WO2016185674A1 - Alliage de soudage et structure d'emballage l'utilisant - Google Patents

Alliage de soudage et structure d'emballage l'utilisant Download PDF

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Publication number
WO2016185674A1
WO2016185674A1 PCT/JP2016/002195 JP2016002195W WO2016185674A1 WO 2016185674 A1 WO2016185674 A1 WO 2016185674A1 JP 2016002195 W JP2016002195 W JP 2016002195W WO 2016185674 A1 WO2016185674 A1 WO 2016185674A1
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WO
WIPO (PCT)
Prior art keywords
mass
content
solder alloy
less
solder
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PCT/JP2016/002195
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English (en)
Japanese (ja)
Inventor
清裕 日根
彰男 古澤
秀敏 北浦
Original Assignee
パナソニックＩｐマネジメント株式会社
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Priority claimed from JP2016021113A external-priority patent/JP6135885B2/ja
Application filed by パナソニックＩｐマネジメント株式会社 filed Critical パナソニックＩｐマネジメント株式会社
Priority to US15/511,231 priority Critical patent/US20170282305A1/en
Priority to CN201680002769.4A priority patent/CN106715040B/zh
Priority to EP16796071.5A priority patent/EP3299113B1/fr
Publication of WO2016185674A1 publication Critical patent/WO2016185674A1/fr

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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
    • 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
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
    • H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
    • H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering

Definitions

  • the present invention mainly relates to a solder alloy used for soldering an electronic component to an electronic circuit board and a mounting structure using the same.
  • the electronic control of automobiles is advancing from the viewpoint of safety and comfort of automobiles and environmental impact.
  • Electronic devices mounted on automobiles are required to have high reliability with respect to loads such as heat, vibration and shock in automobiles.
  • solder alloys used for mounting circuit boards of automotive electronic devices are required to have high reliability and ductility in a high-temperature environment. Since a solder alloy has a lower melting point than a printed circuit board or an electronic component as a member to be joined, the mechanical properties thereof are remarkably deteriorated in a high temperature environment. Also, since the solder alloy has a low elastic modulus, strain due to differences in linear expansion coefficient between components due to temperature changes in the automobile environment, loads due to vibration and impact are concentrated on the solder joints soldered with the solder alloy. Will be added. In particular, when a strain due to a difference in linear expansion coefficient between the constituent members is repeatedly applied, a crack may be generated in the solder joint portion, which may ultimately cause a disconnection. For this reason, solder alloys used in electronic equipment for automobiles are required to have heat-resistant fatigue characteristics against repeated strain generated by temperature changes, and require high strength and ductility in a high-temperature environment.
  • solder alloy having excellent heat fatigue resistance that can be used in conventional electronic equipment for automobiles
  • Ag is 1.0 to 4.0% by mass
  • In is 4.0 to 6.0% by mass
  • Bi is 0.1 to 1%.
  • Solder alloy consisting of 0.0 mass%, the total of one or more elements selected from the group consisting of Cu, Ni, Co, Fe and Sb being 1 mass% or less (excluding 0 mass%), and the balance of Sn
  • the electrode part containing copper of the electronic component is joined to the electrode land containing copper of the substrate by the joint part formed using such a solder alloy.
  • Patent Document 1 describes that such a configuration can prevent the generation and extension of cracks in a temperature cycle test between ⁇ 40 ° C. and 150 ° C.
  • solder alloy having excellent heat fatigue resistance
  • Sn—Ag—In containing 0.5 to 5% by mass of Ag, 0.5 to 20% by mass of In, and 0.1 to 3% by mass of Bi, with the balance being Sn.
  • Sn-based solder alloy characterized by containing 3% by mass or less of at least one selected from Sb, Zn, Ni, Ga, Ge and Cu (patent) Reference 2).
  • Patent Document 2 describes that according to such a solder alloy, deformation of the solder alloy can be prevented in a temperature (cooling) cycle test between ⁇ 40 ° C. and 125 ° C.
  • An object of the present invention is to provide a solder alloy capable of obtaining sufficient reliability to withstand use at 175 ° C.
  • the present inventors have added both Sb and Cu to the Sn—Ag—Bi—In based solder alloy, and have strictly controlled the In content with respect to the Sb content.
  • the inventors independently found that high reliability was obtained even at a high temperature that was not assumed, specifically, 175 ° C., and as a result of further intensive studies, the present invention was completed.
  • a predetermined content is selected for each element except Sn, and in particular, the Sb content is 0.5 mass% or more. , 1.25 mass% or less, the In content is selected in relation to the Sb content so as to satisfy the above formula (I) or (II), and the Cu content is 0.5 mass% or more, 1.2
  • the mass% or less By setting the mass% or less, a solder alloy capable of obtaining sufficient reliability to withstand use at 175 ° C. is realized.
  • solder alloys are not considered for use at such high temperatures. More specifically, the solder alloy described in Patent Document 1 is only supposed to be used up to 150 ° C., and the solder alloy described in Patent Document 2 is only supposed to be used up to 125 ° C. In such a conventional solder alloy, sufficient reliability cannot always be obtained at a temperature of 175 ° C.
  • the solder alloy of this embodiment is 0.5% by mass or more and 1.25% by mass or less of Sb;
  • solder alloy (sample) having a predetermined composition was prepared and evaluated.
  • the sample evaluated in this embodiment was manufactured by the following method.
  • Sn, Ag, Bi, In, Cu, and Sb contained in the solder alloy Ag is 3.5% by mass
  • Bi is 0.5% by mass
  • In is 6.0% by mass
  • Cu is 0.8% by mass.
  • Sb was 0.5 mass%
  • the balance was Sn, and weighed so that the total amount was 100 g.
  • the weighed Sn was put into a ceramic crucible, adjusted to a temperature of 500 ° C. and a nitrogen atmosphere, and placed in an electric jacket heater.
  • a Ag was added and further stirred for 3 minutes.
  • the crucible was taken out from the electric jacket heater and immersed in a container filled with water at 25 ° C. to cool, thereby producing a solder alloy.
  • solder alloy A the alloy composition is represented by Sn-3.5Ag-0.5Bi-6.0In-0.8Cu-0.5Sb.
  • the transformation temperature which is the temperature at which the ⁇ -Sn and ⁇ phase transformations proceed rapidly
  • 10 mg of the solder alloy produced above was taken out and subjected to differential scanning calorimetry (DSC).
  • the temperature increase rate at the time of measurement was 10 ° C./min, and the temperature was measured in the range from 25 ° C. to 250 ° C. The results are shown in FIG.
  • the transformation temperature was determined from the inflection point of a small peak (part A) generated from the low temperature (solid) side to the peak showing the melting point, and the transformation temperature of solder alloy A was 175 ° C.
  • the transformation temperature of Conventional Example 1 was 165 ° C.
  • a tensile test was performed in a 175 ° C. environment using a tensile test piece.
  • the tensile test piece was produced by putting the solder alloy produced above into a crucible, heating it to 250 ° C. with an electric jacket heater, melting it, and pouring it into a graphite mold processed into the shape of a tensile test piece.
  • the tensile test piece had a round bar shape with a constricted portion having a diameter of 3 mm and a length of 15 mm.
  • the result of the tensile test in a 175 degreeC environment is shown in FIG.
  • the horizontal axis indicates the stroke strain of the tensile tester, and the vertical axis indicates the tensile stress.
  • the maximum values are measured as elongation at break and tensile strength, respectively. From FIG. 2, it can be seen that the solder alloy A has a tensile strength equal to or higher than that of the conventional example 1 even in the 175 ° C. environment. It can be seen that the breaking elongation of the solder alloy A is improved by several tens of percent compared to the conventional example 1, and the ductility at high temperature is improved.
  • the solder alloy A does not self-deform even when repeatedly exposed to a high temperature of 175 ° C., and is excellent in the mechanical properties of the solder alloy such as strength and ductility at a high temperature. It becomes possible to improve the heat fatigue resistance.
  • an alloy ( ⁇ -Sn phase) in which In is dissolved in Sn is formed in a low In content region where the In content is about 15% by mass or less.
  • Solid solution is a phenomenon in which a part of the crystal lattice of the base metal is replaced with a solid solution element at the atomic level.
  • the effect of solid solution elements is to suppress the movement of crystal defects such as transitions when stress is applied by generating strain in the crystal lattice of the parent element due to the difference in atomic diameter between the parent metal element and the solid solution element. Can do.
  • the strength of the metal can be improved, while the ductility during stress loading is reduced.
  • the strength improvement of the solder alloy by solid solution increases as the solid solution element content increases.
  • Sb increases the transformation temperature in the Sn—In alloy, such as the transformation temperature of 165 ° C. in Conventional Example 1 and the transformation temperature of solder alloy A of 175 ° C.
  • the mechanical properties of the solder alloy improve the strength of the solder alloy by dissolving Sb in the same manner as the In solid solution.
  • the present inventors have newly found that the solid solution of Sb further promotes the improvement in ductility at a high temperature seen at a specific In content.
  • solder alloys having the metal compositions shown in Table 1 were prepared and evaluated.
  • the method for producing the solder alloy is the same as described above.
  • the transformation temperature of the produced solder alloy is evaluated at 175 ° C. and the mechanical properties (tensile strength and elongation) are evaluated and the results of comprehensive judgment are also shown. Judgment is made when the transformation temperature is 175 ° C. or higher and the mechanical properties are improved as compared with the case of the conventional example 1, especially when the elongation at 175 ° C. is improved by 30% or more. “ ⁇ ” and the effect of the present invention is expressed. The case where the transformation temperature is less than 175 ° C. and the mechanical property value is less than the value in Conventional Example 1 is determined as “x”.
  • Example 2-2 where the Sb content is 0.5 mass%, is compared with Conventional Example 1, it can be seen that the transformation temperature increases due to the Sb content.
  • the In content increases, the transformation temperature decreases, and in Comparative Examples 2-2 and 2-3 where the In content is 6.5% by mass and 7.5% by mass, respectively, the mechanical properties at high temperatures are good. However, since the transformation temperature is less than 175 ° C., the determination is “x”.
  • Comparative Example 2-4 having a large In content of 7.5% by mass, both the transformation temperature and the mechanical properties at 175 ° C. are not sufficient, and the determination is “x”.
  • Comparative Example 2-1 with an In content of 5.0% by mass has a small effect due to the solid solution of In and is 175 compared with Conventional Example 1. The tensile strength at 0 ° C. is small, and the judgment is “x”.
  • solder alloy was prepared and evaluated in the case where the upper limit of the Sb content was 1.25% by mass.
  • the method for producing and evaluating the solder alloy is the same as described above.
  • Example 3-2 when Example 3-2 is compared with Conventional Example 1, it can be seen that the transformation temperature increases due to the Sb content. As in the case of the results shown in Table 2, the transformation temperature decreases as the In content increases, and in Comparative Examples 3-2 and 3-3 where the In content is 7.0% by mass or more, the transformation temperature is 175. Since it is less than ° C., the determination is “x”. Further, focusing on the mechanical properties of tensile strength and elongation, in the case of Comparative Example 3-1, in which the In content is 5.0% by mass, the In-solution effect is not sufficiently exhibited, and the tensile strength in an environment of 175 ° C. Since the intensity is smaller than Conventional Example 1, the determination is “x”.
  • FIG. 3 is a diagram showing the relationship between the In content and the transformation temperature when the Sb content shown in Table 2 is 0.50 mass%.
  • the horizontal axis indicates the In content (% by mass), and the vertical axis indicates the transformation temperature (° C.).
  • a material obtained by subjecting the base material Cu or Ni to various plating or preflux treatment is mainly used.
  • the base material of the member to be joined is Ni
  • the base material of the member to be joined is Ni
  • various electronic components are mounted on a single circuit board. Therefore, when an electronic component of Cu or Ni is mounted on the base material, the In content ratio is determined in advance. Adjustment is difficult.
  • Cu in the solder alloy forms a Cu 6 Sn 5 based alloy layer in the interface reaction layer at the time of soldering, and can prevent the incorporation of In.
  • the selectivity of the joining member is improved.
  • the melting point increases, so that it is desirable that the content be 1.2% by mass or less.
  • the Cu content is 0.5 mass% or more and 1.2 mass% or less.
  • Bi content is contained for the purpose of improving the mechanical strength of the solder material and lowering the melting point.
  • the Bi content is relatively small at 3.0% by mass or less, it dissolves in ⁇ -Sn, and when the Bi content increases, Bi or Bi compounds are present in a precipitated form.
  • the Bi content is preferably 0.1% by mass or more.
  • the upper limit of the Bi content is desirably set to 3.0% by mass or less so that precipitation of Bi or Bi compound does not occur.
  • the Bi content is 0.1 mass% or more and 3.0 mass% or less.
  • Ag content is contained for the purpose of improving wettability during soldering and lowering the melting point, and is present in the form of Ag 3 Sn compound and Ag 2 In in the solder alloy.
  • the reflow peak temperature of the liquidus temperature of the solder alloy + 10 ° C. or more is preferably 240 ° C. or lower.
  • the liquidus temperature of the solder alloy is preferably set to 230 ° C. or less.
  • the Ag content is set to 1.0% by mass or more and 4.0% by mass or less.
  • examples, comparative examples, and conventional solder alloys having the metal compositions shown in Table 5 were prepared, and the heat fatigue resistance was evaluated.
  • the method for producing the solder alloy is the same as described above.
  • the evaluation method of heat fatigue resistance is as follows.
  • solder alloy was processed into solder powder having a particle size of several tens of ⁇ m, the solder powder and the flux were weighed so as to have a weight ratio of 90:10, and these were kneaded to produce a solder paste. .
  • This solder paste was printed on the circuit board electrode on the circuit board using a metal mask having a thickness of 150 ⁇ m.
  • a chip resistor was mounted on the printed solder paste, and reflow heating was performed at a maximum temperature of 240 ° C. to produce a mounting structure.
  • the base material of the circuit board electrode of the used circuit board was Cu and Ni.
  • the mounting structure thus fabricated was subjected to a temperature cycle test of ⁇ 40 ° C./175° C., and the deformation of the solder joint after 2000 cycles was visually observed.
  • the electrical connection is evaluated, and when there is a change in the resistance value of 10% or more from the initial value, the electrical failure is “present”, and there is no change or 10% Those that were less than were judged as electrical failure “none”. Note that “ ⁇ ” in the electrical failure column of Table 5 indicates that no evaluation was performed.
  • Comparative Example 5-6 with a Cu content of 1.5% by mass, Comparative Example 5-7 without Bi, Comparative Example 5-8 with a Bi content of 3.5% by mass, Comparative Example without Ag In 5-9, an electrical failure occurred.
  • solder alloy containing 1.0 mass% or more and 4.0 mass% or less of Ag and the balance being Sn.
  • a solder alloy can be composed of an alloy structure including at least a ⁇ phase and a ⁇ -Sn phase in which Sb is dissolved at 150 ° C. or higher, and forms a joint having excellent heat fatigue resistance even in an environment of 175 ° C. It becomes possible.
  • the solder alloy is 0.5% by mass or more and 1.0% by mass or less of Sb;
  • Such a solder alloy can be composed of an alloy structure including at least a ⁇ phase and a ⁇ -Sn phase in which Sb is dissolved at 150 ° C. or higher, and has a solder joint portion having further excellent heat fatigue resistance even in an environment of 175 ° C. It becomes possible to form.
  • the solder alloy is 0.5% by mass or more and 1.0% by mass or less of Sb;
  • Such a solder alloy can be composed of an alloy structure including a ⁇ phase and a ⁇ -Sn phase in which at least Sb is dissolved at 150 ° C. or higher, and has a particularly excellent solder joint property even in an environment of 175 ° C. It becomes possible to form.
  • the mounting structure of the present invention is characterized in that an electrode part of an electronic component and an electrode part of a circuit board are joined by the solder alloy described above. According to this, even in an environment of 175 ° C., it is possible to provide a mounting structure having a bonding superior in thermal fatigue resistance.
  • the electrode part of the electronic component and the electrode part of the circuit board may be made of any appropriate conductive material, and these may contain Cu and / or Ni as described above as the members to be joined. Good.
  • the solder alloy can have any form, alone (eg, in the form of powder, yarn solder, melt, preform solder, etc.) or together with flux (eg, solder paste or solder containing solder) Can be used for soldering. The soldering conditions can be appropriately selected.
  • the solder alloy may have an Sb content of 0.5% by mass or more and 1.0% by mass or less, and an In content satisfying the above formula (I).
  • the In content may further satisfy that it is 6.1% by mass or less.
  • the solder alloy of the present invention preferably has an alloy structure including a ⁇ phase and a ⁇ -Sn phase in which at least Sb is dissolved at 150 ° C. or higher.
  • a mounting structure in which an electronic component is mounted on a circuit board, and the electrode portion of the electronic component and the electrode portion of the circuit board are joined by the solder alloy of the present invention.
  • the “solder alloy” may contain unavoidably mixed trace metals as long as the metal composition is substantially composed of the enumerated metals.
  • the solder alloy can have any form and can be used for soldering, for example, alone or together with other components other than metal (eg, flux, etc.).
  • solder alloy and mounting structure of the present invention can realize a solder joint having excellent mechanical characteristics even in a high temperature environment of 175 ° C. It is useful for use in a mounting structure of an automobile electrical component that is required to ensure conduction.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacturing & Machinery (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Electric Connection Of Electric Components To Printed Circuits (AREA)

Abstract

L'invention concerne un alliage de soudage qui contient de 0,5 % en masse à 1,25 % en masse (inclus) de Sb, In dans une quantité satisfaisant 5,5 ≤ [In] ≤ 5,50 + 1,06 [Sb] dans les cas où 0,5 ≤ [Sb] ≤ 1,0, tout en satisfaisant 5,5 ≤ [In] ≤ 6,35 + 0,212 [Sb] dans les cas où 1,0 < [Sb] ≤ 1,25 (dans les formules, [Sb] représente la teneur en Sb (% en masse) et [In] représente la teneur en In (% en masse)), de 0,5 % en masse à 1,2 % en masse (inclus) de Cu, de 0,1 % en masse à 3,0 % en masse (inclus) de Bi, et de 1,0 % en masse à 4,0 % en masse (inclus) de Ag, le reste étant constitué de Sn.
PCT/JP2016/002195 2015-05-19 2016-04-26 Alliage de soudage et structure d'emballage l'utilisant WO2016185674A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
US15/511,231 US20170282305A1 (en) 2015-05-19 2016-04-26 Solder alloy and package structure using same
CN201680002769.4A CN106715040B (zh) 2015-05-19 2016-04-26 焊料合金以及使用其的安装结构体
EP16796071.5A EP3299113B1 (fr) 2015-05-19 2016-04-26 Alliage de soudage et structure d'emballage l'utilisant

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
JP2015102180 2015-05-19
JP2015-102180 2015-05-19
JP2016021113A JP6135885B2 (ja) 2015-05-19 2016-02-05 はんだ合金およびそれを用いた実装構造体
JP2016-021113 2016-09-30

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018186218A1 (fr) * 2017-04-07 2018-10-11 株式会社ケーヒン Matériau de brasure
EP3593937A4 (fr) * 2017-03-10 2020-08-05 Tamura Corporation Alliage de soudage sans plomb, pâte à souder, et carte de circuit électronique

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1346728A (zh) * 2001-09-19 2002-05-01 大连理工大学 含稀土多合金组元无铅钎料合金
WO2002040213A1 (fr) * 2000-11-16 2002-05-23 Singapore Asahi Chemical And Solder Industries Pte. Ltd. Brasures sans plomb
JP2013252548A (ja) * 2012-06-08 2013-12-19 Nihon Almit Co Ltd 微細部品接合用のソルダペースト
JP5654716B1 (ja) * 2014-06-24 2015-01-14 ハリマ化成株式会社 はんだ合金、ソルダペーストおよび電子回路基板
JP2015020182A (ja) * 2013-07-17 2015-02-02 ハリマ化成株式会社 はんだ組成物、ソルダペーストおよび電子回路基板

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2002040213A1 (fr) * 2000-11-16 2002-05-23 Singapore Asahi Chemical And Solder Industries Pte. Ltd. Brasures sans plomb
CN1346728A (zh) * 2001-09-19 2002-05-01 大连理工大学 含稀土多合金组元无铅钎料合金
JP2013252548A (ja) * 2012-06-08 2013-12-19 Nihon Almit Co Ltd 微細部品接合用のソルダペースト
JP2015020182A (ja) * 2013-07-17 2015-02-02 ハリマ化成株式会社 はんだ組成物、ソルダペーストおよび電子回路基板
JP5654716B1 (ja) * 2014-06-24 2015-01-14 ハリマ化成株式会社 はんだ合金、ソルダペーストおよび電子回路基板

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3593937A4 (fr) * 2017-03-10 2020-08-05 Tamura Corporation Alliage de soudage sans plomb, pâte à souder, et carte de circuit électronique
WO2018186218A1 (fr) * 2017-04-07 2018-10-11 株式会社ケーヒン Matériau de brasure
JP2018176191A (ja) * 2017-04-07 2018-11-15 株式会社ケーヒン はんだ材料
EP3608050A4 (fr) * 2017-04-07 2020-08-05 Keihin Corporation Matériau de brasure

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