WO2012131861A1 - 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
WO2012131861A1
WO2012131861A1 PCT/JP2011/057532 JP2011057532W WO2012131861A1 WO 2012131861 A1 WO2012131861 A1 WO 2012131861A1 JP 2011057532 W JP2011057532 W JP 2011057532W WO 2012131861 A1 WO2012131861 A1 WO 2012131861A1
Authority
WO
WIPO (PCT)
Prior art keywords
solder
mass
electrode
electrodes
lead
Prior art date
Application number
PCT/JP2011/057532
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 PCT/JP2011/057532 priority Critical patent/WO2012131861A1/ja
Priority to MYPI2013701707A priority patent/MY175023A/en
Priority to US14/005,948 priority patent/US9527167B2/en
Priority to KR1020137027902A priority patent/KR20140025406A/ko
Priority to SG2013068416A priority patent/SG193412A1/en
Priority to PCT/JP2012/058271 priority patent/WO2012133598A1/ja
Priority to EP12764138.9A priority patent/EP2692478B1/en
Priority to CN201280024585.XA priority patent/CN103547408B/zh
Priority to JP2012551410A priority patent/JP5365749B2/ja
Priority to KR1020167022883A priority patent/KR20160104086A/ko
Publication of WO2012131861A1 publication Critical patent/WO2012131861A1/ja
Priority to US15/196,227 priority patent/US9700963B2/en

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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
    • B23K35/02—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
    • 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
    • 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
    • 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
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    • H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
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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
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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 for both a Ni electrode portion such as Au plating and a Cu electrode portion in which a water-soluble preflux is applied to Cu.
  • BGA Bit Grid Array, Chip Size Package, Multi Chip Module: hereinafter referred to as BGA
  • a BGA has a large number of electrodes arranged in a grid pattern on the back side of the BGA substrate.
  • BGA electrode and the land of the printed board are joined by soldering.
  • solder bumps are formed in which solder is placed on the BGA electrodes in advance.
  • 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, a metal mask with holes equal to the lands are placed on the wafer land, and the solder paste is scraped from the metal mask with a squeegee. Then, solder paste is printed on the land of the wafer. Thereafter, the wafer is heated in a reflow furnace to melt the solder paste, thereby forming solder bumps.
  • solder balls made of Sn—Pb alloy were used for forming solder bumps.
  • This Sn-Pb solder ball not only has excellent solderability to the BGA electrode, but in particular, the eutectic composition of Sn-Pb has a melting point that does not affect the BGA element and the substrate during soldering.
  • the eutectic composition of Sn-Pb has a melting point that does not affect the BGA element and the substrate during soldering.
  • it since it has soft Pb, even if the used electronic component or electronic device falls, it absorbs the impact, which greatly contributes 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 are used as the composition of lead-free solder balls for BGA.
  • lead-free solder alloys Is excellent in temperature cycle characteristics, but portable electronic devices using solder balls having these solder alloy compositions are prone to interface debonding from the solder ball connection interface when the electronic device is dropped.
  • solder alloy composition for lead-free solder balls for preventing the drop impact of portable electronic devices any one of Ag 0.05 to 5 mass%, Cu 0.01 to 0.3 mass%, and P, Ge, Ga, Al, and Si One or two or more kinds in total: 0.001 to 0.05 mass%, lead-free solder alloy consisting of the remaining Sn (Japanese Patent Laid-Open No.
  • Patent Document 1 and mass%, (1) Ag : 0.8 to 2.0%, (2) Cu: 0.05 to 0.3%, and (3) In: 0.01% or more, less than 0.1%, Ni: 0.01 to 0.04%, Co: 0.01 to 0.05%, and Pt: 0.01 to 0.1
  • a lead-free solder alloy (WO 2006/129713 A1, Patent Document 2) composed of one or more selected from% and the remaining Sn is disclosed.
  • solder alloy As a solder alloy with improved solder joint strength to the Ni plating electrode, it contains Ag: 1.0-2.0 mass%, Cu: 0.3-1.5 mass%, and consists of the remainder Sn and inevitable impurities Lead-free solder alloy. Further, 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%, 1 There is a solder alloy (see Japanese Patent Application Laid-Open No. 2002-239780, Patent Document 3) that contains seeds or two or more kinds, and the total content of Sb, Zn, Ni, and Fe is 1.5% by mass or less.
  • JP 2004-261863 A WO 2006/129713 A1 JP 2002-239780 A
  • solder balls used for electronic parts such as BGA and CSP used in portable electronic devices lead-containing solder alloys such as Sn-Pb have been used. Since lead-containing solder balls contain soft Pb, even when a portable electronic device is dropped, the solder itself acts as a cushion and is strong against drop impact. However, due to environmental considerations, Pb is regulated worldwide, and solder balls used for electronic parts such as BGA and CSP are also required to be lead-free. At present, Sn-Ag-Cu solder alloys are used for solder balls used in electronic parts such as BGA and CSP, but these lead-free solder alloys have excellent temperature cycle characteristics. In the portable electronic device using the solder ball having the solder alloy composition, when the electronic device is dropped, the interface peeling easily occurs from the solder ball connection interface.
  • Patent Documents 1 and 2 are solder alloys for solder balls that are effective for Cu electrodes. By limiting Cu in the solder alloy, the Cu compound reacts with the Cu electrode to form a Cu6Sn5 metal compound. The layer is thinned to prevent destruction from the joint interface between the Cu electrode and the solder ball.
  • the solder alloys for solder balls of Patent Documents 1 and 2 are very effective for Cu electrodes, but are not always effective when joining solder such as Au-plated electrodes and Ni. The same applies to the solder ball solder alloy disclosed in Patent Document 3. Only the Ni electrode is effective for dropping resistance, and the Cu electrode cannot provide an effect for drop improvement.
  • solder alloys disclosed in Patent Documents 1 to 3 as compositions of solder balls that are good for drop impact, but as described in Patent Documents 1 and 2, they are good for Cu electrodes but suitable for Ni electrodes. Although it can be used with Ni electrode flip chip as in Patent Document 3, if it is used as an electrode outside the BGA or CSP, the Cu electrode has a drop impact property that deteriorates the reliability, and so on. There were no solder balls for drop impact.
  • the problem to be solved by the present invention is that, even when the printed circuit board to be bonded is a Cu electrode, an electrolytic Ni / Au electrode and an electroless Ni / Pd /
  • the goal is to obtain solder balls for BGA and CSP that have good drop impact even for Au electrodes.
  • the present inventors as a solder alloy for solder balls having a drop impact resistance with either a Cu electrode or a Ni electrode, have a Cu content in the vicinity of 0.75 mass% of the eutectic point of the Sn-Ag-Cu ternary composition. As a result, the drop impact resistance against Cu and Ni electrodes has been improved. Also, by adding Ni to the Sn-Ag-Cu ternary solder alloy, the Cu6Sn5 intermetallic compound layer does not become thick without reducing the Cu content in the Sn-Ag-Cu ternary composition. This completes the present invention.
  • the present invention is a lead-free solder ball used for BGA and CSP electrodes comprising Ag 0.3 to 1.1 mass%, Cu 0.7 to 0.8 mass%, Ni 0.05 to 0.07 mass%, and the balance Sn.
  • Conventional drop impact resistant solder balls for Cu electrodes have a Cu content in a ternary composition solder alloy of Sn-Ag-Cu as described in Patent Documents 1 and 2 by suppressing the Cu content to 0.5 mass% or less. It is designed based on the principle that the Cu6Sn5 intermetallic compound layer having hard and brittle properties generated at the interface between the electrode and the solder ball is thinned to prevent the Cu electrode and the solder ball from being broken at the joint interface.
  • solder alloy for a solder ball having a strong strength with respect to a conventional Ni electrode including Au plating Ni is added to a Sn-Ag-Cu ternary solder alloy composition as disclosed in Patent Document 3, 0.05 to By adding 1.5% by mass, a method of suppressing the diffusion of Ni from the Ni plating surface and suppressing the growth of intermetallic compounds has been taken.
  • the solder ball is effective only for the Cu electrode or the solder ball effective for the Ni electrode, or only one of the electrodes is effective for the Cu electrode. In both cases, no effective solder balls existed.
  • the patent of the drop impact resistant solder ball of the present invention has suppressed the formation of intermetallic compounds of Cu6Sn5 at the Cu electrode interface by reducing the Cu content in the Sn-Ag-Cu ternary solder alloy. Unlike the technology in Reference 1 or 2, the Cu content in the solder alloy of Sn-Ag-Cu ternary composition is around 0.75 mass%, which is the eutectic point. The formation of intermetallic compounds of Cu6Sn5 at the Cu electrode interface is suppressed without reducing this.
  • the content of Cu in the Sn—Ag—Cu ternary composition solder alloy of the present invention is limited to the eutectic point of around 0.75 mass%, so that the Cu is saturated Sn—Ag—Cu ternary composition. Cu is prevented from diffusing from the Cu electrode in the solder alloy. Furthermore, by adding a small amount of Ni to the solder alloy of Sn-Ag-Cu ternary composition, the SnCu compound: Cu6Sn5 in the solder becomes finer, and the particles of the intermetallic compound formed at the part and substrate electrode interface also become finer. A bonded interface that is less likely to break is formed.
  • the Cu content in the Sn—Ag—Cu ternary composition solder alloy is about 0.75 mass%, which is the eutectic point.
  • the same effect can be obtained for Ni, which is in a solid solution relationship with Cu, so 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 electrode 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 is less than 0.05% by mass and is too small, the above-described effect is hardly obtained and the drop impact resistance is not improved.
  • the addition amount exceeds 0.07% by mass, the Ni concentration in the bonding interface compound increases, and a brittle and fragile bonding interface is formed, so that the drop impact resistance decreases.
  • excessive addition of Ni is unavoidable for an increase in solder hardness and is not suitable for a drop impact resistance.
  • the amount of Ni added is not appropriate, the drop impact resistance tends to decrease.
  • the present invention by limiting the amount of Ni contained in the Sn—Ag—Cu solder alloy, the effect of improving the drop impact resistance of both the Cu electrode and the Ni electrode is provided.
  • solder balls with drop impact resistance have only effective solder balls for Cu electrodes, effective solder balls for Ni electrodes, or effective solder ball properties for one electrode. There was no effective solder ball in either electrode.
  • solder balls having drop impact resistance in both the Cu electrode and the Ni electrode has the advantage of being able to flexibly deal with frequent electrode design changes.
  • Cu electrodes coated with water-soluble preflux also called OSP, Organic Solderbility Preservatives
  • Ni electrodes can also be bonded to printed circuit boards with BGA and CSP electrodes that have drop impact resistance.
  • 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 having an undersurface electrode.
  • the alloy for solder balls of the present invention should have an Ag content of 0.3 to 1.1% by mass, more preferably 0.9 to 1.1% by mass.
  • the Sn-Ag-Cu-Ni 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.
  • the Cu6Sn5 intermetallic compound layer becomes thick at the Cu electrode interface, and the drop impact resistance deteriorates. If the Cu content of the Sn-Ag-Cu-Ni series solder alloy exceeds 0.8 mass%, it will be separated from the eutectic point of Sn-Ag-Cu, so that the reaction layer of the solder alloy and 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 Cu 0.7 to 0.8 mass%.
  • 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, Ni does not appear and Ni diffuses easily from the Ni electrode. Thus, an intermetallic compound is likely to be 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 0.07% 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. 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 0.07 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 interface delamination occurs due to impact. appear.
  • One or more elements selected from Bi, In, Sb, P, and Ge 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 effect of adding Bi, In, Sb, P, and Ge can prevent an error in bump quality inspection by preventing discoloration due to heat or the like.
  • 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 electrode solder balls for flip-chip embedded CSP and BGA, such as the solder ball of the present invention, should be 0.1 mm or more. It has become 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 produced by the following procedure.
  • Senju Metal Co., Ltd. is used for the CSP module substrate with the electrodes processed by electrolytic Ni / Au, electrolytic Ni / Pd / Au, Cu land with OSP (Organic Solderbility Preservatives) of size 12 x 12mm. Reflow soldering was performed using Flux WF-6400 manufactured by Kogyo Co., Ltd., and CSPs were prepared using solders of various compositions for electrodes.
  • 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 1500G was repeatedly applied, and when the initial resistance value rose 1.5 times, it was regarded as a break and the number of drops was recorded.
  • the discoloration test was performed under the following conditions.
  • the CSP produced in 1 was left in a thermostatic bath at 125 ° C. for 100 hours, and then the yellowing state was visually observed.
  • the case where yellowing did not occur was evaluated as ⁇ , the case where almost no change was observed, ⁇ , the case where slight change was observed, ⁇ , and the case where remarkable change was observed as ⁇ .
  • solder balls using the solder alloys of Patent Document 1 and Patent Document 2 have a drop impact resistance against Cu electrodes, but when soldering a solder ball such as Ni / Au to a Ni electrode Good results have not been obtained. Further, it can be seen that the solder ball using the Sn-Ag-Cu-Ni-based solder alloy containing a large amount of Ni as in Patent Document 3 does not have the drop impact resistance even when soldered to the Ni electrode. .
  • an electrode solder ball having a drop impact resistance in both a Cu electrode and a Ni electrode is provided. If the amount of Ni added to the Sn-Ag-Cu ternary solder alloy exceeds 0.1% by mass, Ni-containing compounds are likely to precipitate on the solder ball surface, resulting in poor fusion with the mounting paste. Easy to wake up.
  • the amount of Ni is suppressed to 0.05 to 0.07% by mass, so that the phenomenon that the compound precipitates on the surface of the solder ball hardly appears, and it is considered that the solder ball is also effective in suppressing the unmelted phenomenon.

Abstract

　落下衝撃に良好なはんだボールの組成として、Cu電極には良好であるがNi電極には向かなかったり、Ni電極への耐落下は向上するがCu電極での落下衝撃性は損なわれて、信頼性が悪くなるなど、Cu電極及びNi電極両方を満たす耐落下衝撃用のはんだボールはなかった。　本発明は、Ag0.3～1.1質量％、Cu0.7～0.8質量％、Ni0.05～0.07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な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、多機能化されてきている。この小型化、多機能化された電子部品としては BGA、CSP、MCM(Ball Grid Array、Chip Size Package、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碁盤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。この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していたのでは多大な手間がかかるばかりでなく、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、前もってBGAの電極にはんだを盛り付けておくというはんだバンプの形成がなされている。
　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てしまい、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。
　BGA用の鉛フリーはんだボールの組成として、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いるが、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、電子機器を落下させると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かった。
　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、Ａｇ０．０５～５質量％、Ｃｕ０．０１～０．３質量％、およびＰ、Ｇｅ、Ｇａ、Ａｌ、Ｓｉのいずれか１種または２種以上を合計で０．００１～０．０５質量％、残部Ｓｎからなる鉛フリーはんだ合金（特開２００４－２６１８６３号公報、特許文献１）や質量％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（ＷＯ２００６／１２９７１３Ａ１、特許文献２）などが開示されている。
　Niめっき電極へのはんだ付け接合強度を向上させたはんだ合金として、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％以下であるはんだ合金（特開２００２－２３９７８０号公報、特許文献３）がある。
特開２００４－２６１８６３号公報 ＷＯ２００６／１２９７１３Ａ１公報 特開２００２－２３９７８０号公報
　携帯電子機器に用いられるBGAやCSPなどの電子部品に用いられるはんだボールは、Sn-Pbなどの鉛入りのはんだ合金が用いられてきた。鉛入りのはんだボールは柔らかいPbを含有しているため、携帯電子機器を落とした場合でも、はんだ自体がクッションの役割を果たすので落下衝撃に強かった。しかし、環境への配慮から世界的にPbが規制されるようになり、BGAやCSPなどの電子部品に用いられるはんだボールも鉛フリー化が求められるようになった。現在、BGAやCSPなどの電子部品に用いられるはんだボールは、Sn-Ag-Cu系のはんだ合金が用いられているが、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、電子機器を落下させるとはんだボール接続界面から剥離される界面剥離が発生し易かった。
　これを解決するために提案されたのが、特許文献１～３の鉛フリーはんだ合金である。特許文献１及び２は、Cu電極に有効なはんだボール用のはんだ合金で、はんだ合金中のCuを限定することによって、Cu電極とはんだが反応してCu電極界面に形成されるCu6Sn5の金属化合物層を薄くして、Cu電極とはんだボールとの接合界面から破壊されることを防止している。特許文献１及び２のはんだボール用のはんだ合金はCu電極には非常に有効であるが、Auめっきの電極などのはんだとNiを接合するときは必ずしも有効ではなかった。特許文献3のはんだボール用はんだ合金に関しても同様で、Ni電極のみ耐落下に有効で、Cu電極においては落下改善への効果が得られない。
　落下衝撃に良好なはんだボールの組成として、特許文献１～３に開示されているはんだ合金があるが、特許文献１～２のように、Cu電極には良好であるがNi電極には向かなかったり、特許文献３のようにNi電極のフリップチップでは使用可能でも、BGAやCSPの外側の電極に用いると、Cu電極では落下衝撃性損なわれて信頼性が悪くなるなど、全てを満たす耐落下衝撃用のはんだボールはなかった。
　本発明が解決しようとする課題は、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電極においても落下衝撃性が良好な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、Cu電極でもNi電極でも耐落下衝撃性を有するはんだボール用のはんだ合金として、Cuの含有量をSn-Ag-Cuの３元組成の共晶点の0.75質量％近辺にすることで、Cu電極、Ni電極に対する耐落下衝撃性の向上を実現した。また、Sn-Ag-Cuの３元組成のはんだ合金にNiを添加することによって、Sn-Ag-Cuの３元組成中のCuの含有量を減らさなくともCu6Sn5の金属間化合物層が厚くならないことによって本発明を完成させた。
　本発明は、Ag0.3～1.1質量％、Cu0.7～0.8質量％、Ni0.05～0.07質量％、残部SnからなるBGAやCSPの電極に用いられる鉛フリーはんだボールである。
　従来のCu電極用の耐落下衝撃性はんだボールは、特許文献１や２のようにSn-Ag-Cuの３元組成のはんだ合金中のCuの含有量を0.5質量％以下に抑えることによってCu電極とはんだボールとの界面に発生する硬く、脆い特性を持つCu6Sn5金属間化合物層を薄くして、Cu電極とはんだボールが接合界面で破壊されることを防止する原理によって設計されている。
　従来のAuめっきを含むNi電極に対して強い強度を有するはんだボール用のはんだ合金としては、特許文献３のようにSn-Ag-Cuの３元組成のはんだ合金組成にNiを０．０５～１．５質量％添加することによって、Niめっき表面からのNiの拡散を抑制して、金属間化合物の成長を抑制する方法などが取られていた。
　これらの特許文献１～３の発明では、Cu電極に有効なはんだボールか、Ni電極に有効なはんだボールか一方の電極に有効なはんだボール特性しか有しておらず、Cu電極にもNi電極にも共に有効なはんだボールが存在していなかった。
　本発明の耐落下衝撃性はんだボールは、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又は２に技術と異なり、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。さらにSn-Ag-Cu３元組成のはんだ合金中に少量のNi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。
　本発明の耐落下衝撃性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って、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。
　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0.07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。
　本発明では、Sn-Ag-Cuはんだ合金に含有させたNiの量を限定することで、Cu電極及びNi電極双方の耐落下衝撃性改善の効果を持たせている。
　従来の耐落下衝撃性を有するはんだボールは、Cu電極に有効なはんだボールか、Ni電極に有効なはんだボールか一方の電極に有効なはんだボール特性しか有しておらず、Cu電極にもNi電極にも共に有効なはんだボールが存在していなかった。Cu電極とNi電極の両方において耐落下衝撃性を有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電極も耐落下衝撃性を有する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０．３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０．３～１．１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、Cu0.7～0.8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０．０７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。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0.05～0.07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（Organic Solderbility Preservatives）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。
４．変色試験に対しては、次の条件で実施した。１で作製したCSPを125℃の恒温槽に100時間放置した後、目視にて黄変状態を観察した。表１記載の判定は、黄変が生じないものを◎、殆ど生じないものを○、やや変化がみられるものを△、顕著なものを×とした。
　結論として、特許文献１及び特許文献２のはんだ合金を使用したはんだボールは、Cu電極に対しては耐落下衝撃性を有するが、Ni/AuなどのはんだボールをNi電極とはんだ付けするときは良好な結果を得られていない。また、特許文献３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。
　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0.05～0.07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、未溶融現象の抑制にも効果があると考えられる。

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、Ag0.3～1.1質量％、Cu0.7～0.8質量％、Ni0.05～0.07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％、Ni0.05～0.07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。
  3. 前記はんだ組成が、Ag1.0質量％、Cu0.75質量％、Ni0.06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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