WO2014002283A1 - 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
WO2014002283A1
WO2014002283A1 PCT/JP2012/066822 JP2012066822W WO2014002283A1 WO 2014002283 A1 WO2014002283 A1 WO 2014002283A1 JP 2012066822 W JP2012066822 W JP 2012066822W WO 2014002283 A1 WO2014002283 A1 WO 2014002283A1
Authority
WO
WIPO (PCT)
Prior art keywords
solder
mass
solder ball
electrode
lead
Prior art date
Application number
PCT/JP2012/066822
Other languages
English (en)
French (fr)
Inventor
芳恵 山中
賢 立花
俊策 吉川
野村　光
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
Priority to ES12879828.7T priority Critical patent/ES2665854T3/es
Priority to KR1020137004268A priority patent/KR20140015242A/ko
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 JP2014503897A priority patent/JP5633837B2/ja
Priority to MX2015000222A priority patent/MX347776B/es
Priority to PCT/JP2012/066822 priority patent/WO2014002283A1/ja
Priority to EP12879828.7A priority patent/EP2886243B1/en
Priority to CN201280075513.8A priority patent/CN104602862B/zh
Priority to KR1020147020911A priority patent/KR20140100585A/ko
Priority to KR1020147027283A priority patent/KR20150016208A/ko
Priority to SG11201408766YA priority patent/SG11201408766YA/en
Priority to US14/409,412 priority patent/US9780055B2/en
Priority to CN201610934617.XA priority patent/CN106964917B/zh
Priority to KR1020147020908A priority patent/KR101455966B1/ko
Priority to BR112014032941A priority patent/BR112014032941A2/pt
Priority to KR1020147027281A priority patent/KR101455967B1/ko
Priority to TW102122957A priority patent/TWI535518B/zh
Publication of WO2014002283A1 publication Critical patent/WO2014002283A1/ja
Priority to PH12014502831A priority patent/PH12014502831B1/en
Priority to HK15105350.6A priority patent/HK1204779A1/xx
Priority to US15/642,894 priority patent/US20180005970A1/en
Priority to US16/193,357 priority patent/US20190088611A1/en
Priority to US18/766,832 priority patent/US20240363571A1/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
    • B23K35/22—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
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—Means for bonding being attached to, or being formed on, the surface to be connected, e.g. chip-to-package, die-attach, "first-level" interconnects; Manufacturing methods related thereto
    • H01L24/10—Bump connectors ; Manufacturing methods related thereto
    • H01L24/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L24/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • 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
    • B23K35/0255—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in welding
    • B23K35/0261—Rods, electrodes, wires
    • 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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    • B23K35/26—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
    • 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
    • C22C13/02—Alloys based on tin with antimony or bismuth as the next major constituent
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    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
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    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
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    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/01—Chemical elements
    • H01L2924/01049—Indium [In]
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    • H01L2924/0105—Tin [Sn]
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    • H01L2924/01078—Platinum [Pt]
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    • H01L2924/01083—Bismuth [Bi]
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    • H01L2924/013—Alloys
    • H01L2924/0132—Binary Alloys
    • H01L2924/01322—Eutectic Alloys, i.e. obtained by a liquid transforming into two solid phases
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    • H01L2924/013—Alloys
    • H01L2924/014—Solder alloys
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    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1531—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface
    • H01L2924/15311—Connection portion the connection portion being formed only on the surface of the substrate opposite to the die mounting surface being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1532—Connection portion the connection portion being formed on the die mounting surface of the substrate
    • H01L2924/15321—Connection portion the connection portion being formed on the die mounting surface of the substrate being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/151—Die mounting substrate
    • H01L2924/153—Connection portion
    • H01L2924/1532—Connection portion the connection portion being formed on the die mounting surface of the substrate
    • H01L2924/1533—Connection portion the connection portion being formed on the die mounting surface of the substrate the connection portion being formed both on the die mounting surface of the substrate and outside the die mounting surface of the substrate
    • H01L2924/15331—Connection portion the connection portion being formed on the die mounting surface of the substrate the connection portion being formed both on the die mounting surface of the substrate and outside the die mounting surface of the substrate being a ball array, e.g. BGA
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/15—Details of package parts other than the semiconductor or other solid state devices to be connected
    • H01L2924/181—Encapsulation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2924/00—Indexing scheme for arrangements or methods for connecting or disconnecting semiconductor or solid-state bodies as covered by H01L24/00
    • H01L2924/20—Parameters
    • H01L2924/207—Diameter ranges
    • H01L2924/2076—Diameter ranges equal to or larger than 100 microns
    • 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
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/04—Soldering or other types of metallurgic bonding
    • H05K2203/041—Solder preforms in the shape of solder balls

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 has few defects due to unfusion.
  • BGA Bit Grid Array
  • CSP Chip Size Package
  • MCM Multi Chip Module
  • BGA solder bumps are formed using solder balls, solder paste, or the like.
  • adhesive flux is applied to the BGA electrodes, and the solder balls are placed on the electrodes to which the fluxes have been applied.
  • 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 is generically called a module substrate.
  • solder bumps are formed on the wafer lands with solder paste, a metal mask with holes of the same size as the lands are placed at locations that coincide with the wafer lands, and the solder paste is applied over the metal mask. Use a squeegee to stir and print solder paste 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 are 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, printed circuit board, etc. during the soldering. .
  • the eutectic composition of Sn-Pb 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 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 Pb-free solder balls for BGA. Although these Pb-free solder alloys are excellent in heat fatigue resistance, portable electronic devices using solder balls having these solder alloy compositions tend to cause interface peeling that peels off from the solder ball connection interface when dropped. Inferior to drop impact. In order to improve the drop impact resistance, a Sn—Ag—Cu—Ni based solder alloy with Ni added has been developed.
  • solder paste is used for mounting, the solder component of the molten solder ball and the solder component of the solder paste are not completely mixed, and an Sn oxide film layer appears between the solder ball and the solder paste. Is a problem.
  • unfused phenomenon an example of joining a BGA and a printed board is shown in FIG. The solder bumps 3 that join the BGA component 1 and the mounting substrate 2 are fused, but the solder bumps 4 are unfused.
  • FIG. 2 shows a solder bump composed of a solder ball 5 and a solder paste 6 in which an unfused phenomenon after mounting heating has occurred. Since the unfused joint portion 7 that can be confirmed in FIG. 3 enlarged from FIG. 2 is merely in contact, the joint portion is easily broken when an external impact is applied. When unfusion occurs, an electronic device equipped with a BGA is likely to break down when an external impact such as dropping is applied.
  • the composition of Sn-Ag-Cu-Ni solder balls for BGA, etc. is (1) Ag: 0.8 to 2.0%, (2) Cu: 0.05 to 0.3%, and (3) In: 0.01% or more, Lead-free solder alloy consisting of one or more selected from 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, A lead-free solder alloy comprising: Patent Document 2), Ag: 1.0 to 2.0% by mass, Cu: 0.3 to 1.5% by mass, the balance being Sn and inevitable impurities.
  • 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 3 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 4), 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 publications, Patent Document 5) are disclosed.
  • solder alloy powder for example, solder paste consisting of Sn—Ag—Cu alloy powder and flux is printed on the mounting substrate, and Sn—Ag—Cu based solder alloy bumps are formed on BGA etc.
  • solder paste consisting of Sn—Ag—Cu alloy powder and flux
  • Sn—Ag—Cu based solder alloy bumps are formed on BGA etc.
  • a process of soldering by mounting electronic components and melting them by heating is common. Recently, in this process, even when mounting at a temperature sufficiently exceeding the melting point of the solder alloy, the solder bumps and the solder paste of the module substrate such as BGA or the lead parts and the solder paste are not fused, resulting in poor conduction. The “unfused” phenomenon is a problem.
  • the soldering between the module and the printed circuit board is different from the soldering between the printed circuit board and a chip component with little warpage, and the module and the printed circuit board are characterized in that a large amount of warpage is generated by heating due to reflow. This phenomenon has been confirmed even before component electrodes have become lead-free, but since many occurrences have been confirmed when component electrodes have become lead-free, countermeasures with lead-free solder electrodes, which will become the mainstream in the future, are urgently needed. It was.
  • the unfused phenomenon is mainly caused by the influence of corrosion on the solder bump surface of modules such as BGA and the warpage of the board and parts.
  • a strong oxide film is formed on the bump surface.
  • the flux in the solder paste printed on the printed circuit board by the surface mounting method is responsible for cleaning the surface oxide film.
  • the surface oxide film is strong and the surface is difficult to reduce, and if the board or component warps during heat mounting, the printed solder paste and the component solder bumps will be separated.
  • the occurrence rate is said to be ppm level in the market report, but when exposed to high temperature and high humidity that corrodes the ball surface experimentally, it can rise to a level of 50-70%. It has been confirmed.
  • the present inventors have found that the compound formed inside the solder, Cu6Sn5 or (Cu, Ni) 6Sn5, due to the composition of the solder ball, has an influence other than the above-mentioned causes as uncaused.
  • mounting a solder ball-bonded component on a mounting board mounting is performed with the electrode side to which the solder ball of a module such as BGA is bonded facing down on the mounting board on which solder paste is printed and applied. . After that, heating is performed, and the solder balls are melted together with the melting of the solder paste, resulting in fusion.
  • the inventors of the present invention have found that Ni added for improving the drop impact of the solder ball is caused by unfusion, and forms an intermetallic compound with Sn and Cu and precipitates on the surface of the solder ball. It has been found that the cause is that the components, solder paste, and solder components are prevented from being mixed. Further, the wettability of the solder balls is also due to the unfused phenomenon with the solder paste, and the wettability decrease accompanying the reduction of the Ag amount plays a part in the occurrence of the unfused phenomenon.
  • the amount of Sn, Cu and Ni is set within a certain range, thereby suppressing the amount of Sn, Cu and Ni intermetallic compound produced, and solder balls
  • the inventors have found that unfusion can be drastically reduced by exhibiting sufficient wettability for fusion with solder paste, thereby completing the present invention.
  • the present invention is a solder ball which is attached to a module substrate for BGA or CSP and used as an electrode, and Ag 1.6 to 2.9 mass%, Cu 0.7 to 0.8 mass%, Ni 0.05 to A lead-free solder ball having a solder composition of 0.08% by mass and the balance Sn.
  • intermetallic compounds such as Sn and Ag, Sn, Cu and Ni are formed by adding Ag, Cu or Ni into the solder.
  • a strong solder alloy is formed by forming a network in a network.
  • a method of adding Ni instead of reducing the hard Ag content as in Patent Document 4 is employed.
  • Ni added to increase the strength easily forms an intermetallic compound with Cu, so that it easily becomes a compound and precipitates on the surface of the solder ball, thereby deteriorating the wettability of the solder ball.
  • the applicant of the present application can reduce Sn, Cu, and Ni by reducing the amount of Cu that reacts with Ni. It was noted that no intermetallic compound was deposited on the solder ball surface. However, if the amount of Cu is reduced, the drop impact resistance is reduced by soldering with the Cu electrode. Therefore, the applicant sets the amount of Cu added to the solder alloy to around 0.75% by mass near the eutectic point, thereby consuming Cu due to network formation and Cu consumption due to Cu and Ni compound formation. It was found that a large amount of Cu and Ni compounds did not precipitate on the surface of the solder balls, and no unfusion occurred.
  • a quaternary alloy composition of 1.6 to 2.9% by mass of Ag, 0.7 to 0.8% by mass of Cu, and 0.05 to 0.08% by mass of Ni in the solder ball composition Since there is a network of Sn—Ag—Cu intermetallic compounds and a Cu—Ni intermetallic compound in which Cu and Ni are consumed and reduced, Cu and Ni do not react preferentially. The intermetallic compound of Cu and Ni does not precipitate on the surface of the solder ball. Therefore, even if it solders with a printed circuit board and a solder paste, it shows a good wettability and no unfusion occurs.
  • solder ball of the present invention since the intermetallic compound of Sn, Cu and Ni having poor wettability is not deposited on the surface of the solder ball, good soldering is possible, and soldering is performed using a printed circuit board and a solder paste. However, good soldering that does not cause unfusion is possible.
  • the solder ball of the present invention can obtain a solder joint between an electrode such as BGA and a printed circuit board, which is excellent in both heat fatigue resistance and drop impact resistance in soldering both the Cu electrode and the Ni electrode.
  • FIG. 2 is a diagram showing the occurrence of unfusion at the solder ball / solder paste joint interface in FIG.
  • the figure which shows the BGA side electrode of Example 2 of Table 1 The figure which shows the BGA side electrode of the cited example 6 of Table 1
  • solder ball that does not cause unfusion according to the present invention and is excellent in both heat fatigue resistance and drop impact resistance for bump formation on a package component such as a BGA having a bottom electrode.
  • the alloy for solder balls of the present invention preferably has an Ag content of 1.6 to 2.9% by mass. More preferably, it is 1.9 to 2.3% by mass.
  • the Sn—Ag—Cu—Ni based solder alloy of the solder ball of the present invention is used as a Cu electrode, it is separated from the eutectic point of Sn—Ag—Cu when the Cu content is less than 0.7 mass%. Further, when Cu diffuses 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. Next, when the Cu content of the Sn—Ag—Cu—Ni-based solder alloy exceeds 0.8 mass%, the amount of intermetallic compound of Cu and Ni in the solder ball increases, and Cu and Cu are formed on the surface of the solder ball. Since the amount of Ni intermetallic compound precipitates, unfusion increases.
  • the Cu content exceeds 0.8 mass%, the Cu—Sg—Cu intermetallic compound is easily formed in the reaction layer of the solder alloy and the Cu electrode because the Cu—Sg—Cu eutectic point is separated. As a result, the intermetallic compound of Cu6Sn5 formed at the interface between the Cu electrode and the solder joint becomes thicker. Therefore, the content of Cu contained in the Sn—Ag—Cu—Ni solder alloy of the solder ball excellent in drop impact resistance without occurrence of unfusion according to the present invention is 0.7 to 0.8 mass%. There must be.
  • the Sn—Ag—Cu—Ni solder alloy of the solder ball of the present invention has poor drop impact resistance when the Ni content is less than 0.05 mass%. Further, if the Ni content is less than 0.05% by mass, the effect of adding Ni does not appear and Ni is easily diffused from the Ni electrode, and an intermetallic compound is easily formed at the interface. Therefore, Sn—Ag— The content of Ni in the Cu—Ni solder alloy must be 0.05% by mass or more. Similarly, if the Ni content exceeds 0.08 mass%, the amount of Sn, Cu and Ni intermetallic compound in the solder ball increases, so the amount of Sn, Cu and Ni intermetallic compound on the solder ball surface. As a result of precipitation, the unfusion occurrence rate increases.
  • 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 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 BGAs and CSPs 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 Table 1 was produced, and a solder ball having a diameter of 0.3 mm was produced by an air ball-making method. Using this solder ball, unfused, thermal fatigue test and drop impact test were evaluated.
  • the number of unfused occurrences was evaluated by the following procedure.
  • the produced solder balls of each composition were subjected to an aging treatment at a temperature of 110 ° C., a humidity of 85%, and a time of 24 hours.
  • Glass epoxy board (FR-4) printed with solder paste according to electrode pattern, mounted with aging solder balls, 220 ° C to 40 seconds, peak temperature 245 ° C Reflow was performed under the conditions of The number of unfused solder balls and solder paste was measured using a stereomicroscope.
  • the thermal fatigue test and the drop impact test were performed according to the following procedure.
  • the produced solder balls of each composition are reflow soldered to a CSP module substrate having a size of 12 ⁇ 12 mm using a flux WF-6400 manufactured by Senju Metal Industry Co., Ltd., and the CSP using the solder of each composition as an electrode. Was made.
  • the thermal fatigue test was conducted under the following conditions. Using the evaluation board prepared in 2, the resistance was constantly measured by a series circuit. Using a thermal shock absorber TSA101LA manufactured by ESPEC, 10 minutes was repeatedly applied in an environment of ⁇ 40 ° C. and + 125 ° C., respectively, and when the resistance value exceeded 15 ⁇ was regarded as fracture, the number of thermal fatigue cycles was recorded.
  • Example 2 of Table 1 the content of Ag, Cu, and Ni is within the optimum range, and therefore excellent results have been obtained in all of unfusion, thermal fatigue resistance, and drop impact resistance.
  • FIG. 4 shows the bonding interface compound layer of Example 2, and it can be seen that a thin intermetallic compound layer of Cu 6 Sn 5 is formed at the bonding portion between the BGA electrode 9 and the solder ball 5.
  • solder ball alloy composition containing Ag content exceeding 2.9% by mass in Comparative Examples 1, 4, and 11 exhibits an improvement effect against thermal fatigue and unfusion, but Ag content against drop impact Since the optimum is not obtained, the durability is not obtained, and the number of drops is less than 20, which is not sufficient as an improvement.
  • Comparative Examples 5, 6, 7, and 8 have selected the optimal Ag content, since the optimization of the Cu and Ni content has not been achieved, it has an improvement effect on unfused and drop impacts. Not a result.
  • FIG. 5 shows the bonding interface compound layer of Comparative Example 6, and it can be seen that the intermetallic compound layer of Cu6Sn5 is formed thick.
  • solder composition comprising 1.6 to 2.9 Ag mass%, 0.7 to 0.8 Cu mass%, 0.05 to 0.08 Ni mass%, and the remaining Sn, unfusion is suppressed, and heat A solder alloy having both fatigue and drop impact can be obtained.
  • an electrode solder ball excellent in both heat fatigue resistance and drop impact resistance is provided. Suppressing unfusion leads to a reduction in initial manufacturing defects.
  • solder composition it was necessary to select the solder composition according to the required characteristics of the product, but by providing resistance to both the drop impact and thermal fatigue characteristics, it can be used in a wide range of fields from portable devices to personal computer equipment and in-vehicle equipment. It will also be possible to expand into new fields such as mobile PC, which is currently undergoing rapid development.

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

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、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、Ａｇ１．６～２．９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、耐熱疲労性と耐落下衝撃性の両方に優れた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、未融合による不具合が少ない、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基板の裏面に電極として基板目状位置に設置される。
　ＢＧＡをプリント基板に実装するためには、ＢＧＡの電極とプリント基板のランドをはんだで接合するが、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り、また、基板の中程にある電極は外部からはんだを供給することはできない。そこで、あらかじめＢＧＡの電極にはんだを盛り付けておく方法が用いられている。これをはんだバンプの形成という。
　ＢＧＡ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を形成する場合には、ＢＧＡの電極に粘着性のフラックスを塗布して、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、そのＢＧＡ基板をリフロー炉などの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。尚、ＢＧＡ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には、ウエハーのランドと一致した箇所にランドと同じ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て、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やプリント基板等に熱影響を与えない融点を有する。しかも、柔らかいＰｂを有しているため、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、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Ｐｂ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Ｐｂフリーはんだ合金は耐熱疲労性に優れているが、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いため耐落下衝撃性に劣る。この耐落下衝撃性を改善するため、Ｎｉを加えたＳｎ－Ａｇ－Ｃｕ－Ｎｉ系のはんだ合金が開発された。
　しかし、これらのはんだボールに用いられるＳｎ－Ａｇ－Ｃｕ系やＳｎ－Ａｇ－Ｃｕ－Ｎｉ系のはんだ組成は、従来のＳｎ－Ｐｂ系はんだと比較してぬれ性が悪いため、ＢＧＡをプリント基板にソルダペーストを用いて搭載する時に、溶融したはんだボールのはんだ成分とソルダペーストのはんだ成分が完全に混ざり合わずに、はんだボールとソルダペーストの間にＳｎの酸化皮膜の層が現れる「未融合」という現象が発生することが問題となっている。未融合現象の一例として、ＢＧＡとプリント基板の接合例を図１に示す。ＢＧＡ部品１と実装基板２を接合するはんだバンプ３は融合しているが、はんだバンプ４は未融合が生じている。図２は、実装加熱後の未融合現象が生じたはんだボール５とはんだペースト６からなるはんだバンプである。図２を拡大した図３で確認できる未融合が生じた接合部７は、単に接触しているだけであるため、外的衝撃が加わると簡単に接合部が破壊される。そして、未融合が発生すると、ＢＧＡを搭載した電子機器に落下などの外的衝撃が加わると故障し易くなる。
　未融合による不具合を防止するために、電子機器の製造メーカーは電子機器の抵抗値を測定するなどの方法で、未融合が発生した接合を事前に検査することで、未融合が発生したプリント基板を修正または交換して故障を未然に防止している。
　出願人は、ＢＧＡ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、ＢＧＡ等モジュールの電極部にポストフラックスを塗布する方法（ＷＯ２００６－１３４８９１Ａ公報、特許文献１）を開示している。
　ＢＧＡ等用のＳｎ－Ａｇ－Ｃｕ－Ｎｉ系のはんだボールの組成としては、(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２）、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３）、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４）、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５）が開示されている。
ＷＯ２００６／１３４８９１Ａ公報 ＷＯ２００６／１２９７１３Ａ公報 特開２００２－２３９７８０号公報 ＷＯ２００７／０８１００６Ａ公報 ＷＯ２００７／１０２５８８Ａ公報
　ＢＧＡ等を使用した実装においては、はんだ合金粉末、例えばＳｎ－Ａｇ－Ｃｕ合金粉末とフラックスからなるソルダペーストを実装基板に印刷し、ＢＧＡ等にＳｎ－Ａｇ－Ｃｕ系のはんだ合金バンプが形成された電子部品を搭載し、加熱溶解することで、はんだ付けを行う工程が一般的である。最近、この工程において、はんだ合金の融点を十分に超えた温度で実装しても、ＢＧＡ等のモジュール基板のはんだバンプとソルダペースト、或いは、リード部品とソルダペーストが融合せず、導通不良を引き起こすという「未融合」現象が問題となっている。未融合は、導通不良を引き起こすことは言うまでも無く、電子機器製品として機能を満たさないことに繋がり、場合によっては、市場クレームにまで発展する可能性がある。モジュールとプリント基板とのはんだ付けは、プリント基板と反りの少ないチップ部品とのはんだ付けと違い、モジュールとプリント基板共にリフローによる加熱で大きな反りの発生することが特徴である。この現象は、部品電極が鉛フリー化する以前にも確認されているが、部品電極の鉛フリー化で発生が多く確認されているので、今後主流となる鉛フリーはんだ電極での対策が急務となっていた。
　未融合現象は、ＢＧＡ等モジュールのはんだバンプ表面に対する腐食の影響や、基板や部品の反りが主要因として作用している。特に、はんだバンプ表面が、バンプ形成時に使用するフラックスの洗浄不良、部品が高温高湿下に曝された場合等は、バンプ表面に強固な酸化皮膜を生じる。本来、この表面酸化皮膜を清浄化する役割を担うのが、表面実装工法でプリント基板に印刷されるソルダペースト中のフラックスである。しかし、前述のような表面酸化皮膜が強固で、表面が還元しづらい状態に加えて、加熱実装時に基板や部品の反りが生じた場合、印刷したソルダペーストと部品のはんだバンプが離れてしまうこともあり、未融合発生の可能性が高まる。その発生率は、市場報告ではｐｐｍレベルと言われているのに対して、実験的にボール表面を腐食させる高温高湿に曝した場合には、５０～７０％のレベルにも上昇することが確認されている。
　今回本発明者らは、未融合の原因として、前述した原因以外にはんだボールの組成によるはんだ内部に形成する化合物、Ｃｕ６Ｓｎ５または(Ｃｕ、Ｎｉ)６Ｓｎ５が影響していることを見い出した。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、ＢＧＡなどのモジュールの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未融合を引き起こす要因になっていることが判る。（図３）
　未融合対策としては、部品や実装基板に生じる反りを皆無にすること、ソルダペーストの活性を高めることなどが考えられる。しかし、現在の技術では、基板の反りを無くすことは現実的に不可能であり、ソルダペースト中フラックスの活性化は、はんだ粉末との反応を促進するため、経時的変化の面からペースト信頼性を損なう恐れがあるため困難であり、効果的な融合不良の対策は無かった。そのため、工程が増加してコストアップに繋がってしまうが、特許文献１のような方法で未融合を解消することが一般的であった。
　本発明が解決する課題は、特許文献１のような工程が増加する方法を取らずに、はんだボールの組成のみで、未融合を解消できる方法を見出すことである。
　本発明者らは、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Ｃｕ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であると見出した。また、はんだボールのぬれ性もソルダペーストとの未融合現象に起因しており、Ａｇ量低減に伴うぬれ性低下も未融合現象が発生する一端を担っている。
　そこで、Ｓｎ－Ａｇ－ＣｕにＮｉを含む４元合金において、ＳｎとＣｕとＮｉの量をある範囲に設定することで、ＳｎとＣｕとＮｉの金属間化合物の生成量を抑制し、はんだボール表面に析出する化合物を少なくすることに加え、ソルダペーストとの融合に十分なぬれ性を発揮することで未融合を劇的に低減できることを見出し、本発明を完成させた。
　本発明は、ＢＧＡや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、Ａｇ１．６～２．９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である。
　はんだボールの熱疲労特性を向上させるためには、はんだ中にＡｇやＣｕやＮｉを添加することよってＳｎとＡｇ、ＳｎとＣｕとＮｉなどの金属間化合物を形成して、その金属間化合物が網目状にネットワークを形成することによって、強固なはんだ合金を形成する。また、耐落下衝撃性を高めるには、特許文献４のように硬いＡｇの含有量を低減する代わりにＮｉを添加する方法が取られている。しかし、強度を高めるために添加したＮｉは、Ｃｕと金属間化合物を形成し易いために容易に化合物となり、はんだボール表面に析出して、はんだボールのぬれ性を悪くする。このはんだボール表面に発生したぬれ性が悪い部分は、プリント基板に搭載させてソルダペーストと共に過熱しても、リフローの加熱時間内ではソルダペーストとなじまず、境界線が現れたまま固まる。これが未融合である。
　本出願人は、Ｓｎ－Ａｇ－Ｃｕ－Ｎｉ組成のはんだ合金において、はんだボール表面に析出するＮｉ化合物の量を少なくするために、Ｎｉと反応するＣｕの量を少なくすればＳｎとＣｕとＮｉの金属間化合物がはんだボール表面に析出しないことに注目した。しかし、Ｃｕ量を少なくすると、Ｃｕ電極とのはんだ付けでは耐落下衝撃性が低下する。そこで出願人は、はんだ合金中に添加したＣｕの量を共晶点付近である０．７５質量％近辺に設定することにより、ネットワーク形成によるＣｕの消費とＣｕとＮｉの化合物形成によるＣｕの消費とが釣り合い、ＣｕとＮｉの化合物がはんだボール表面に多く析出しなくなり、未融合が発生しなくなることを見い出した。
　すなわち、はんだボール組成中に１．６～２．９質量％のＡｇと０．７～０．８質量％のＣｕと０．０５～０．０８質量％のＮｉの４元合金組成にすることで、Ｓｎ－Ａｇ－Ｃｕの金属間化合物のネットワークと、それに消費されて低減したＣｕとＮｉが反応したＣｕ－Ｎｉの金属間化合物が存在するので、ＣｕとＮｉが優先的に反応せずに、はんだボール表面にＣｕとＮｉの金属間化合物がはんだボール表面に析出することもない。そのため、プリント基板とソルダペーストではんだ付けしても良好なぬれ性を示し、未融合が発生することはない。
　本発明のはんだボールは、はんだボール表面にぬれ性の悪いＳｎとＣｕとＮｉの金属間化合物が析出していないので、良好なはんだ付けが可能で、プリント基板とソルダペーストを用いてはんだ付けしても、未融合を起こすことがない良好なはんだ付けが可能である。
また、本発明のはんだボールはＣｕ電極とＮｉ電極の双方のはんだ付けにおいて耐熱疲労性及び耐落下衝撃性の両方に優れたＢＧＡ等の電極とプリント基板とのはんだ接合を得ることができる。
ＢＧＡとプリント基板の接合例 図１の４の拡大図 図２のはんだボールとソルダペースト接合界面の未融合発生を示す図 表１の実施例２のＢＧＡ側電極を示す図 表１の引用例６のＢＧＡ側電極を示す図
　本発明の未融合が発生せず、耐熱疲労性及び耐落下衝撃性の両方に優れたはんだボールは、下面電極を有するＢＧＡ等のパッケージ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１．６質量％未満では、はんだボールのぬれ性が低下してしまうことにより、ソルダペーストへの濡れも劣り融合性が悪くなり、未融合が発生しやすくなる。また、Ａｇの含有量が１．６質量％未満では、はんだの強度が低下し、耐熱疲労性が悪くなる。Ａｇの含有量が２．９質量％を越えると、はんだボールが硬くなり、耐落下衝撃性が悪くなる。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１．６～２．９質量％が良い。より好ましくは１．９～２．３質量％である。
　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。
　次に、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
はんだボール中のＣｕとＮｉの金属間化合物量が増加して、はんだボール表面にＣｕとＮｉの金属間化合物量が析出するため、未融合が多くなる。また、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、本発明の未融合が発生せず耐落下衝撃性に優れたはんだボールの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。
　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、耐落下衝撃性が悪くなる。さらに、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、はんだボール中のＳｎとＣｕとＮｉの金属間化合物量が増加するので、はんだボール表面にＳｎとＣｕとＮｉの金属間化合物量が析出するため、未融合発生率が高くなる。さらに、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。
　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ＢＧＡやＣＳＰ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。
　表１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、未融合、そして熱疲労試験と落下衝撃試験を評価した。
Figure JPOXMLDOC01-appb-T000001
１．未融合の発生数評価は以下の手順で行った。作製した各組成のはんだボールを温度１１０℃、湿度８５％、時間２４ｈｒの時効処理を施した。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、時効処理を施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。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計測した。
２．次に、熱疲労試験と落下衝撃試験は以下の手順で実施した。作製した各組成のはんだボールをサイズ１２×１２ｍｍの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。
３．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い、評価基板を作製した。
４．熱疲労試験は次の条件で実施した。２で作製した評価基板を用い、直列回路により抵抗を常時測定した。エスペック製冷熱衝撃装置ＴＳＡ１０１ＬＡを用いて－４０℃、＋１２５℃の環境下でそれぞれ１０分を繰り返し負荷させ、抵抗値が１５Ωを超えた時点を破断とみなし、熱疲労サイクル回数を記録した。
５．落下衝撃においても熱疲労試験と同様の評価基板を用い、次の条件で落下衝撃試験を実施した。試験方法は、評価基板を台座から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。
　表１の実施例２は、Ａｇ、Ｃｕ、Ｎｉの含有量が最適値の範囲内であるため、未融合、耐熱疲労性、耐落下衝撃性の全てにおいて優れた結果が出ている。図４は実施例２の接合界面化合物層であり、ＢＧＡ電極９とはんだボール５の接合部には、Ｃｕ６Ｓｎ５の金属間化合物層が薄く形成されていることがわかる。
　比較例１、４、１１におけるＡｇ含有量が２．９質量％を超えて含有するはんだボール合金組成は、熱疲労や未融合に対しては改善効果を発揮するものの、落下衝撃に対するＡｇ含有量の最適が得られていないため耐性が得られず、落下回数が２０回を下回り改善として十分ではない。
　また、比較例２、３、９、１０については、Ａｇ含有量が１．６質量％を下回るため、熱疲労への耐性が失われサイクル回数が１５００回に到達しない。Ａｇ含有量不足によるぬれ性低下も起因し未融合発生数が１０を超え、抑制効果を失う結果が得られている。
　さらに、比較例５、６、７、８は、最適なＡｇ含有量を選択しているものの、ＣｕとＮｉ含有量の最適化が図れていないため、未融合や落下衝撃への改善効果を兼ね備える結果ではない。図５は比較例６の接合界面化合物層であり、Ｃｕ６Ｓｎ５の金属間化合物層が厚く形成されていることがわかる。
　結論として、１．６～２．９Ａｇ質量％、０．７～０．８Ｃｕ質量％、０．０５～０．０８Ｎｉ質量％、残部Ｓｎからなるはんだ組成において、未融合を抑制し、且つ、熱疲労と落下衝撃のいずれにも兼ね備えたはんだ合金が得られる。
　本発明により、未融合抑制の効果があり、Ｃｕ電極（Ｃｕ－ＯＳＰ電極、Ｃｕ上に水溶性フラックスを塗布したもの）においても、Ｎｉ電極（電解Ｎｉ／Ａｕ電極、無電解Ｎｉ／Ｐｄ／Ａｕ電極）においても、耐熱疲労性と耐落下衝撃性の両方に優れた電極用はんだボールが提供される。未融合を抑制することによって製造上の初期不良の低減につながる。また、これまでは製品の要求特性に応じてはんだ組成を選択する必要が生じていたが、落下衝撃と熱疲労の両特性の耐性を持たせることで、携帯機器からパソコン機器、車載といった幅広い分野と、現在急速な発展を遂げているモバイルＰＣといった新規分野への展開も可能となる。
　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 　 Ｃｕ６Ｓｎ５の金属間化合物層

Claims (9)

  1. 　ＢＧＡや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、Ａｇ１．６～２．９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、Ａｇ１．９～２．３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、Ａｇ２．０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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US20190088611A1 (en) 2019-03-21
US20240363571A1 (en) 2024-10-31
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