CN105834611B - A kind of high conductance high reliability Ce Sn Ag Cu solders suitable for Electronic Packaging - Google Patents

A kind of high conductance high reliability Ce Sn Ag Cu solders suitable for Electronic Packaging Download PDF

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Publication number
CN105834611B
CN105834611B CN201610288123.9A CN201610288123A CN105834611B CN 105834611 B CN105834611 B CN 105834611B CN 201610288123 A CN201610288123 A CN 201610288123A CN 105834611 B CN105834611 B CN 105834611B
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CN
China
Prior art keywords
solder
solders
electronic packaging
high reliability
solder joint
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
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CN201610288123.9A
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Chinese (zh)
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CN105834611A (en
Inventor
王斌
涂晓萱
王亚军
李金州
樊学农
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
DONGGUAN JINZHONG ELECTRONICS Co Ltd
Central South University
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DONGGUAN JINZHONG ELECTRONICS Co Ltd
Central South University
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Application filed by DONGGUAN JINZHONG ELECTRONICS Co Ltd, Central South University filed Critical DONGGUAN JINZHONG ELECTRONICS Co Ltd
Priority to CN201610288123.9A priority Critical patent/CN105834611B/en
Publication of CN105834611A publication Critical patent/CN105834611A/en
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Publication of CN105834611B publication Critical patent/CN105834611B/en
Expired - Fee Related legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24Selection of soldering or welding materials proper
    • B23K35/26Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262Sn as the principal constituent
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B23MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23KSOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing

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  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

The invention discloses a kind of high conductance high reliability Ce Sn Ag Cu solders suitable for Electronic Packaging, the main metal element of solder alloy is Ce, Sn, Ag, Cu and Be.The solder of the present invention, by adding micro Be in Ce Sn Ag Cu solder alloy solders, unexpectedly improve the high oxidation and corrosion resistance and electrical and thermal conductivity performance of solder alloy, the dimensional stability of postwelding solder joint is high, solder joint anti-dropping capability is strong, can meet the rigors of existing Electronic Packaging.

Description

A kind of high conductance high reliability Ce-Sn-Ag-Cu solders suitable for Electronic Packaging
Technical field
The present invention relates to a kind of high performance solder, more particularly to a kind of high conductance high reliability suitable for Electronic Packaging Ce-Sn-Ag-Cu solders.
Background technology
Develop along with electronic product to thin, light, small and digitlization, multifunction direction, the miniaturization of electronic component, The development trend of precise treatment and high performance will further speed up so that the number of welds for Electronic Packaging increases, size Diminish, spacing it is more and more narrow, and calorifics that it is born, electricity, mechanical loading more and more higher.Research shows, electronic device Failure have 70% be as caused by the failure for encapsulating and assembling, wherein, solder joint failure is chief reason.
Solder joint can be used as electrical path in Electronic Packaging, and and can provides the same of mechanical connection between chip and substrate Shi Tigao thermal conductivitys, it is used widely in electronics load, so welding spot reliability problem has very important research meaning Justice.
The development of the ultra-fine pitch electronic encapsulation of High Density Integration is necessarily faced with the challenge of welding spot reliability decline, wherein, Interconnection short circuit caused by being concentrated between chip bump and pad due to thermal stress between fillet lifting and salient point is electronic product In relatively common failure mode.In order to avoid occurring, it is necessary to the dimensionally stable of accurate effective control solder joint for such case Property and be on active service during electrical and thermal conductivity performance.
To study bright, Ce-Sn-Ag-Cu solders have electric conductivity more more preferable than traditional Sn-Pb solders and density, Although fusion temperature is more slightly higher than Sn-Pb solder, all within the scope of existing soldering processes are acceptable.The wetting of solder, Sprawl result of the test to show, Ce-Sn-Ag-Cu solders are on Au/Ni/Cu substrates than having preferably wetting on Cu substrates Performance.Micro Ce elements are added, the wetting of Sn-Ag-Cu solders, spreading property can be made to increase significantly, solder is in substrate On spreading area increase, wetting time shorten, wetting power improve, angle of wetting reduce.Ce addition is left 0.03% ~ 0.05% When right, the wetting and spreading performance of Ce-Sn-Ag-Cu solders is optimal, and its wetting time shortens than being not added with Ce Sn-Ag-Cu solders 20%~40%.Ce is surface active element, there is enrichment phenomenon on Sn-Ag-Cu solders surface, and Ce surface enrichment reduces molten Melt the surface tension of solder, be effectively improved wetting, the spreading property of lead-free brazing.Solder joint mechanical property test result table Tensile force and the shearing force of plate resistor solder joint bright, that Ce addition will all improve its QFP pin solder joint.When Ce contents exist When 0.03% or so, the mechanical property of Ce-Sn-Ag-Cu solder joints is optimal.For QFP32, QFP100 and three kinds of electronics of plate resistor Component, tensile force (shearing force) values of Sn-Ag-Cu-0.03Ce solder joints improves 4.56% than Sn-Ag-Cu solder joint respectively, 4.06% and 3.81%.Theory analysis shows, due to rare earth element ce has " close Sn " effects, i.e. Ce elements preferentially with Sn element knots Close, therefore, Ce addition can make the structure refinement of brazing filler metal alloy and solder joint, homogenization, can be effectively prevented from Sn elements and Ag elements, which combine, generates thick Ag3Sn intermetallic compounds, so as to improve the mechanical property of solder joint.It is unleaded to QFP pins Solder joint and plate resistor Lead-Free Solder Joint carry out thermal cycling test (the actual military service situation of simulating solder joint) result and found, experienced After Long Time Thermal cyclic test, solder joint mechanical property gradually reduces with the increase in thermal cycle cycle, and trace rare-earth element Ce addition can delay the deterioration of solder joint mechanical property, so as to effectively improve the reliability of solder joint.
However, the electrical conductance of Ce-Sn-Ag-Cu solders, reliability can not still meet that the harshness of existing Electronic Packaging will Ask.Develop a kind of more excellent solder of performance.
The content of the invention
It is an object of the invention to provide a kind of high conductance high reliability Ce-Sn-Ag-Cu welderings suitable for Electronic Packaging Material.
The technical solution used in the present invention is:
A kind of high conductance high reliability Ce-Sn-Ag-Cu solders suitable for Electronic Packaging, the major metal of solder alloy Element is Ce, Sn, Ag, Cu and Be.
As the further improvement of above-mentioned solder, the mass percent of main metal element is in solder alloy:Ag :2.0 ~3.8%, Cu:0.4~0.7%, Ce:0.01~0.7%, Be:0.01~1.0%, surplus Sn.
As the further improvement of above-mentioned solder, the mass percent of main metal element is in solder alloy:Ag :3.0 ~3.8%, Cu:0.5~0.7%, Ce:0.02~0.7%, Be:0.2~0.5%, surplus Sn.
As the further improvement of above-mentioned solder, Ag and Cu quality addition ratio is in solder alloy(5~6):1, preferably , Ag and Cu quality addition ratio are(5~5.4):1.
As the further improvement of above-mentioned solder, Ce and Be quality addition is than being 1 in solder alloy:(1~2), preferably , Ce and Be quality addition are than being 1:(1~1.5).
A kind of circuit board, has solder joint on circuit board, and solder joint is highly reliable by the above-mentioned high conductance suitable for Electronic Packaging Property Ce-Sn-Ag-Cu solders weld to obtain.
The beneficial effects of the invention are as follows:
The solder of the present invention, by adding micro Be in Ce-Sn-Ag-Cu solder alloy solders, is unexpectedly improved The high oxidation and corrosion resistance and electrical and thermal conductivity performance of solder alloy, the dimensional stability of postwelding solder joint is high, solder joint anti-drop Can be strong, the rigors of existing Electronic Packaging can be met.
Brief description of the drawings
Fig. 1 is comparative example 1, the metallograph of the solder alloy of comparative example 2;
Fig. 2 is the metallograph of the solder alloy of embodiment 1;
Fig. 3 is the solder alloy SEM figures of comparative example 1;
Fig. 4 is comparative example 2 and the solder alloy SEM figures of embodiment 1;
Fig. 5 comparative examples 1, comparative example 2 and the tensile strength of solder joint comparison diagram of embodiment 1,2,3;
The solder joint pictorial diagram of Fig. 6 embodiments 1,2,3,4;
Fig. 7 is the welding point interface figure of comparative example 1, comparative example 2;
Fig. 8 is the welding point interface figure of embodiment 1.
Embodiment
A kind of high conductance high reliability Ce-Sn-Ag-Cu solders suitable for Electronic Packaging, the major metal of solder alloy Element is Ce, Sn, Ag, Cu and Be.Inevitable impurity element can also be contained in solder.
As the further improvement of above-mentioned solder, the mass percent of main metal element is in solder alloy:Ag :2.0 ~3.8%, Cu:0.4~0.7%, Ce:0.01~0.7%, Be:0.01~1.0%, surplus Sn.
As the further improvement of above-mentioned solder, the mass percent of main metal element is in solder alloy:Ag :3.0 ~3.8%, Cu:0.5~0.7%, Ce:0.02~0.7%, Be:0.2~0.5%, surplus Sn.
As the further improvement of above-mentioned solder, Ag and Cu quality addition ratio is in solder alloy(5~6):1, preferably , Ag and Cu quality addition ratio are(5~5.4):1.
As the further improvement of above-mentioned solder, Ce and Be quality addition is than being 1 in solder alloy:(1~2), preferably , Ce and Be quality addition are than being 1:(1~1.5).
A kind of circuit board, has solder joint on circuit board, and solder joint is highly reliable by the above-mentioned high conductance suitable for Electronic Packaging Property Ce-Sn-Ag-Cu solders weld to obtain.
The solder of the present invention can be prepared according to a conventional method, i.e., formed according to the alloy of solder, weigh corresponding metal Melting is uniform under element or alloy, vacuum state or protection gas shielded, and secondary melt back is uniform afterwards, uses routine side as needed Method manufactured Board, band, paper tinsel, thread or ultra-fine welding powder.
With reference to embodiment, technical scheme is further illustrated.
For the sake of convenient comparison, the solder of following examples and comparative example is prepared as follows:
1) corresponding raw metal is weighed by solder composition, in vacuum intermediate-frequency induction melting furnace, in argon atmosphere In be warming up to 850~1000 DEG C of meltings, be incubated 0.5h;
2) 400~500 DEG C of remeltings 3 times are cooled to, to ensure that the structural constituent that alloy is made is uniform, subsequent air cooling, are made Solder ingot blank;
3) as needed, solder ingot blank is used directly as solder, or the method using machinings such as pressure rolling, extruding Manufactured Board, band, paper tinsel, gage solder, or using Close-Coupled Gas Atomization equipment be atomized into 15~25 μm, 20~38 μm of ultra-fine welding powders with It is standby to use.
The solder of embodiment and comparative example composition is as follows:
With reference to experiment, the performance difference of different solders is further illustrated.
Fig. 1 is comparative example 1, the metallograph of the solder alloy of comparative example 2, and Fig. 2 is that the metallographic of the solder alloy of embodiment 1 shines Piece.It can be seen that by adding Be elements in Ce-Sn-Ag-Cu solders, β-Sn tissues can be refined significantly, form From original bar-shaped to granular transformation, and the distribution of crystal grain more disperse is tiny.
Fig. 3 is the solder alloy SEM figures of comparative example 1, and Fig. 4 is comparative example 2 and the solder alloy SEM figures of embodiment 1.From figure In as can be seen that the present invention solder, moreover it is possible to refined eutectic structure, on the basis of Sn-Ag-Cu-Ce solders add Be elements Can significantly Ag in refined eutectic structure3The size of Sn phases, it can effectively improve the mechanical property of solder alloy.
Fig. 5 comparative examples 1, comparative example 2 and the tensile strength of solder joint comparison diagram of embodiment 1,2,3.It can be seen that utilize Solder joint prepared by the solder of the present invention has more preferable mechanical property.
The solder joint pictorial diagram of Fig. 6 embodiments 1,2,3,4.It can be seen that the sold joint that the solder of the present invention is formed Excellent, the surface zero defect of property.
Fig. 7 is the welding point interface figure of comparative example 1, comparative example 2, and Fig. 8 is the welding point interface figure of embodiment 1.Can be with from figure To find out, welding point interface of the invention is straight, by adding Be elements so that welding point interface is changed from scallop shape to straightened, and The growth of welding point interface brittle compound layer is inhibited, improves the mechanical property of welding point interface to a certain extent.

Claims (7)

1. a kind of high conductance high reliability Ce-Sn-Ag-Cu solders suitable for Electronic Packaging, the major metal member of solder alloy Element is Ce, Sn, Ag, Cu and Be, and the mass percent of main metal element is:Ag:2.0~3.8%, Cu:0.4~0.7%, Ce:0.01~0.7%, Be:0.01~1.0%, surplus Sn.
2. the high conductance high reliability Ce-Sn-Ag-Cu solders according to claim 1 suitable for Electronic Packaging, its feature It is:The mass percent of main metal element is:Ag:3.0~3.8%, Cu:0.5~0.7%, Ce:0.02~0.7%, Be:0.2~0.5%, surplus Sn.
3. the high conductance high reliability Ce-Sn-Ag-Cu solders according to claim 1 suitable for Electronic Packaging, its feature It is:Ag and Cu quality addition ratio is (5~6):1.
4. the high conductance high reliability Ce-Sn-Ag-Cu solders suitable for Electronic Packaging according to claim 1 or 3, its It is characterised by:Ce and Be quality addition is than being 1:(1~2).
5. the high conductance high reliability Ce-Sn-Ag-Cu solders according to claim 3 suitable for Electronic Packaging, its feature It is:Ag and Cu quality addition ratio is (5~5.4):1.
6. the high conductance high reliability Ce-Sn-Ag-Cu solders according to claim 4 suitable for Electronic Packaging, its feature It is:Ce and Be quality addition is than being 1:(1~1.5).
7. a kind of circuit board, there is solder joint on circuit board, it is characterised in that:Solder joint is as described in claim 1~6 any one Weld to obtain suitable for the high conductance high reliability Ce-Sn-Ag-Cu solders of Electronic Packaging.
CN201610288123.9A 2016-05-04 2016-05-04 A kind of high conductance high reliability Ce Sn Ag Cu solders suitable for Electronic Packaging Expired - Fee Related CN105834611B (en)

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Publication number Priority date Publication date Assignee Title
CN106825983B (en) * 2017-03-10 2020-05-05 南京达迈科技实业有限公司 SnAgSbNi series lead-free soldering tin alloy and preparation method and application thereof
CN113857713B (en) * 2021-09-15 2023-02-28 昆明理工大学 Low-silver Sn-Ag-Cu lead-free solder and preparation method thereof

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CN1203960C (en) * 2003-01-15 2005-06-01 深圳市亿铖达工业有限公司 Oxidation-inhibited lead-free welding materials
CN1570166A (en) * 2004-05-09 2005-01-26 邓和升 Lead free solder alloy and its preparation method
CN1990161A (en) * 2005-12-30 2007-07-04 上海飞轮有色冶炼厂 Lead free solder alloy and its preparation method
JP5210323B2 (en) * 2006-12-29 2013-06-12 イルジン カッパー ホイル カンパニー リミテッド Lead-free solder alloy
JP5245568B2 (en) * 2008-06-23 2013-07-24 新日鉄住金マテリアルズ株式会社 Electronic member having lead-free solder alloy, solder ball and solder bump
CN105149809B (en) * 2015-10-10 2017-09-26 南京青锐风新材料科技有限公司 It is a kind of suitable for antioxidant of SnAgCu or SnCu solders and preparation method thereof

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