WO2012133598A1 - 鉛フリーはんだボール - Google Patents

鉛フリーはんだボール Download PDF

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Publication number
WO2012133598A1
WO2012133598A1 PCT/JP2012/058271 JP2012058271W WO2012133598A1 WO 2012133598 A1 WO2012133598 A1 WO 2012133598A1 JP 2012058271 W JP2012058271 W JP 2012058271W WO 2012133598 A1 WO2012133598 A1 WO 2012133598A1
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WO
WIPO (PCT)
Prior art keywords
solder
mass
electrode
solder ball
lead
Prior art date
Application number
PCT/JP2012/058271
Other languages
English (en)
French (fr)
Inventor
大西　司
芳恵 山中
賢 立花
Original Assignee
千住金属工業株式会社
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
Application filed by 千住金属工業株式会社 filed Critical 千住金属工業株式会社
Priority to SG2013068416A priority Critical patent/SG193412A1/en
Priority to JP2012551410A priority patent/JP5365749B2/ja
Priority to US14/005,948 priority patent/US9527167B2/en
Priority to EP12764138.9A priority patent/EP2692478B1/en
Priority to KR1020167022883A priority patent/KR20160104086A/ko
Priority to KR1020137027902A priority patent/KR20140025406A/ko
Priority to CN201280024585.XA priority patent/CN103547408B/zh
Publication of WO2012133598A1 publication Critical patent/WO2012133598A1/ja
Priority to TW102109029A priority patent/TWI540015B/zh
Priority to US15/196,227 priority patent/US9700963B2/en

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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
    • B23K35/02—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
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • 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
    • B23K1/00—Soldering, e.g. brazing, or unsoldering
    • B23K1/0008—Soldering, e.g. brazing, or unsoldering specially adapted for particular articles or work
    • B23K1/0016—Brazing of electronic components
    • 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
    • B23K35/02—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
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B23K35/025—Pastes, creams, slurries
    • 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
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    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/01—Layered products comprising a layer of metal all layers being exclusively metallic
    • B32B15/018—Layered products comprising a layer of metal all layers being exclusively metallic one layer being formed of a noble metal or a noble metal alloy
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
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    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/10—Details of components or other objects attached to or integrated in a printed circuit board
    • H05K2201/10613—Details of electrical connections of non-printed components, e.g. special leads
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    • H05K2201/10734—Ball grid array [BGA]; Bump grid array

Definitions

  • the present invention relates to a lead-free solder ball used for an electrode of an electronic component such as a semiconductor.
  • the present invention relates to a lead-free solder ball that can be used together with a Ni electrode portion such as Au plating and a Cu electrode portion in which a water-soluble preflux is applied to Cu and has a low failure mode when an electronic component on which the electrode is mounted falls. .
  • BGA Bit Grid Array
  • CSP Chip Size Package
  • MCM Multi Chip Module
  • solder bump formation When mounting a BGA on a printed circuit board, supplying solder to each electrode and soldering is not only troublesome, but it is also impossible to supply solder from the outside to the electrode in the middle of the board. Therefore, in order to mount the BGA on a printed circuit board, a method of placing solder on the BGA electrode in advance has been performed. This is called solder bump formation.
  • solder balls, solder paste, etc. are used to form solder bumps on the BGA.
  • an adhesive flux is applied to the BGA electrode, and the solder balls are placed on the electrode to which the flux has been applied. Thereafter, the BGA substrate is heated by a heating device such as a reflow furnace to melt the solder balls, thereby forming solder bumps on the electrodes.
  • a semiconductor substrate such as a BGA substrate or a CSP substrate is generically called a module substrate.
  • solder bumps are formed on the wafer lands with solder paste, place a metal mask with holes of the same size as the lands on the wafer land and match the solder paste on the metal mask with a squeegee. Stir and apply solder paste to the land of the wafer. Thereafter, the wafer is heated in a reflow furnace to melt the solder paste, thereby forming solder bumps.
  • Sn—Pb alloy solder balls are used for forming solder bumps.
  • This Sn-Pb solder ball not only has excellent solderability to the BGA electrode, but the eutectic composition of Sn-Pb in particular has a melting point that does not affect the BGA element or the substrate during the soldering. Moreover, since it has a soft Pb, it absorbs the impact even if the used electronic component or electronic device falls, thus greatly contributing to the life of the electronic component or electronic device.
  • the use of Pb has been regulated on a global scale, and of course, the eutectic composition of Sn—Pb that has been used in conventional soldering has also been regulated.
  • Sn—Ag—Cu solder alloys such as Sn-3.0Ag-0.5Cu and Sn-4.0Ag-0.5Cu have been used as the composition of lead-free solder balls for BGA. Although these lead-free solder alloys are excellent in temperature cycle characteristics, portable electronic devices using solder balls with these solder alloy compositions are prone to interface debonding from the solder ball connection interface when dropped. It has been thought to be inferior in drop impact.
  • solder alloy composition for lead-free solder balls that prevents the drop impact of portable electronic devices is (%) (%) 0.8% to 2.0%, (2) Cu: 0.05% to 0.3%, and (3)
  • Lead-free solder alloy consisting of one or more selected from 0.01% or more, less than 0.1%, Ni: 0.01-0.04%, Co: 0.01-0.05%, and Pt: 0.01-0.1%, the balance Sn WO 2006 / 129713A, Patent Document 1), Ag: 1.0 to 2.0% by mass, Cu: 0.3 to 1.5% by mass, comprising the remainder Sn and inevitable impurities, lead-free solder alloy.
  • Sb 0.005 to 1.5 mass%
  • Zn 0.05 to 1.5 mass%
  • Ni 0.05 to 1.5 mass%
  • Fe 0.005 to 0.5 mass%
  • Patent Document 2 0% by mass% Lead-free solder comprising 1 to 1.5% Ag, 0.5 to 0.75% Cu, Ni satisfying the relationship of 12.5 ⁇ Cu / Ni ⁇ 100, the remainder Sn and inevitable impurities Alloy (WO2007 / 081006A, Patent Document 3), Ag: 1.0 to 2.0 mass%, Cu: 0.3 to 1.0 mass%, Ni: 0.005 to 0.10 mass% , The remainder Sn and inevitable impurities lead-free solder alloy (WO2007 / 1025 8A publication, there is a patent document 4). Further, as an unfused solution that occurs at the time of joining a module such as a BGA board and a printed board, a method of applying a flux to the electrode part of the module board (WO 2006-134891A, Patent Document 5) is disclosed.
  • Patent Documents 1 to 4 in order to improve the drop impact resistance of Sn—Ag—Cu based solder balls, the content of Ag is reduced to lower the hardness of the solder and to improve the impact absorption amount.
  • the Cu content is reduced and the intermetallic compound layer such as Cu6Sn5 generated on the joint surface between the land and the solder is thinned to prevent peeling at the joint interface, and the content of Ag and Cu is reduced.
  • the strength of the solder itself generated is improved by adding iron group elements such as Ni, Fe and Co.
  • the following may be considered as the cause of unfusion.
  • the solder balls and the solder paste are separated.
  • the surface of the solder ball is oxidized by a high temperature. If the flux that exudes from the solder paste covers the surface of the solder ball and this flux loses its activity, the warp will return during the cooling process, and even if the solder paste comes into contact with the solder ball, it will oxidize the surface of the solder ball. Since the membrane cannot be removed, it becomes unfused. As a countermeasure against this, the method of Patent Document 5 is effective.
  • Drop impact resistance is required for solder balls used for BGA and CSP.
  • One effective means against drop impact resistance is modification of the interfacial compound, and as disclosed in Patent Documents 1 to 4, Ni addition is a means for improvement.
  • Ni is also an element that forms a compound, so the amount that can be added is limited.
  • Cu or Ni addition is suppressed in consideration of unfusion, the drop impact resistance characteristics are lost, so that it is not suitable for solder balls that are frequently used in portable devices such as BGA and CSP.
  • the problem to be solved by the present invention is a solder alloy for a solder ball which does not cause unfusion even if it is a solder ball of Sn—Ag—Cu—Ni composition with improved solder strength such as drop impact resistance.
  • the failure mode when the electronic component falls is low by suppressing the interfacial peeling at the solder ball joint interface and suppressing the non-fusion occurring between the solder ball and the solder paste, Even when the printed circuit board to be bonded is a Cu electrode, the BGA and the electroless Ni / Au electrode and the electroless Ni / Pd / Au electrode in which the Ni base is subjected to Au plating or Au / Pd plating surface treatment are effective. It is to obtain a solder ball for CSP. *
  • the present inventors have found that the solder ball solder alloy having a low drop impact resistance and a low unfusion occurrence rate has few problems due to the drop of the portable electronic device, and that of an iron genus such as Ni contained in the drop impact resistant solder alloy. If the metal is deposited on the surface of the solder ball, the unfusion occurrence rate is high, many defects due to dropping of portable electronic devices occur, and by specifying the amount of Ni added in the solder alloy, unfusion, As a result, it has been found that problems caused by dropping of the portable electronic device are reduced, and the present invention has been completed.
  • the Sn—Ag—Cu solder as the base is 0.5 to 1.1 mass% of Ag, 0.7 to 0.8 mass% of Cu, and the remaining Sn.
  • the solder ball of the present invention suppresses the formation of an intermetallic compound of Cu6Sn5 at the Cu electrode interface by reducing the Cu content in the Sn—Ag—Cu ternary composition solder alloy.
  • the Cu content in the solder of Sn—Ag—Cu ternary composition is about 0.75 mass%, which is the eutectic point. The formation of an intermetallic compound of Cu6Sn5 at the Cu electrode interface is suppressed without reducing the content of.
  • the content of Cu in the Sn—Ag—Cu ternary composition solder alloy of the present invention is limited to around 0.75 mass%, which is the eutectic point, so that Cu is saturated Sn—Ag—Cu 3.
  • Cu is prevented from diffusing from the Cu electrode.
  • solder ball of the present invention is that the Cu content in the Sn—Ag—Cu ternary composition solder alloy is set to be around 0.75 mass%, which is the eutectic point, so that Cu from the Cu electrode can be obtained.
  • the same effect can be obtained for Ni which is in a solid solution relationship with Cu, so that the Ni electrode also has a function of suppressing Ni diffusion.
  • the effect of suppressing the diffusion of Ni and Cu from the component electrode and the substrate electrode is enhanced, and the Ni interface is also resistant to the Ni electrode by forming a bonding interface with a fine intermetallic compound. Drop impact resistance is improved.
  • the amount of Ni added to the solder composition for solder balls of 0.5 to 1.1 mass%, Cu of 0.7 to 0.8 mass%, and remaining Sn is 0.05 to 0.08. % By mass.
  • Ni is concentrated on the Sn—Ag—Cu solder ball surface.
  • the content of Cu in the Sn—Ag—Cu ternary composition solder alloy is around 0.75 mass%, which is the eutectic point
  • Ni the content of Cu in the solder is not reduced.
  • formation of an intermetallic compound of Cu6Sn5 is suppressed at the Cu electrode interface.
  • SnCu compound: Cu6Sn5 in the solder is refined and particles of intermetallic compound formed at the interface between the component and the substrate electrode As a result, the joint interface is formed to be finer and less likely to break.
  • both the Cu electrode and the Ni electrode have a drop impact resistance, and the failure mode is low when an electronic component on which the electrode is mounted is dropped due to the effect of suppressing unfusion.
  • the ability to use solder balls is advantageous in that it can flexibly cope with frequent electrode design changes.
  • Cu electrodes coated with water-soluble preflux (OSP, also called Organic Solder Preservatives) on Cu lands also include electrodes that use Ni as the base such as Au plating or Pd / Au plating. Also in the Ni electrode, it is possible to obtain a bond between the printed circuit board and the BGA or CSP electrode having a low failure mode when the electronic component is dropped.
  • OSP water-soluble preflux
  • solder ball having the drop impact resistance for both the Cu electrode and the Ni electrode of the present invention is used for forming a bump on a PKG component such as a BGA or a CSP cage having a bottom electrode.
  • the alloy for solder balls of the present invention should have an Ag content of 0.5 to 1.1% by mass, more preferably 0.9 to 1.1% by mass.
  • the Sn—Ag—Cu—Ni based solder alloy of the solder ball of the present invention is separated from the eutectic point of Sn—Ag—Cu when the Cu content is less than 0.7% by mass. If Cu is diffused from the Cu electrode into the solder, the intermetallic compound layer of Cu6Sn5 becomes thick at the Cu electrode interface, and the drop impact resistance deteriorates. When the Cu content of the Sn—Ag—Cu—Ni solder alloy exceeds 0.8 mass%, the Sn—Ag—Cu eutectic point is separated, so that the reaction layer of the solder alloy and the Cu electrode contains Cu6Sn5.
  • the intermetallic compound of Cu6Sn5 formed at the interface between the Cu electrode and the solder joint becomes thick. Therefore, the content of Cu contained in the Sn—Ag—Cu—Ni solder alloy of the solder ball of the present invention must be 0.7 to 0.8 mass%.
  • the Ni content in the Sn—Ag—Cu—Ni solder alloy of the solder ball of the present invention when the Ni content is less than 0.05% by mass, the effect of adding Ni does not appear and Ni can easily diffuse from the Ni electrode. Therefore, an intermetallic compound is easily formed at the interface, so the Ni content in the Sn—Ag—Cu—Ni solder alloy must be 0.05% by mass or more. Similarly, if the Ni content exceeds 0.08% by mass, the Ni concentration in the intermetallic compound formed at the bonding interface will increase and the bonding strength will decrease. When loaded, interfacial delamination tends to occur. On the other hand, when the Ni content exceeds 0.08% by mass, the unfusion occurrence rate increases. Therefore, the Ni content in the Sn—Ag—Cu—Ni solder alloy of the solder ball of the present invention needs to be 0.05 to 0.08 mass%.
  • One or more elements selected from Fe, Co, and Pt may be added to the Sn—Ag—Cu—Ni solder alloy of the solder ball of the present invention in a total amount of 0.003 to 0.1 mass%. .
  • the addition of Fe, Co, and Pt elements to the alloy for solder balls has the effect of improving the drop because the intermetallic compound layer formed at the bonding interface is refined and the thickness is suppressed. If the element selected from Fe, Co, and Pt is less than 0.003% by mass, the above effect is very difficult to obtain, and if added over 0.1% by mass, the solder bump hardness increases and interfacial delamination occurs due to impact. The evil of doing appears.
  • solder balls of the present invention are used for electrodes.
  • the diameter of the solder ball is 0.1 mm or more, preferably 0.3 mm or more, more preferably 0.5 mm or more.
  • solder balls of 0.1 mm or less are generally used for flip chip bonding, and solder balls for electrodes intended for CSPs and BGAs incorporating flip chips, such as the solder balls of the present invention, are 0.1 mm. The above is the mainstream.
  • a solder alloy having the composition shown in the following table was made, and a solder ball having a diameter of 0.3 mm was produced by the air ball-making method. Using this solder ball, a CSP substrate was prepared by the following procedure.
  • solder balls of various compositions are electrolytic Ni / Au of size 12 ⁇ 12 mm, electrolytic Ni / Pd / Au, Cu module board for CSP having OSP-treated electrodes, and flux made by Senju Metal Industry Co., Ltd. Reflow soldering was performed using WF-6400, and a CSP using the solder of each composition as an electrode was produced.
  • a drop impact test was conducted under the following conditions.
  • the CSP-mounted glass epoxy substrate prepared in 2 was used, and both ends of the substrate were fixed using a dedicated jig at a position 10 mm above the pedestal.
  • a dedicated jig at a position 10 mm above the pedestal.
  • an impact with an acceleration of 1500 G was repeatedly applied, and the time when the initial resistance value increased 1.5 times was regarded as a break, and the number of drops was recorded.
  • solder ball using the Sn—Ag—Cu—Ni-based solder alloy containing a large amount of Ni as in Patent Document 2 does not have a drop impact resistance even when soldered to the Ni electrode.
  • the produced solder balls of each composition were treated at a temperature of 110 ° C., a humidity of 85%, and a time of 24 hours.
  • Comparative Examples 7, 9, 10, 11, and 13 are solder ball alloy compositions containing a Cu content exceeding 0.8% by mass or a Ni content exceeding 0.07% by mass, unfusion occurs. The rate exceeds 8% and the suppression effect is not obtained.
  • the unfusion occurrence rate of the solder composition Sn-1.5Ag0.5Cu-0.5Ni described in Patent Document 2 in Comparative Example 13 is remarkably increased. This is because the Ni content in the solder is too large, the amount of the generated compound is excessive, and the fusion with the paste is hindered. As a result, the occurrence rate of unfusion is increased.
  • Comparative Examples 1 and 2 since the amount of Ag is small, a significant decrease in wetting spread is observed. Actually, compared with Example 1, the wet spread area is reduced by about 20% or more. If the wetting spread is insufficient, there is a possibility that good bonding cannot be obtained and the bonding strength cannot be maintained sufficiently.
  • the Cu content in Sn1Ag is fixed at 0.7% by mass and attention is paid to the Ni content.
  • the Ni content exceeds 0.08% by mass and is selected to be 0.1% by mass, the unfusion occurrence rate is remarkably increased.
  • it is less than 0.05% by mass and 0.02% by mass is selected, there is an effect of suppressing unfusion, but resistance to drop characteristics is not obtained.
  • the Ni content from 0.05 to 0.08% by mass, a solder alloy having both unfusion suppression and drop resistance improvement can be obtained.
  • the range with unfusion suppression and drop resistance improvement is confirmed for the Cu content when the Ni content in Sn1Ag is fixed at 0.05% by mass.
  • the Cu content exceeds 0.8 mass% and 1 mass% is selected, the unfusion occurrence rate is remarkably increased.
  • 0.5 mass% is selected below 0.7 mass%, it is judged that a Cu content of 0.7 to 0.8 mass% is optimal as a solder alloy that does not have a drop improvement effect and has both. .
  • the Ni electrode part such as Au plating and Cu It can be used with both Cu electrode parts coated with water-soluble preflux and has both the effect of suppressing interfacial debonding and the effect of suppressing unfusion, so failure mode when an electronic component equipped with an electrode falls A low solder alloy is obtained.
  • an electrode solder ball having a drop impact resistance in both a Cu electrode and a Ni electrode. If the amount of Ni added to the Sn-Ag-Cu ternary composition solder alloy exceeds 0.1% by mass, Ni-containing compounds are likely to precipitate on the solder ball surface and fuse with the mounting paste. Prone to defects. In the solder ball of the present invention, the amount of Ni is suppressed to 0.05 to 0.08% by mass, so that the phenomenon that the compound precipitates on the surface of the solder ball hardly appears, and it is effective in suppressing the unfusion phenomenon.

Abstract

　はんだボールの接合界面における界面剥離を抑制し、且つ、はんだボールとソルダペーストと間に生じる未融合を抑制した、電子部品が落下した時の故障モードが低いはんだボールであって、ＡｕめっきなどのＮｉ電極部とＣｕに水溶性プリフラックスが塗布されたＣｕ電極部共に使用可能なはんだボールを提供する。　本発明は、Ａｇ０．５～１．１質量％、Ｃｕ０．７～０．８質量％、Ｎｉ０．０５～０．０８質量％、残部ＳｎのＢＧＡやＣＳＰの電極用鉛フリーはんだボールであり、接合されるプリント基板がＣｕ電極でも、表面処理にＡｕめっきやＡｕ／Ｐｄめっきを用いるＮｉ電極でも落下衝撃性が良好である鉛フリーはんだボールである。さらに、この組成にＦｅ、Ｃｏ、Ｐｔから選択される元素を１種以上を合計で０．００３～０．１質量％、又はＢｉ、Ｉｎ、Ｓｂ、Ｐ、Ｇｅから選択される元素を１種以上を合計で０．００３～０．１質量％添加しても良い。

Description

鉛フリーはんだボール
　本発明は、半導体などの電子部品の電極に用いる鉛フリーはんだボールに関する。特に、ＡｕめっきなどのＮｉ電極部とＣｕに水溶性プリフラックスが塗布されたＣｕ電極部共に使用可能であり、電極が搭載された電子部品が落下した時の故障モードが低い鉛フリーはんだボールに関する。
　近時、電子機器の小型化、電気信号の高速化等から、電子機器に使用される電子部品も小型化、多機能化されている。小型化、多機能化された電子部品としてはＢＧＡ（Ｂａｌｌ　Ｇｒｉｄ　Ａｒｒａｙ）、ＣＳＰ（Ｃｈｉｐ　Ｓｉｚｅ　Ｐａｃｋaｇｅ）、ＭＣＭ （Ｍｕｌｔｉ　Ｃｈｉｐ　Ｍｏｄｕｌｅ）（以下代表してＢＧＡという）がある。ＢＧＡは、ＢＧＡ基板の裏面に多数の電極が基板目状位置に設置されている。ＢＧＡをプリント基板に実装する場合は、ＢＧＡの電極とプリント基板のランドをはんだで接合することにより行われる。ＢＧＡのプリント基板への実装時には、電極毎にはんだを供給してはんだ付けするのでは多大な手間がかかるばかりでなく、基板の中程にある電極に外部からはんだを供給することはできない。そこで、ＢＧＡをプリント基板に実装するために、予めＢＧＡの電極にはんだを盛り付けておく方法が行われている。これをはんだバンプの形成という。
　ＢＧＡへのはんだバンプ形成には、はんだボール、ソルダペースト等を使用する。はんだボールではんだバンプ形成する場合は、ＢＧＡ電極に粘着性のフラックスを塗布し、該フラックスが塗布された電極上にはんだボールを載置する。その後、該ＢＧＡ基板をリフロー炉のような加熱装置で加熱して、はんだボールを溶融することにより、電極上にはんだバンプを形成するものである。ＢＧＡ基板やＣＳＰ基板などの半導体基板を総称してモジュール基板という。また、ソルダペーストでウエハーのランドにはんだバンプを形成する場合、ウエハーのランドと一致した所にランドと同程度の穴が穿設されたメタルマスクを置き、メタルマスクの上からソルダペーストをスキージで掻きならしてウエハーのランドにソルダペーストを印刷塗布する。その後、ウエハーをリフロー炉で加熱し、ソルダペーストを溶融させることにより、はんだバンプを形成する。
　ところで従来のＢＧＡでは、はんだバンプ形成用としてＳｎ－Ｐｂ合金のはんだボールを用いていた。このＳｎ－Ｐｂはんだボールは、ＢＧＡの電極に対するはんだ付け性に優れているばかりでなく、特にＳｎ－Ｐｂの共晶組成は、はんだ付け時にＢＧＡ素子や基板等に熱影響を与えない融点を有し、しかも柔らかいＰｂを有しているので使用した電子部品や電子機器等が落下しても衝撃を吸収し、電子部品や電子機器等の寿命に大きな貢献をしていた。現在、世界的規模でＰｂの使用が規制されるようになってきており、当然、従来のはんだ付けで使用されてきたＳｎ－Ｐｂの共晶組成も規制されてきている。
　従来、ＢＧＡ用の鉛フリーはんだボールの組成としては、Ｓｎ－３．０Ａｇ－０．５ＣｕやＳｎ－４．０Ａｇ－０．５ＣｕなどのＳｎ－Ａｇ－Ｃｕ系のはんだ合金が用いられてきた。これらの鉛フリーはんだ合金は温度サイクル特性に優れているが、これらのはんだ合金組成のはんだボールを用いた携帯電子機器は落下した時、はんだボール接続界面から剥離する界面剥離が発生し易く、そのため落下衝撃性に劣ると考えられてきた。
　携帯電子機器の落下衝撃を防止する鉛フリーはんだボール用のはんだ合金組成としては、質量％で、(1) Ａｇ: 0.8～2.0％、(2) Ｃｕ: 0.05～0.3％、ならびに (3) In: 0.01％以上、0.1％未満、Ｎｉ: 0.01～0.04％、Co: 0.01～0.05％、およびPt: 0.01～0.1％から選ばれた1種もしくは2種以上、残部Ｓｎからなる鉛フリーはんだ合金（ＷＯ２００６／１２９７１３Ａ公報、特許文献１）、Ａｇ：１．０～２．０質量％、Ｃｕ：０．３～１．５質量％を含み、残部Ｓｎ及び不可避不純物からなることを特徴とする無鉛ハンダ合金。更にＳｂ：０．００５～１．５質量％、Ｚｎ：０．０５～１．５質量％、Ｎｉ：０．０５～１．５質量％、Ｆｅ：０．００５～０．５質量％の１種又は２種以上を含み、Ｓｂ、Ｚｎ、Ｎｉ、Ｆｅの合計含有量が１．５質量％以下である無鉛ハンダ合金（特開２００２－２３９７８０号公報、特許文献２）、ｍａｓｓ％で、０．１～１．５％のＡｇと、０．５～０．７５％のＣｕと、１２．５≦Ｃｕ／Ｎｉ≦１００の関係を満たすＮｉと、残部Ｓｎ及び不可避的不純物からなる鉛フリーはんだ合金（ＷＯ２００７／０８１００６Ａ公報、特許文献３）、Ａｇ：１．０～２．０質量％、Ｃｕ：０．３～１．０質量％、Ｎｉ：０．００５～０．１０質量％を含有し、残部Ｓｎ及び不可避不純物からなる鉛フリーはんだ合金（ＷＯ２００７／１０２５８８Ａ公報、特許文献４）がある。また、BGA基板のようなモジュールとプリント基板の接合時に発生する未融合の解決法として、モジュール基板の電極部にフラックスを塗布する方法（ＷＯ２００６－１３４８９１Ａ公報、特許文献５）が開示されている。
ＷＯ２００６／１２９７１３Ａ公報 特開２００２－２３９７８０号公報 ＷＯ２００７／０８１００６Ａ公報 ＷＯ２００７／１０２５８８Ａ公報 ＷＯ２００６／１３４８９１Ａ公報
　これらの特許文献１～４は、Ｓｎ－Ａｇ－Ｃｕ系はんだボールの耐落下衝撃性の改善のために、Ａｇの含有量を低減してはんだの硬度を低下させ衝撃吸収量を向上させたり、Ｃｕの含有量を低減してランドとはんだとの接合面に発生するＣｕ６Ｓｎ５などの金属間化合物層を薄くし、接合界面で剥離するのを防止したものであり、ＡｇとＣｕの含有量を低減したことにより発生するはんだ自体の強度をＮｉ、Ｆｅ、Ｃｏなどの鉄族元素を添加することで改善している。
　しかし、特許文献１～４のような耐落下衝撃性対策のはんだボールを採用しても、電子機器の落下による不具合が減少しないという問題点が発生した。この点を解析すると、従来のＳｎ－Ｐｂはんだに比較して増加している電子機器の落下による故障は、特許文献１～５にしたようなはんだボールと基板の接合界面だけで発生するのではないことが解ってきた。ＢＧＡ基板などのモジュール基板とプリント基板に接合するときに、ＢＧＡの電極に用いられるはんだボールのはんだ成分とプリント基板のはんだ付けに用いられるソルダペーストのはんだ成分が混じり合わない（図１）「未融合」と呼ばれる不具合が、従来のＳｎ－Ｐｂはんだから、鉛フリーはんだへの移行に伴い新たに不具合として発生したからである。
　しかし、未融合の発生はＳｎ－３．０Ａｇ－０．５Ｃｕ組成のはんだボールから、耐落下衝撃性対策として開発されたＳｎ－Ａｇ－Ｃｕ－Ｎｉ組成のはんだボールに移行するに従い多く発生することが解ってきた。どうやら、未融合の原因が、はんだボールの落下衝撃改善のために添加したＮｉがＳｎと金属間化合物を形成して、はんだボール表面に析出することで、はんだボールのはんだ成分とソルダペーストとはんだ成分とが混じり合うのを妨害していることが原因と考えられる。
　また、未融合の発生原因として以下も考えられる。プリント基板が加熱され大きく反った時に、はんだボールとソルダペーストとが離れる。はんだボールとソルダペーストが離れたまま加熱されると、はんだボールは高温により表面が酸化する。ソルダペーストからにじみ出たフラックスがはんだボールの表面を覆い、このフラックスが活性力を失うと、冷却の過程で反りが戻った時に、ソルダペーストがはんだボールと接触しても、はんだボールの表面の酸化膜を除去することができないため、未融合になる。この対策として特許文献５の方法が有効である。
　そして実施例からは、未融合がはんだボールの組成によって、はんだボール内部に形成する化合物、Ｃｕ６Ｓｎ５または(Ｃｕ、Ｎｉ)６Ｓｎ５に起因することが判明した。はんだボールが接合された部品を実装基板に搭載する際、ソルダペーストが印刷塗布された実装基板に対して、はんだボールが接合されている電極側は下向きにして搭載が行われる。その後加熱が行われ、ソルダペーストの溶融とともにはんだボールも溶融し融合に至る。　しかし、はんだボール内部に形成する化合物Ｃｕ６Ｓｎ５または(Ｃｕ、Ｎｉ)６Ｓｎ５が多く生成する場合、はんだボール溶融時に化合物がボール内部を沈降し、バンプ最表面付近に析出する現象が発生する。この現象により、ペーストとの融合を阻害し融合不良を引き起こす要因になっていることを確認した（図２、図３）。
　ＢＧＡやＣＳＰに用いられるはんだボールには、耐落下衝撃が求められる。耐落下衝撃に対する有効な手段の一つに界面化合物の改質があり、特許文献１～４に開示されているように、Ｎｉ添加が改善の手段となっている。しかし、未融合の観点においてはＮｉも化合物を生成する元素になるため、添加できる量は限られる。未融合を考慮しＣｕやＮｉ添加を抑止すると、耐落下衝撃特性が失われるため、ＢＧＡやＣＳＰなど携帯機器に多用に搭載されるはんだボールには不向きとなってしまう。
　本発明が解決しようとする課題は、耐落下衝撃性などのはんだ強度を向上させたＳｎ－Ａｇ－Ｃｕ－Ｎｉ組成のはんだボールであっても、未融合の発生がないはんだボール用のはんだ合金を開発することであり、はんだボールの接合界面における界面剥離を抑制し、且つ、はんだボールとソルダペーストと間に生じる未融合を抑制することにより、電子部品が落下した時の故障モードが低く、接合されるプリント基板がＣｕ電極においても、Ｎｉ下地に対してＡｕめっきやＡｕ／Ｐｄめっき表面処理を施した電解Ｎｉ／Ａｕ電極および無電解Ｎｉ／Ｐｄ／Ａｕ電極においてもその効果があるＢＧＡやＣＳＰ用のはんだボールを得ることである。　
　本発明者らは、耐落下衝撃性と未融合発生率が共に低いはんだボール用はんだ合金が携帯電子機器の落下による不具合が少ないこと、耐落下衝撃性はんだ合金に含有するＮｉなどの鉄属の金属がはんだボール表面に析出してしまうと未融合発生率が高くなり、携帯電子機器の落下による不具合が多く発生すること、はんだ合金中に添加したＮｉの量を規定することで、未融合、ひいては携帯電子機器の落下による不具合が少なくなることを
見い出し、本発明を完成させた。
　本発明では、ベースとなるＳｎ－Ａｇ－ＣｕはんだをＡｇが０．５～１．１質量％、Ｃｕが０．７～０．８質量％、残Ｓｎとしている。この理由としては、本発明のはんだボールは、Ｓｎ－Ａｇ－Ｃｕ３元組成のはんだ合金中のＣｕの含有量を減少させることによって、Ｃｕ電極界面にＣｕ６Ｓｎ５の金属間化合物の形成を抑制していた特許文献１～４の技術と異なり、Ｓｎ－Ａｇ－Ｃｕ３元組成のはんだ合金中のＣｕの含有量が共晶点である０．７５質量％近辺において、Ｎｉを添加することではんだ中のＣｕの含有量を減らさなくともＣｕ電極界面にＣｕ６Ｓｎ５の金属間化合物の形成を抑制している。
　これは、本発明のＳｎ－Ａｇ－Ｃｕ３元組成のはんだ合金中のＣｕの含有量を共晶点である０．７５質量％近辺に限定することで、Ｃｕが飽和状態のＳｎ－Ａｇ－Ｃｕ３元組成のはんだ合金中にＣｕ電極からＣｕが拡散することを抑制している。
　本発明のはんだボールのもう１つの特徴は、Ｓｎ－Ａｇ－Ｃｕ３元組成のはんだ合金中のＣｕの含有量を共晶点である０．７５質量％近辺にすることによって、Ｃｕ電極からのＣｕ拡散の抑制だけではなく、Ｃｕと全率固溶の関係にあるＮｉへも同様の効果が得られるため、Ｎｉ電極においてもＮｉ拡散を抑える働きを持つことである。さらに、はんだ中にＮｉを予め添加することにより、部品電極および基板電極からのＮｉ及びＣｕの拡散抑制効果が高まると共に、微細な金属間化合物による接合界面の形成により、Ｎｉ電極に対しても耐落下衝撃性が向上する。
　本発明のＡｇが０．５～１．１質量％、Ｃｕが０．７～０．８質量％、残Ｓｎのはんだボール用はんだ組成に添加するＮｉの量は、０．０５～０．０８質量％である。本発明では、Ｓｎ－Ａｇ－Ｃｕのはんだ合金中に添加するＮｉ量を０．０５～０．０８質量％とすることで、Ｓｎ－Ａｇ－Ｃｕはんだボール表面にＮｉが集中的に析出することもない、温度サイクル特性と耐落下衝撃性が共に優れたＢＧＡ用電極用のはんだボールを得ることができる。
　本発明では、Ｓｎ－Ａｇ－Ｃｕ３元組成のはんだ合金中のＣｕの含有量が共晶点である０．７５質量％近辺において、Ｎｉを添加することではんだ中のＣｕの含有量を減らさなくともＣｕ電極界面にＣｕ６Ｓｎ５の金属間化合物の形成を抑制している。さらにＳｎ－Ａｇ－Ｃｕ３元組成のはんだ合金中に本発明の少量のＮｉ量を添加することによって、はんだ中のＳｎＣｕ化合物：Ｃｕ６Ｓｎ５が微細化し、部品および基板電極界面に形成する金属間化合物の粒子も細かくなり、破壊が起こりにくい接合界面が形成される。
　Ｎｉ添加量が０．０５質量%未満になり少なすぎる場合、前記の効果は得られにくく耐落下衝撃性の向上は実現しない。また、添加量が０．０８質量％を越え過剰であると、接合界面化合物中のＮｉの濃度が上昇し、脆く壊れやすい接合界面が形成されるため、耐落下衝撃性が減少する。また、過剰なＮｉ添加ははんだ硬度の上昇も免れず、耐落下衝撃には不向きである。このようにＮｉ添加量が適正で無い場合、耐落下衝撃性は低下する傾向にある。　
　本発明のはんだボールを用いることによって、Ｃｕ電極とＮｉ電極の両方において耐落下衝撃性を有し、且つ、未融合抑制の効果により電極が搭載された電子部品が落下した時の故障モードが低いするはんだボールが使用できることは、頻繁に行われる電極の設計変更に柔軟に対応できるという利点がある。
　本発明のはんだボールを用いることによって、Ｃｕランドに水溶性プリフラックス（ＯＳＰ、Ｏｒｇａｎｉｃ　Ｓｏｌｄｅｒｂｉｌｉｔｙ　Ｐｒｅｓｅｒｖａｔｉｖｅｓとも呼ぶ）を塗布したＣｕ電極もＡｕめっきやＰｄ／ＡｕめっきなどのＮｉを下地に使用する電極を含むＮｉ電極においても、電子部品が落下した時の故障モードが低いＢＧＡやＣＳＰの電極とプリント基板との接合を得ることができる。
　本発明のＣｕ電極にもＮｉ電極にも耐落下衝撃性を有するはんだボールは、下面電極を有するＢＧＡやＣＳＰ などのＰＫＧ部品へのバンプ形成に用いるのが好ましい。
　本発明のはんだボールのＳｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金で、Ａｇの含有量が０．５質量％未満でははんだの強度が低下し、落下等による衝撃応力を負荷させた場合、はんだ破壊が容易に起こりやすくなるという問題がある。Ａｇの含有量が１．１質量％を越えるとはんだの硬度は高くなり衝撃吸収が低下するため、界面での剥離が引き起こされてしまう。したがって、本発明のはんだボール用の合金は、Ａｇの含有量が０．５～１．１質量％、より好ましくは０．９～１．１質量％でなければならない。
　また、本発明のはんだボールのＳｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金は、Ｃｕの含有量が０．７質量％未満では、Ｓｎ－Ａｇ－Ｃｕの共晶点から離れるので、Ｃｕ電極に用いたときにＣｕ電極からはんだ中にＣｕが拡散することでＣｕ電極界面にＣｕ６Ｓｎ５の金属間化合物層が厚くなり、耐落下衝撃性が悪くなる。Ｓｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金のＣｕの含有量が０．８質量％を越えるとＳｎ－Ａｇ－Ｃｕの共晶点から離れるので、はんだ合金とＣｕ電極との反応層中にＣｕ６Ｓｎ５の金属間化合物ができ易くなり、結果としてＣｕ電極とはんだ接合部界面に形成されるＣｕ６Ｓｎ５の金属間化合物が厚くなる。したがって、本発明のはんだボールのＳｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金に含有されるＣｕの含有量は０．７～０．８質量%でなければならない。
　さらに、本発明のはんだボールのＳｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金は、Ｎｉの含有量が０．０５質量％未満では、Ｎｉを添加した効果が現れずにＮｉ電極からＮｉが拡散しやすくなり、界面に金属間化合物が形成され易くなるので、Ｓｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金中のＮｉの含有量は、０．０５質量％以上でなければならない。同様に、Ｎｉの含有量が０．０８質量％を越えると、接合界面に形成する金属間化合物中のＮｉ濃度が上昇し接合強度が低下してしまう他、はんだ硬度の上昇が伴うため衝撃が負荷された場合、界面剥離が発生しやすくなる。また、Ｎｉの含有量が０．０８質量％を越えると、未融合発生率が高くなる。そのため、本発明のはんだボールのＳｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金中のＮｉの含有量は０．０５～０．０８質量％である必要がある。
　本発明のはんだボールのＳｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金に、さらにＦｅ、Ｃｏ、Ｐｔから選択される元素を１種以上を合計で０．００３～０．１質量％添加しても良い。Ｆｅ、Ｃｏ、Ｐｔ元素のはんだボール用の合金への添加は、接合界面に形成する金属間化合物層を微細化し、厚みを抑制するため、落下改善の効果がある。Ｆｅ、Ｃｏ、Ｐｔから選択される元素が０．００３質量％未満では上記の効果が極めて得られにくく、０．１質量％を越えて添加するとはんだバンプ硬度が上昇し衝撃に対し界面剥離が発生するという弊害が現れる。
　本発明のはんだボールのＳｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金に、さらにＢｉ、Ｉｎ、Ｓｂ、Ｐ、Ｇｅから選択される元素を１種以上を合計で０．００３～０．１質量％添加しても良い。
はんだボールはモジュール基板に搭載された後、画像認識によってはんだ付けされているか否かの判定が行われる。もし、はんだボールに黄色などの変色があると、画像認識において不具合と判定される。そのため、はんだボールはリフローで変色されない方がよい。
　Ｂｉ、Ｉｎ、Ｓｂ、Ｐ、Ｇｅの添加による効果は、熱などによる変色を防止することで、バンプ品質検査におけるエラーを回避することができる。Ｂｉ、Ｉｎ、Ｓｂ、Ｐ、Ｇｅから選択される元素が、０．００３質量％未満では上記の効果が極めて得られにくく、０．１質量％を越えて添加するとはんだバンプの硬度が増し、落下改善効果が損なわれる恐れがある。
　本発明のはんだボールは電極用として使用される。はんだボールの直径は、０．１ｍｍ以上、好ましくは０．３ｍｍ以上、より好ましくは０．５ｍｍ以上である。近年では電子機器の小型化が進み、電子部品に搭載されるはんだボールも微細化し続けている。フリップチップの接合には０．１mm以下のはんだボールが汎用的に使用されており、本発明はんだボールのような、フリップチップを内蔵するCSPやBGAを対象とした電極用はんだボールは０．１ｍｍ以上が主流となっている。
　次の表の組成のはんだ合金を作り、気中造球法で直径０．３ｍｍのはんだボールを作製した。このはんだボールを用いて、以下の手順でＣＳＰ基板を作製した。
Figure JPOXMLDOC01-appb-T000001
　１．作製した各組成のはんだボールをサイズ１２×１２ｍｍの電解Ｎｉ／Ａｕ、電解Ｎｉ／Ｐｄ／Ａｕ、ＣｕランドにＯＳＰで処理された電極を有するＣＳＰ用のモジュール基板に、千住金属工業株式会社製フラックスＷＦ－６４００を用いてリフローはんだ付けをし、各組成のはんだを電極用として用いたＣＳＰを作製した。
　２．サイズ３０×１２０ｍｍ、厚み０．８ｍｍのガラスエポキシ基板（ＦＲ－４）にソルダペーストで電極パターンに従い印刷して、１で作製したＣＳＰを搭載して、２２０℃以上４０秒、ピーク温度２４５℃の条件でリフローを行った。
　３．次の条件で、落下衝撃試験を実施した。試験方法は、２で作製したＣＳＰ搭載ガラスエポキシ基板を用い、台座から１０ｍｍ浮かせた位置に専用治具を用いて基板両端を固定させた。ＪＥＤＥＣ規格に則り、加速度１５００Ｇの衝撃を繰り返し加え、初期抵抗値から１．５倍上昇した時点を破断とみなし、落下回数を記録した。
　特許文献２のようなＮｉを多く含有したＳｎ－Ａｇ－Ｃｕ－Ｎｉ系はんだ合金を使用したはんだボールでは、Ｎｉ電極とはんだ付けする場合でも耐落下衝撃性が得られていないことが判る。
　未融合発生率においても同様のはんだボールを用い、以下の手順でＣＳＰ基板を作製した。
　１．作製した各組成のはんだボールを温度１１０℃、湿度８５％，時間２４ｈｒの処理を施した。
　２．サイズ３６×５０ｍｍ、厚み１．２ｍｍガラスエポキシ基板（ＦＲ－４）にソルダペーストで電極パターンに従い印刷を行い、１で作製したはんだボールを搭載して、２２０℃以上４０秒、ピーク温度２４５℃の条件でリフローを行った。
　３．実体顕微鏡を用いて、はんだボールとソルダペーストの未融合数を記録し、未融合発生率を算出した。
　続いて作製したはんだボールを用いて、濡れ広がり試験を以下の手順で実施した。使用した基板材質は未融合発生率を調査した基板と同様のものを用いた。
　１．０．２４ｍｍ×１６ｍｍのスリット状の電極を形成した厚み１．２ｍｍガラスエポキシ基板（ＦＲ－４）を用い、０．２４ｍｍφ×厚み０．１ｍｍの千住金属工業株式会社製フラックスＷＦ－６４００を印刷し、はんだボールを搭載して、２２０℃以上４０秒、ピーク温度２４５℃の条件でリフローを行った。
２　.実体顕微鏡を用いて、濡れ広がり面積を測定した。
　比較例７、９、１０、１１、１３はＣｕ含有量が０．８質量％を超え、もしくはＮｉ含有量が０．０７質量％を超えて含有するはんだボール合金組成であるため、未融合発生率が８％を上回り抑制効果は得られていない。
　特に、比較例１３における特許文献２記載のはんだ組成Ｓｎ－１．５Ａｇ０．５Ｃｕ－０．５Ｎｉの未融合発生率は、格段に増加している。これは、はんだ中におけるＮｉ含有量が多すぎるため、生成化合物量が過多となりペーストとの融合性を阻害、結果として未融合の発生率を増加させてしまっている。
　同様に比較例１０、１１は、Ｃｕ含有量が多すぎるために生成化合物が過多となり未融合発生を誘引している。
　さらに、比較例１～２においては、Ａｇ量が少ないために著しい濡れ広がりの低下が見られる。実際に実施例１と比較すると、濡れ広がり面積が約２０％以上低下している。濡れ広がりが不十分である場合、良好な接合が得られず接合強度が十分に保てない可能性がある。
　比較例３～６、８、１２、１４、１５においては、未融合発生率が５％を下回り、かつ十分な濡れ広がりを確保しているものの、Ａｇ、Ｃｕ、Ｎｉ含有量が最適化されていないため、落下改善効果が得られなくなる。　
　ここで、Ｓｎ１ＡｇにおけるＣｕ含有量を０．７質量％に固定しＮｉ含有量について着目する。Ｎｉ含有量が０．０８質量％を超え０．１質量％を選択した場合、未融合発生率は著しく増加してしまう。逆に０．０５質量％を下回り０．０２質量％を選択した場合、未融合への抑制効果は有するが、落下特性の耐性が得られていない。このようにＮｉ含有量を０．０５～０．０８質量％で選択することにより未融合抑制と耐落下改善を兼ね備えたはんだ合金が得られる。
　続いて、Ｓｎ1ＡｇにおけるＮｉ含有量を０．０５質量％に固定した場合でのＣｕ含有量について、未融合抑制および耐落下改善を伴う範囲を確認する。Ｃｕ含有量が０．８質量％を超え１質量％を選択した場合、未融合発生率が著しく増加。さらに０．７質量％を下回り０．５質量％を選択した場合、落下改善効果が伴わず、両者を兼ね備えるはんだ合金としては、Ｃｕ含有量０．７～０．８質量％が最適と判断する。
　結論として、Ａｇ０．５～１．１質量％、Ｃｕ０．７～０．８質量％、Ｎｉ０．０５～０．０８質量％、残部Ｓｎからなるはんだ組成において、ＡｕめっきなどのＮｉ電極部とＣｕに水溶性プリフラックスが塗布されたＣｕ電極部共に使用可能であり、界面剥離抑制効果と未融合抑制効果の両方を兼ね備えていることから、電極が搭載された電子部品が落下した時の故障モードが低いはんだ合金が得られる。
　本発明により、Ｃｕ電極においてもＮｉ電極においても耐落下衝撃性を有する電極用はんだボールが提供される。Ｓｎ－Ａｇ－Ｃｕの３元組成のはんだ合金に添加するＮｉの量が０．１質量%を超え過剰になると、はんだボール表面にＮｉを含む化合物が析出しやすくなると共に、実装ペーストとの融合不良を起こし易い。本発明のはんだボールはＮｉ量を０．０５～０．０８質量%に抑えているので、化合物がはんだボール表面へ析出する現象が現れ難く、未融合現象の抑制にも効果がある。
未融合現象の一例 はんだボール内部の化合物によるソルダペーストとの融合阻害例 はんだボール内部の化合物によるソルダペーストとの融合阻害例 拡大写 実施例２における接合界面化合物層 比較例９における接合界面化合物層 比較例１０における接合界面化合物層 界面剥離の模式図 未融合の模式図
　１　　　ＢＧＡ部品
　２　　　実装基板
　３　　　はんだバンプ　融合
　４　　　はんだバンプ　未融合
　５　 　 実装加熱後のはんだボール
　６　　　実装加熱後のソルダペースト
　７　　　未融合箇所
　８　 　 融合阻害要因の化合物
　９　 　 ＢＧＡ側電極
　１０ 　 耐落下特性を有する接合界面化合物
　１１ 　 はんだバンプ
　１２ 　 Ｃｕ含有量不足による耐落下特性を有しない接合界面化合物
　１３ 　 Ｎｉ含有量不足による耐落下特性を有しない接合界面化合物
　１４　　ランド

Claims (9)

  1. 　ＢＧＡ、ＣＳＰ用のモジュール基板に取り付けられ、電極用として使用するはんだボールであって、Ａｇ０．５～１．１質量％、Ｃｕ０．７～０．８質量％、Ｎｉ０．０５～０．０８質量％、残部Ｓｎからなるはんだ組成の鉛フリーはんだボール。
  2. 　前記はんだ組成が、Ａｇ０．９～１．１質量％、Ｃｕ０．７～０．８質量％、Ｎｉ０．０５～０．０８質量％、残部Ｓｎからなるはんだ組成の請求項１記載の鉛フリーはんだボール。
  3. 　前記はんだ組成が、Ａｇ１．０質量％、Ｃｕ０．７５質量％、Ｎｉ０．０７質量％、残部Ｓｎからなるはんだ組成の請求項１記載の鉛フリーはんだボール。
  4. 　前記はんだ組成に、Ｆｅ、Ｃｏ、Ｐｔから選択される元素を１種以上を合計で０．００３～０．１質量％添加したことを特徴とする請求項１～３のいずれかに記載のはんだボール。
  5. 　前記はんだ組成に、Ｂｉ、Ｉｎ、Ｓｂ、Ｐ、Ｇｅから選択される元素を１種以上を合計で０．００３～０．１質量％添加したことを特徴とする請求項１～３のいずれかに記載のはんだボール。
  6. 　前記はんだボールは、直径が０．１ｍｍ以上の径を有する請求項１～５のいずれかに記載の鉛フリーはんだボール。
  7. 　前記はんだボールは、直径が０．３ｍｍ以上の径を有する請求項１～５のいずれかに記載の鉛フリーはんだボール。
  8. 　前記はんだボールは、直径が０．５ｍｍ以上の径を有する請求項１～５のいずれかに記載の鉛フリーはんだボール。
  9. 　電解Ｎｉ／Ａｕ電極、無電解Ｎｉ／Ｐｄ／Ａｕ電極、Ｃｕ－ＯＳＰ電極から選択した電極を有するモジュール基板に対してはんだバンプを形成する方法であって、請求項１～８のいずれかに記載のはんだボールを用いてはんだ付けするモジュール基板のはんだバンプ形成方法。
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WO2012131861A1 (ja) 2012-10-04
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