating sn-ag-cu-in |
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| US6176947B1 (en) * | 1998-12-31 | 2001-01-23 | H-Technologies Group, Incorporated | Lead-free solders |
| KR100407448B1 (en) * | 2000-06-12 | 2003-11-28 | 가부시키가이샤 히타치세이사쿠쇼 | Electronic apparatus and semiconductor device |
| JP3776361B2 (en) * | 2001-02-09 | 2006-05-17 | 大豊工業株式会社 | Lead-free solder and solder joints |
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| US20030021718A1 (en) * | 2001-06-28 | 2003-01-30 | Osamu Munekata | Lead-free solder alloy |
| JP2005040847A (en) * | 2003-07-25 | 2005-02-17 | Hitachi Metals Ltd | Manufacturing method of solder bowl |
| JP2005046882A (en) * | 2003-07-29 | 2005-02-24 | Hitachi Metals Ltd | Solder alloy, solder ball, and solder joined body |
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- 2007-05-25 KR KR1020070050905A patent/KR100797161B1/en active IP Right Grant
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- 2008-04-11 US US12/081,195 patent/US20080292493A1/en not_active Abandoned
- 2008-04-14 JP JP2008104956A patent/JP2008290150A/en active Pending
- 2008-04-30 CN CNA2008100938399A patent/CN101569965A/en active Pending
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Also Published As
| Publication number | Publication date |
|---|---|
| JP2008290150A (en) | 2008-12-04 |
| US20080292493A1 (en) | 2008-11-27 |
| KR100797161B1 (en) | 2008-01-23 |
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