CN108526748A - A kind of SnBiAgSbIn low temperature lead-free solder alloys - Google Patents

A kind of SnBiAgSbIn low temperature lead-free solder alloys Download PDF

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Publication number
CN108526748A
CN108526748A CN201810266729.1A CN201810266729A CN108526748A CN 108526748 A CN108526748 A CN 108526748A CN 201810266729 A CN201810266729 A CN 201810266729A CN 108526748 A CN108526748 A CN 108526748A
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CN
China
Prior art keywords
temperature lead
snbiagsbin
low temperature
solder
free solder
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.)
Pending
Application number
CN201810266729.1A
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Chinese (zh)
Inventor
滕媛
白海龙
陈东东
刘宝权
徐凤仙
赵玲彦
吕金梅
武信
秦俊虎
古列东
张欣
孙维
孙绍福
禹锐
孙彪
肖倩
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YUNNAN TIN MATERIAL CO Ltd
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YUNNAN TIN MATERIAL CO Ltd
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Priority to CN201810266729.1A priority Critical patent/CN108526748A/en
Publication of CN108526748A publication Critical patent/CN108526748A/en
Pending legal-status Critical Current

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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
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • 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
    • B23K35/22—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
    • B23K35/264—Bi as the principal constituent

Abstract

The invention discloses a kind of SnBiAgSbIn low temperature lead-free solder alloys, belong to low-temperature solder alloy technical field.The present invention low-temperature lead-free solder by weight percentage, including：30 60% Bi, 0 3.5% Ag, 0.1 3% Sb, 0 3.0% In, 0 0.11% Ge, 0 0.11% P, two or more rare earth elements, the Sn of surplus and inevitable impurity.The present invention can inhibit the segregation of Bi elements, improve solder joint mechanical performance, solving current binary SnBi solders, the problems such as cavity, bad mechanical property, easily peelable solder joint easily occurs in solder joint in use.

Description

A kind of SnBiAgSbIn low temperature lead-free solder alloys
Technical field
The present invention relates to a kind of SnBiAgSbIn low temperature lead-free solder alloys, belong to low-temperature solder alloy technical field.
Background technology
Since electronic solder is unleaded, widely used is SnCu systems, SnAgCu systems solder alloy, these types Widely used solder alloy fusing point is higher.But with the lasting propulsion of Moore's Law, chip is to Highgrade integration, light Thinning develops, and when being welded using existing welding procedure, the defective workmanships such as warpage, pillow nest, bridging easily occurs.And due to weldering Jointing temp is higher, causes the heated crash rate of chip higher.In view of the above-mentioned problems, the relevant enterprises such as solder industry are actively opened at present Low temperature lead-free solder alloy is sent out, current solder includes SnBi systems, SnZn systems, SnIn systems etc..Wherein, SnZn inoxidizability Can be poor, solder joint is perishable.The eutectic composition of SnIn is respectively the In for the Sn and 52% that mass fraction is 48%, and eutectic temperature is 117 DEG C, SnIn solders dissolve soon on Cu, and interface compound structure is influenced by solubility of the Cu in SnIn, easily forms Cu2 (Sn, In) and Cu2In3Sn, and Cu2In3Sn is in the rich sides In.In can improve the wetability of solder, but In is dilute scattered gold Belong to, global resources reserves are extremely low, higher price, do not have the foreground of large-scale use, and a kind of trace element can only be used as to carry out Addition uses.Using it is more be SnBi series low-temperature leadless solder alloys, the addition of Bi can effectively reduce the fusing point of solder, but It is SnBi solder alloys since Bi is easily segregated, causes welding performance to be deteriorated, solder joint brittleness is big, such as the fusing point of eutectic solder Sn58Bi It it is 139 DEG C, under the conditions of medium cooling velocity, eutectic phase SnBi is in the form of sheets；Under Slow cooling speed, crystal grain is larger, soldering The crackle of connector is generally extended along crystal boundary；And the recrystallization of soldered fitting can cause volume expansion, to aggravate the crisp of alloy Change.When by impact and stress, the micro-cracks of generation extend welding point along crystal boundary, and then solder joint is caused to be broken and lose Effect.
Invention content
Present invention seek to address that the deficiencies in the prior art, a kind of segregation can inhibit Bi elements is provided, improves solder joint machinery The SnBiAgSbIn low-temperature lead-free solders of performance.
The technical solution adopted by the present invention is as follows：
The weight percent group of a kind of SnBiAgSbIn low temperature lead-free solder alloys, the leadless welding alloy becomes：30- 60% Bi；The Ag of 0-3.5%；The Sb of 0.1-3%；The In of 0-3.0%；The Ge of 0-0.11%；The P of 0-0.11%；With it is optional The compound addition of two or more following rare earth elements：The Y of 0-0.5%；The La of 0-0.5%；The Ce of 0-0.5%；0-0.5%'s Pr；The Sn of surplus and inevitable impurity.
A kind of SnBiAgSbIn low temperature lead-free solder alloys, by weight percentage, including：
The Bi of 30-60%；
The Ag of 0-3.5%；
The Sb of 0.1-3%；
The In of 0-3.0%；
The Ge of 0-0.11%；
The P of 0-0.11%；
With the compound addition of optional two or more following rare earth elements：
The Y of 0-0.5%；
The La of 0-0.5%；
The Ce of 0-0.5%；
The Pr of 0-0.5%；
The Sn of surplus and inevitable impurity.
In preparation process, Y element is added the low temperature lead-free solder alloy in the form of BiY intermediate alloys, Ag, In, Sb, Ge, P, La, Ce, Pr are prepared into the addition of SnX intermediate alloy forms, and insufficient Sn and Bi are added with pure Sn and pure Bi.
Above-mentioned intermediate alloy prepares ratio and smelting temperature：
Y：Bi-82%Y, 1400 DEG C；
Ag：Sn-3%Ag, 400 DEG C；
In：Sn-52%In, 350 DEG C；
Sb：Sn-10%Sb, 500 DEG C；
Ge：Sn-1%Ge, 400 DEG C；
P：Sn-1%P, 450 DEG C；
La：Sn-90%La, 900 DEG C；
Ce：Sn-1.8%Ce, 450 DEG C；
Pr：Sn-3%Pr, 400 DEG C.
In order to reduce the segregation of Bi elements in solder alloy, low temperature lead-free solder alloy of the invention is added to a certain amount of Sb and the compound addition for combining a variety of rare earth elements can effectively inhibit Bi elements under the effect of " pinning " of Sb and rare earth element Segregation, improve the mechanical performance of solder joint, rare earth element can also improve the surface characteristic of fusion welding, reduce the table of fusion welding Face tension promotes the wetting of solder, improves the welding performance of solder alloy.When In contents are relatively low, In can be solid-solubilized in Sn, The In atoms of solid solution can hinder the movement of dislocation.The present invention adds micro In, can improve the welding performance of solder alloy And effectively control the cost of solder.
Description of the drawings
Fig. 1 is the low temperature lead-free solder alloy SnBi55Ag0.3Sb0.1In2.6DSC curves of embodiment 7；
Fig. 2 be embodiment 7 low temperature lead-free solder alloy SnBi55Ag0.3Sb0.1In2.6 sample tensile tests after obtain Load-displacement curves.
Specific implementation mode
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited In the content.
The alloy formula of specific embodiments of the present invention and comparative example is (being calculated in mass percent) as shown in table 1, wherein right Ratio is the comparison that SnBi58 eutectic solders alloy carries out properties with embodiment.
1 embodiment of table and comparative example
Alloy Bi Ag In Sb Ge P Y La Ce Pr
Range 30-60 0-3.5 0-3.0 0.1-3 0-0.11 0-0.11 0-0.5 0-0.5 0-0.5 0-0.5
Embodiment 1 40 2.5 0.1 0.5 0.08 0.002 0.01 0.01 0 0.1
Embodiment 2 42 1.5 0.3 0.6 0.04 0.01 0 0.02 0.03 0
Embodiment 3 44 0.12 2.0 2.4 0.06 0.02 0.25 0 0 0.01
Embodiment 4 48 3.0 0 1.5 0.11 0.008 0 0.25 0.05 0
Embodiment 5 30 1.0 1.3 2 0.01 0.10 0.03 0 0.25 0
Embodiment 6 50 3.5 0.8 1.0 0.05 0.11 0.5 0.1 0 0.01
Embodiment 7 55 0.3 2.6 0.1 0 0.06 0 0.5 0.02 0
Embodiment 8 32 0 1.0 0.2 0.02 0.006 0 0 0.01 0.5
Embodiment 9 60 2.0 1.5 1.2 0.008 0.01 0.05 0 0.5 0.05
Embodiment 10 35 0.1 3.0 3.0 0.004 0.008 0 0 0.1 0.25
Comparative example 58 0 0 0 0 0 0 0 0 0
In preparation process, Y element is added low temperature lead-free solder alloy in the form of BiY intermediate alloys, Ag, In, Sb, Ge, P, La, Ce, Pr are prepared into the addition of SnX intermediate alloy forms, and insufficient Sn and Bi are added with pure Sn and pure Bi.The centre Alloy prepares ratio and smelting temperature：
Y：Bi-82%Y, 1400 DEG C；
Ag：Sn-3%Ag, 400 DEG C；
In：Sn-52%In, 350 DEG C；
Sb：Sn-10%Sb, 500 DEG C；
Ge：Sn-1%Ge, 400 DEG C；
P：Sn-1%P, 450 DEG C；
La：Sn-90%La, 900 DEG C；
Ce：Sn-1.8%Ce, 450 DEG C；
Pr：Sn-3%Pr, 400 DEG C.
In smelting furnace in fusion process, to prevent the oxidization burning loss of alloy part, covers one layer on the surface of melt and prevent Oxidation solvent.
By 1 alloyage of table, to its alloy test fusing point, tensile strength.Using DSC131evo type differential scanning calorimetries point Analyzer tests fusing point, heating rate 5K/min；Using REGER type mechanics machine tested for tensile strength, tensile speed is 2mm/min；The wetting power of solder is measured using MUST SYSTEM II type Weldability detectors, base material is Fine copper silk, scaling powder be KESTER 985-M, 240 DEG C of experimental temperature, immersion depth 3mm, when immersing speed 10mm/s, immersing Between 5s.
The fusing point of embodiment and comparative example, tensile strength, the results are shown in Table 2 for wetting power：
2 alloy performance test result of table
From table 2 it can be seen that the fusion temperature of 1~10 any low temperature lead-free solder alloy of the embodiment of the present invention is not high In 150 DEG C, or even there is fusion temperature ratio SnBi58 slightly lower, and compared with SnBi58, the tensile strength of alloy, wetting power are all It is greatly improved.
Lead-free solder form of the present invention be powdery, paste, BGA soldered balls, centreless or have core welding wire shape, rodlike, strip, Any one of ingot shape, foil-like etc..The state of product is unlimited, according to demand depending on.

Claims (3)

1. a kind of SnBiAgSbIn low temperature lead-free solder alloys, which is characterized in that the weight percent group of the leadless welding alloy Become：
The Bi of 30-60%；
The Ag of 0-3.5%；
The Sb of 0.1-3%；
The In of 0-3.0%；
The Ge of 0-0.11%；
The P of 0-0.11%；
With the compound addition of optional two or more following rare earth elements：
The Y of 0-0.5%；
The La of 0-0.5%；
The Ce of 0-0.5%；
The Pr of 0-0.5%；
The Sn of surplus and inevitable impurity.
2. a kind of SnBiAgSbIn low temperature lead-free solder alloys as described in claim 1, which is characterized in that the low-temperature lead-free In preparation process, Y element is added solder alloy in the form of BiY intermediate alloys, prepared by Ag, In, Sb, Ge, P, La, Ce, Pr It is added at SnX intermediate alloy forms, insufficient Sn and Bi are added with pure Sn and pure Bi.
3. a kind of SnBiAgSbIn low temperature lead-free solder alloys as claimed in claim 2, which is characterized in that the intermediate alloy Preparation ratio and smelting temperature are respectively：
Y：Bi-82%Y, 1400 DEG C；
Ag：Sn-3%Ag, 400 DEG C；
In：Sn-52%In, 350 DEG C；
Sb：Sn-10%Sb, 500 DEG C；
Ge：Sn-1%Ge, 400 DEG C；
P：Sn-1%P, 450 DEG C；
La：Sn-90%La, 900 DEG C；
Ce：Sn-1.8%Ce, 450 DEG C；
Pr：Sn-3%Pr, 400 DEG C.
CN201810266729.1A 2018-03-28 2018-03-28 A kind of SnBiAgSbIn low temperature lead-free solder alloys Pending CN108526748A (en)

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108994480A (en) * 2018-10-10 2018-12-14 云南锡业锡材有限公司 A kind of SnBiAgCu high-reliability lead-free solder alloy
CN109128569A (en) * 2018-10-08 2019-01-04 深圳市上煌实业有限公司 A kind of middle low-temperature lead-free solder and preparation method thereof
CN111590241A (en) * 2020-06-11 2020-08-28 中山翰华锡业有限公司 Low-temperature environment-friendly multi-element alloy soldering paste and preparation method thereof
CN112372177A (en) * 2020-11-03 2021-02-19 哈尔滨理工大学 High-wettability brazing filler metal and preparation method thereof
CN112372176A (en) * 2020-11-03 2021-02-19 哈尔滨理工大学 Multi-element lead-free solder with high interface reliability and preparation method and application thereof
CN112440030A (en) * 2020-12-04 2021-03-05 太仓巨仁光伏材料有限公司 Lead-free solder for heterojunction low-temperature solder strip and smelting furnace
CN113579557A (en) * 2021-08-12 2021-11-02 北京康普锡威科技有限公司 SnBi material alloy, and preparation method and application thereof
CN114850725A (en) * 2022-05-24 2022-08-05 雅拓莱焊接科技（惠州）有限公司 Ultrathin tin-bismuth system preformed welding ring and preparation process thereof
CN115383349A (en) * 2022-10-09 2022-11-25 云南锡业集团（控股）有限责任公司研发中心 Method for obtaining high-toughness lead-free tin bismuth solder by micro-alloying regulation and control of microstructure
CN115430949A (en) * 2022-10-09 2022-12-06 云南锡业集团（控股）有限责任公司研发中心 Five-membered eutectic high-toughness low-temperature tin-bismuth series solder and preparation method thereof

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Cited By (15)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109128569A (en) * 2018-10-08 2019-01-04 深圳市上煌实业有限公司 A kind of middle low-temperature lead-free solder and preparation method thereof
CN108994480A (en) * 2018-10-10 2018-12-14 云南锡业锡材有限公司 A kind of SnBiAgCu high-reliability lead-free solder alloy
CN111590241A (en) * 2020-06-11 2020-08-28 中山翰华锡业有限公司 Low-temperature environment-friendly multi-element alloy soldering paste and preparation method thereof
CN112372176B (en) * 2020-11-03 2022-10-25 哈尔滨理工大学 Multi-element lead-free solder with high interface reliability and preparation method and application thereof
CN112372177A (en) * 2020-11-03 2021-02-19 哈尔滨理工大学 High-wettability brazing filler metal and preparation method thereof
CN112372176A (en) * 2020-11-03 2021-02-19 哈尔滨理工大学 Multi-element lead-free solder with high interface reliability and preparation method and application thereof
CN112440030A (en) * 2020-12-04 2021-03-05 太仓巨仁光伏材料有限公司 Lead-free solder for heterojunction low-temperature solder strip and smelting furnace
CN112440030B (en) * 2020-12-04 2023-08-22 太仓巨仁光伏材料有限公司 Lead-free solder for heterojunction low-temperature welding strip and smelting furnace
CN113579557A (en) * 2021-08-12 2021-11-02 北京康普锡威科技有限公司 SnBi material alloy, and preparation method and application thereof
CN114850725A (en) * 2022-05-24 2022-08-05 雅拓莱焊接科技（惠州）有限公司 Ultrathin tin-bismuth system preformed welding ring and preparation process thereof
CN114850725B (en) * 2022-05-24 2024-04-26 雅拓莱焊接科技（惠州）有限公司 Ultrathin tin-bismuth system preformed welding ring and preparation process thereof
CN115383349A (en) * 2022-10-09 2022-11-25 云南锡业集团（控股）有限责任公司研发中心 Method for obtaining high-toughness lead-free tin bismuth solder by micro-alloying regulation and control of microstructure
CN115430949A (en) * 2022-10-09 2022-12-06 云南锡业集团（控股）有限责任公司研发中心 Five-membered eutectic high-toughness low-temperature tin-bismuth series solder and preparation method thereof
CN115383349B (en) * 2022-10-09 2023-11-07 云南锡业集团（控股）有限责任公司研发中心 Method for obtaining high-toughness lead-free tin-bismuth solder by microalloying regulation and control microstructure
CN115430949B (en) * 2022-10-09 2024-04-05 云南锡业集团（控股）有限责任公司研发中心 Five-membered eutectic high-toughness low-Wen Xibi-series solder and preparation method thereof

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Application publication date: 20180914