CN103978320B - The low silver-colored series lead-free solder that a kind of particle adds - Google Patents
The low silver-colored series lead-free solder that a kind of particle adds Download PDFInfo
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- CN103978320B CN103978320B CN201410228874.2A CN201410228874A CN103978320B CN 103978320 B CN103978320 B CN 103978320B CN 201410228874 A CN201410228874 A CN 201410228874A CN 103978320 B CN103978320 B CN 103978320B
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- free solder
- hollow ball
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
- H01L2924/30—Technical effects
- H01L2924/36—Material effects
- H01L2924/365—Metallurgical effects
- H01L2924/3651—Formation of intermetallics
Abstract
The present invention relates to a kind of low silver-colored series lead-free solder of the interpolation Co nano-hollow ball particle for solders such as electronic devices and components welding and surface mount, it taking low silver be tin-base lead-free solder as matrix, add a small amount of nano Co particle. The composition of this scolder is by percentage to the quality: Ag0.3-1.3%, and Co nano-hollow ball particle 0.05-1%, all the other are Sn. The present invention compared with common lead-free solder, melting point depression, wetting power improves, wetting time shortens, and interface pessimum intermetallic compound Cu3Sn thickness reduction, welding performance is more excellent.
Description
Technical field
The present invention relates to a kind of solder lead-free solder for electronic devices and components welding and surface encapsulation, specifically a kind of CoThe low silver-colored series lead-free solder of nano-hollow ball particle strengthening, adding low silver by Co nano-hollow ball particle is tin-base lead-free solder, shapeBecome the lead-free solder of reinforced by nanoparticles.
Background technology
Connect in industry at electronics, as the tin-lead solder of connecting material dominate [1] always for a long time. But, peopleClass society finds in to the long-term use of lead, plumbously can cause serious threat to the mankind's health. And leaded discarded object because ofDealing with improperly and atmosphere pollution, soil and even underground water, is that ecological environment is destroyed; Ecological environment effect conversely again simultaneouslyIn mankind itself, make people absorb too much harmful substance from the food of air, drinking water and the every day of breathing. [2]
Electronic product is just towards ultraminiaturization and high reliability future development, thereby to the various electricity including electronics connecting materialSub-device or electronic material have all proposed to upgrade higher requirement [3]. Meanwhile, in the world in the restriction of the industrial department such as electronics orBan use of plumbous cry day by day surging. Meet the needs of RoHS instruction for adapting to the industries such as electronics, household electrical appliances, in the urgent need to developmentDevelop New Lead-free Solder alternative Sn-Pb scolder, that there is good welding performance and dependability. [4]
In order to adapt to different technological requirements, scientific workers develop the lead-free solder of different-alloy composition. But in realityIn, the property indices to lead-free solder and drive in the wrong direction consider after, Electronic Packaging industrial circle is solder alloy to Sn-AgBe the most good. [5]
But Ag is as noble metal, expensive, make the cost of argentiferous scolder used for electronic packaging high, the cost of silver is severalAccount for the half of totle drilling cost. Developing low-cost, available low silver-colored series lead-free solder becomes the urgent need of Electronic Packaging industryAsking, is also one of focus of domestic and international scolder research. [6] present low silver-colored series lead-free solder is all the base at Sn-Ag-Cu scolderOn plinth, develop, although SAC0307 and SAC105 etc. can apply, the minimizing of silver content has much bad to the performance of scolderImpact, scolder Melting point elevation, wetability variation, reliability of solder joints reduces, the too thick joint longevity causing of weld interface IMCThe lower degradation of life. [7]
Summary of the invention
For the problems referred to above, the technical problem to be solved in the present invention is that exploitation is a kind of for electronic devices and components welding and surface-pastedThe low silver-colored series lead-free solder of Co nano-hollow ball particle strengthening. Feature of the present invention is that Co nano-hollow ball particle is added to lowSilver is in tin-base lead-free solder. The present invention, containing Pb element, has not protected environment; The content of Ag is reduced to below 1.3%, fallsLow lead-free solder preparation cost; The Co nano-hollow ball particle that has added preparation, has improved solderability, has significantly reduced scolderThe pessimum phase Cu of/Cu substrate interface place3The thickness of Sn and controlled intermetallic compound Cu6Sn5Thereby thickness heightened weldingReliability.
The object of the invention is to be achieved through the following technical solutions.
A low silver-colored series lead-free solder for Co nano-hollow ball particle strengthening, is characterized in that: only 0.3-1.3 of tin solder silver content(wt.%), the Co nano-hollow ball grain diameter of interpolation is about 600nm, and its content is 0.05-1 (wt.%), and all the other are Sn.
Principle of the present invention is: the effect of dispersion-strengtherning is played in the interpolation of Co nano-hollow ball particle, and is grown at crystal by itIn play the effect of heterogeneous forming core, in welding process, can promote fast formation and the growth of intermetallic compound, form goodWetting interface; And due to the existence of Co nano-hollow ball particle, suppress the diffusion of Cu, made Cu3The growth of Sn obtainsSuppress, improved the thickness of compound between interface metal.
Further preferably, in above-mentioned leadless welding alloy, described leadless welding alloy contains the percentage by weight of following compositionFor:
Ag:1%; Co nano-hollow ball particle: 0.1%-0.5%; All the other are Sn.
Further preferably, in above-mentioned leadless welding alloy, described leadless welding alloy contains the percentage by weight of following compositionFor:
Ag:1%; Co nano-hollow ball particle: 0.5%; All the other are Sn.
Brief description of the drawings
The DSC test gained fusing point statistics of Fig. 1 scolder of the present invention;
The wetting power test result of Fig. 2 scolder of the present invention;
The wetting time test result of Fig. 3 scolder of the present invention;
Compound sectional view between the interface metal that Fig. 4 scolder of the present invention (embodiment 2) and Cu substrate form through reflux digestion;
Between the interface metal that Fig. 5 scolder of the present invention (it is 1% that Ag content accounts for scolder percentage by weight) and Cu substrate form through reflux digestionCompound thickness statistical chart.
Detailed description of the invention
Describe the present invention below in conjunction with embodiment.
Embodiment 1
The preparation of 1.Co nano-hollow ball particle
(1) iron core preparation:
A. get 69.5gFeSO4·7H2O, joins the solution 500mL of 0.5mol/L;
B. in 150mL ammoniacal liquor, add 50mL deionized water for subsequent use, weigh 4.5gNaBH4Add in above-mentioned ammoniacal liquor for subsequent use;
C. under mechanical agitation, above-mentioned both mix and are heated to 80 DEG C, and after approximately 15 minutes, wall of cup has bright silver mirror, and bubble disappearsLose, reaction finishes, and iron core generates.
(2) coated Co:
A. take respectively 21gCoSO4And sodium potassium tartrate tetrahydrate, 10gNaOH, gets respectively a certain amount of distilled water and dissolves, and mixes and joins afterwardsBecome complexing than the PH of 1:1 > 13 solution, with volumetric flask constant volume 1L, take 500mL;
The iron core of b. getting above-mentioned steps adds 500mL plating solution, take 10mL hydrazine hydrate be diluted to 40mL add gradually start anti-Should, ultrasonic agitation at 50 DEG C, after 20-40 minutes, mixed solution clarification, without bubble, almost colourless, and reaction finishes.
(3) dissolve core:
Get hydrochloric acid moon 9mL and be diluted to the particle that adds above-mentioned preparation under about 800mL normal temperature, treat that dissolved ferric iron is complete, can obtain finally and produceThing Co nano-hollow ball particle.
The scanning electron microscope (SEM) photograph of gained Co nano-hollow ball particle as shown in Figure 1.
2. scolder preparation
In prepared scolder, it is as shown in the table for Sn ball, Ag powder and Co nano-hollow ball granular powder relevant parameter.
Table: metal used when melting solder alloy
Scolder melting: just Sn ball, Ag powder mix and put into Al according to certain proportioning2O3In ceramic crucible, and be heated to480 DEG C, insulation 10min, makes its fusing. Then continue heating with resistance furnace, furnace temperature is set to 600 DEG C. After fusing, open completelyBeginning timing, then be incubated 120min. During this period, stir once with ceramic rod every 10min, make full and uniformization of alloying component.After two hours, Co nano-hollow ball particle is added to crucible, keep temperature and stir 10 minutes. Hot crucible is taken out from stove,Be placed in air and be cooled to room temperature (20 DEG C), then from crucible, take out. The cooling rear alloy cast ingot any surface finish of mold, without obviousDefect. Said process all carries out under nitrogen protection.
3. scolder detects
A. melted scolder is done to DSC test, test result is added up as shown in Figure 2. Add 0.1%Co nano-hollow varioleThe fusing point of the scolder of grain declines to some extent.
B. melted scolder is made to Φ 4 × 4mm3Cylinder do wetting power test, test result is as shown in Figure 3,4. AddThe wetting power of Co nano-hollow ball particle scolder increases, and wetting time declines to some extent.
C. melted scolder is placed in and processes on clean copper coin, reflux through classical reflux temperature curve, form good solder joint.Through 48-300 hours agings, between observation interface metal, compound was (as shown in Figure 5, with scolder (Co0.5wt.%) againWith Cu substrate form intermetallic compound be example) growth thickness, test result is as shown in Figure 6. Add Co nano-hollowBall particle scolder and copper coin are through the pessimum intermetallic compound Cu refluxing, different time forms after aging3Sn thickness obviously declines.
Embodiment 2
The low silver-colored series lead-free solder that the Co nano-hollow ball particle of the present embodiment adds is tin solder and Co nanometer sky by low silverBulbus cordis particle composition, wherein Co nano-hollow ball grain diameter is about 600nm. This lead-free solder consists of:
This composition scolder preparing is done to compound observation between wetting power test, DSC test, interface metal, result as Fig. 2,3,, shown in 4,6, all kinds of performances are all significantly improved.
[1] Shangguan east happy. environmental protection strategy guiding electronics manufacturing is gone on unleaded [A]. sees: the 14 the international SMT skill in ShanghaiThe senior Conference Papers collection of art [C], Shanghai, 2004,14-22
[2]RoadmapIPC.Aguideforassemblyoflead-freeelectronics[J].DraftIV,June,2000.
[3]ZhangL,HeC,GuoY,etal.DevelopmentofSnAg-basedleadfreesoldersinelectronicspackaging[J].MicroelectronicsReliability,2012,52(3):559-578.
[4]ChidambaramV,HattelJ,HaldJ.High-temperaturelead-freesolderalternatives[J].MicroelectronicEngineering,2011,88(6):981-989.
[5] Guo Fu. Lead-Free Soldering Technology technology and application [M]. Beijing: Science Press, 2005.86-87
[6]CheFX,ZhuWH,PohESW,etal.ThestudyofmechanicalpropertiesofSn–Ag–Culead-freesolderswithdifferentAgcontentsandNidopingunderdifferentstrainratesandtemperatures[J].JournalofAlloysandCompounds,2010,507(1):215-224.
[7]SuhD,KimDW,LiuP,etal.EffectsofAgcontentonfractureresistanceofSn–Ag–Culead-freesoldersunderhigh-strainrateconditions[J].MaterialsScienceandEngineering:A,2007,460:595-603.
Claims (3)
1. the low silver-colored series lead-free solder that Co nano-hollow ball particle adds, is characterized in that at low silver be in tin-base lead-free solderAdd Co nano-hollow ball particle, the composition of this scolder is by percentage to the quality:
Ag:0.3-1.3%; Co nano-hollow ball particle: 0.05%-1%; All the other are Sn, wherein Co nano-hollow ball particleFootpath is 20-60nm.
2. lead-free solder according to claim 1, is characterized in that the percentage by weight that Ag accounts for solder compositions is 1%, CoThe percentage by weight that nano-hollow ball particle accounts for solder compositions is 0.1%-0.5%.
3. lead-free solder according to claim 2, is characterized in that Co nano-hollow ball particle accounts for the weight of solder compositionsPercentage is 0.5%.
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| CN103978320B true CN103978320B (en) | 2016-05-25 |
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| EP3235588B1 (en) * | 2014-12-15 | 2019-11-06 | Senju Metal Industry Co., Ltd | Solder alloy for plating and electronic component |
Citations (6)
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| US6513728B1 (en) * | 2000-11-13 | 2003-02-04 | Concept Alloys, L.L.C. | Thermal spray apparatus and method having a wire electrode with core of multiplex composite powder its method of manufacture and use |
| CN101362259A (en) * | 2008-09-24 | 2009-02-11 | 上海大学 | Nano leadless soldering paste |
| CN102189270A (en) * | 2011-05-04 | 2011-09-21 | 上海大学 | Method for chemically synthesizing nano lead-free solder particles with low melting point |
| JP2011184723A (en) * | 2010-03-05 | 2011-09-22 | Tohoku Univ | Method for synthesizing nanocrystalline alloy |
| CN102438776A (en) * | 2009-07-16 | 2012-05-02 | 应用纳米粒子研究所株式会社 | Composite nanometal paste of two-metallic-component type, bonding method, and electronic part |
| CN103097588A (en) * | 2010-07-19 | 2013-05-08 | 莱顿大学 | Process to prepare metal nanoparticles or metal oxide nanoparticles |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8493746B2 (en) * | 2009-02-12 | 2013-07-23 | International Business Machines Corporation | Additives for grain fragmentation in Pb-free Sn-based solder |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6513728B1 (en) * | 2000-11-13 | 2003-02-04 | Concept Alloys, L.L.C. | Thermal spray apparatus and method having a wire electrode with core of multiplex composite powder its method of manufacture and use |
| CN101362259A (en) * | 2008-09-24 | 2009-02-11 | 上海大学 | Nano leadless soldering paste |
| CN102438776A (en) * | 2009-07-16 | 2012-05-02 | 应用纳米粒子研究所株式会社 | Composite nanometal paste of two-metallic-component type, bonding method, and electronic part |
| JP2011184723A (en) * | 2010-03-05 | 2011-09-22 | Tohoku Univ | Method for synthesizing nanocrystalline alloy |
| CN103097588A (en) * | 2010-07-19 | 2013-05-08 | 莱顿大学 | Process to prepare metal nanoparticles or metal oxide nanoparticles |
| CN102189270A (en) * | 2011-05-04 | 2011-09-21 | 上海大学 | Method for chemically synthesizing nano lead-free solder particles with low melting point |
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