WO2021161953A1 - 鉛フリーかつアンチモンフリーのはんだ合金、はんだボール、およびはんだ継手 - Google Patents
鉛フリーかつアンチモンフリーのはんだ合金、はんだボール、およびはんだ継手 Download PDFInfo
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- WO2021161953A1 WO2021161953A1 PCT/JP2021/004570 JP2021004570W WO2021161953A1 WO 2021161953 A1 WO2021161953 A1 WO 2021161953A1 JP 2021004570 W JP2021004570 W JP 2021004570W WO 2021161953 A1 WO2021161953 A1 WO 2021161953A1
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- WIPO (PCT)
- Prior art keywords
- solder
- free
- alloy
- antimony
- lead
- Prior art date
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- 229910000679 solder Inorganic materials 0.000 title claims abstract description 176
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 114
- 239000000956 alloy Substances 0.000 title claims abstract description 114
- 229910052802 copper Inorganic materials 0.000 claims abstract description 36
- 239000000203 mixture Substances 0.000 claims abstract description 33
- 229910052709 silver Inorganic materials 0.000 claims abstract description 17
- 229910052718 tin Inorganic materials 0.000 claims abstract description 14
- 229910052759 nickel Inorganic materials 0.000 claims description 26
- 229910052732 germanium Inorganic materials 0.000 claims description 12
- 229910052804 chromium Inorganic materials 0.000 claims description 4
- 229910052737 gold Inorganic materials 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052750 molybdenum Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052763 palladium Inorganic materials 0.000 claims description 4
- 229910052698 phosphorus Inorganic materials 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 2
- 239000013078 crystal Substances 0.000 abstract description 10
- 230000004927 fusion Effects 0.000 abstract description 6
- 150000001875 compounds Chemical class 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- 239000000470 constituent Substances 0.000 description 14
- 239000000758 substrate Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 8
- 230000003628 erosive effect Effects 0.000 description 8
- 230000004907 flux Effects 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- 229910052751 metal Inorganic materials 0.000 description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- 239000000843 powder Substances 0.000 description 6
- 229910052710 silicon Inorganic materials 0.000 description 6
- 239000010703 silicon Substances 0.000 description 6
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 238000005304 joining Methods 0.000 description 4
- 238000005476 soldering Methods 0.000 description 4
- 229910017944 Ag—Cu Inorganic materials 0.000 description 3
- 229910017482 Cu 6 Sn 5 Inorganic materials 0.000 description 3
- 230000004888 barrier function Effects 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 238000009792 diffusion process Methods 0.000 description 3
- 238000002845 discoloration Methods 0.000 description 3
- 229910000765 intermetallic Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 229910001887 tin oxide Inorganic materials 0.000 description 3
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 238000013461 design Methods 0.000 description 2
- 230000006355 external stress Effects 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 230000010354 integration Effects 0.000 description 2
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007670 refining Methods 0.000 description 2
- 230000000717 retained effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 238000007711 solidification Methods 0.000 description 2
- 230000008023 solidification Effects 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 229910006414 SnNi Inorganic materials 0.000 description 1
- 238000003916 acid precipitation Methods 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000001747 exhibiting effect Effects 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 244000144972 livestock Species 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 238000012858 packaging process Methods 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000001629 suppression Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000003685 thermal hair damage Effects 0.000 description 1
- 238000012795 verification Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
- B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
- B23K35/24—Selection of soldering or welding materials proper
- B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
- B23K35/262—Sn as the principal constituent
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
- B23K3/00—Tools, devices, or special appurtenances for soldering, e.g. brazing, or unsoldering, not specially adapted for particular methods
- B23K3/06—Solder feeding devices; Solder melting pans
- B23K3/0607—Solder feeding devices
- B23K3/0623—Solder feeding devices for shaped solder piece feeding, e.g. preforms, bumps, balls, pellets, droplets
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C13/00—Alloys based on tin
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/30—Assembling printed circuits with electric components, e.g. with resistor
- H05K3/32—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits
- H05K3/34—Assembling printed circuits with electric components, e.g. with resistor electrically connecting electric components or wires to printed circuits by soldering
- H05K3/3457—Solder materials or compositions; Methods of application thereof
- H05K3/3463—Solder compositions in relation to features of the printed circuit board or the mounting process
-
- 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 lead-free and antimony-free solder alloys, solder balls, and solder joints.
- QFP Quad Flat Package
- a packaging process is adopted in which a silicon chip cut out from a silicon wafer is die-bonded to a lead frame.
- a silicon chip and a lead frame are die-bonded with a solder alloy to form a solder joint.
- a back metal having a Ni layer on the outermost layer is formed on the silicon chip, for example, in order to improve the wettability with the solder and improve the adhesion strength.
- a barrier layer such as Ti is usually formed on the back metal in order to prevent Ni from diffusing into the silicon chip.
- the wettability of the solder alloy to Ti is very poor, so that the back metal wets and repels the molten solder. Further, even if a small amount of Ni layer remains, Ni atoms diffuse into the molten solder and Ti hardly diffuses into Ni. For this reason, voids increase at the atomic level at the interface between the Ti layer and the Ni layer, which are barrier layers, and the adhesive strength at the interface between the remaining Ni layer and the Ti layer is extremely lowered. As a result, the joint portion after die bonding may be inferior in impact resistance and heat cycle resistance. As described above, it is extremely important for die bonding to leave the Ni layer of the back metal.
- solder bumps are formed using solder balls.
- an adhesive flux is applied to the microelectrode, and the solder ball is placed on the electrode to which the flux is applied. After that, the solder balls are melted by heating in a reflow furnace, and the molten solder gets wet with the microelectrodes, so that solder bumps are formed on the microelectrodes.
- the solder ball is used, wettability with an electrode is required.
- Sn-Ag-Cu solder alloys have been widely used in the past, and are used in the form of solder balls as well as for die bonding. However, when this solder alloy is used, it may be necessary to improve heat cycle resistance, impact resistance, and discoloration resistance in various recent demands. Therefore, various studies have been made on Sn—Ag—Cu solder alloys, which have been widely used conventionally, in order to improve these characteristics.
- Patent Document 1 discloses a solder alloy containing Ni as an optional element and Ge or the like as a selective essential element in the Sn—Ag—Cu solder alloy. It is disclosed that this solder alloy exhibits heat cycle resistance when it contains Ni, and exhibits impact resistance and discoloration resistance when it contains Ge.
- solder alloy disclosed in Patent Document 1 is an excellent alloy capable of simultaneously exhibiting the three effects of impact resistance, discoloration resistance, and heat cycle resistance. However, it is considered that there was room for further improvement in alloy design.
- solder alloy is an integral combination of all the constituent elements, and since each constituent element influences each other, the constituent elements are contained in a well-balanced manner as a whole. Need to be.
- the content of each constituent element is individually optimized, and in order to obtain the effect described in Patent Document 1 at the time of filing the application of Patent Document 1, it is necessary to obtain the effect described in Patent Document 1. That seems to be sufficient.
- the content of each constituent element has been individually optimized so that each property can be improved at the same time, and then further. , It is necessary to contain the constituent elements in a well-balanced manner.
- An object of the present invention is to provide a lead-free and antimony-free solder alloy, a solder ball, and a solder joint, which can improve the shear strength by refining the crystal grains at the bonding interface and suppress unfusion. Is.
- the solder alloy is composed of two or more kinds of elements, and the effect of each of them may affect the characteristics of the entire solder alloy. However, as mentioned above, all the constituent elements are integrated. Each constituent element is interrelated. The present inventors have improved the share strength and suppressed unfusion so that the same constituent elements as the solder alloy described in Patent Document 1 can be applied not only to BGA but also to QFP. We focused on designing. Specifically, the present inventors reexamined the significance of adding each constituent element, and then conducted a detailed composition search in consideration of the balance of each constituent element.
- Pb is conventionally used for a substrate and then landfilled, acid rain may cause Pb to elute and flow into groundwater. Then, it may affect the human body by accumulating in livestock and humans from groundwater. Therefore, Pb is designated as a regulated substance by the RoHS Directive.
- Sb which may improve the heat cycle property of Sn-based solder alloys, is increasingly lead-free and antimony-free because there is an increasing demand to avoid using it for environmental and health reasons. The alloy composition was studied so that the desired properties could be obtained.
- the paste contains flux, it is difficult to remove the oxide film and improve the wettability at the same time. Further, since the volume of the solder ball is several times larger than the volume of the solder powder used for the paste, it is more appropriate to solve the problem on the solder ball side than to solve the unfusion on the paste side.
- the present inventors have also studied the miniaturization of intermetallic compounds formed at the bonding interface in order to improve the bonding strength of the solder joint in addition to preventing unfusion. Since a compound of Cu and Sn is formed at the bonding interface, the content ratio of Cu and Sn needs to be in a predetermined range. Further, in the compound of Cu and Sn, miniaturization of the compound is realized by substituting a part of Cu with Ni. More specifically, when a solder joint is formed of a solder alloy containing Cu and Ni, (Cu, Ni) 6 Sn 5 is formed at the bonding interface, so that the metal has a finer crystal structure than Cu 6 Sn 5. An intermetallic layer is formed.
- the joint strength of the solder joint is improved by improving the strength of the intermetallic compound.
- the present inventors have focused on Ge as an element that easily concentrates on the surface of the solder alloy and dissolves in Ni to distort the crystal structure of the compound. When Ge is a predetermined amount, it is dissolved in Ni in the compound to distort the crystal structure of the compound, and (Cu, Ni) 6 Sn 5 is solid-solved and strengthened.
- the alloy composition is 0.01% by mass of one or more selected from the group consisting of Mn, Pd, P, Au, Pt, Cr, Fe, Co, V, Mo, and Nb.
- Alloy composition (1) 0.1-4.5% Ag Ag is an element that improves the strength of the solder alloy by precipitating fine Ag 3 Sn at the grain boundaries. If the Ag content is less than 0.1%, the effect of adding Ag is not sufficiently exhibited.
- the lower limit of the Ag content is 0.1% or more, preferably 0.5% or more, more preferably 1.0% or more, further preferably 1.2% or more, and particularly preferably 2 It is 0.0% or more, and most preferably 2.5% or more.
- the upper limit of the Ag content is 4.5% or less, preferably 4.0% or less, more preferably 3.5% or less, further preferably 3.2% or less, and particularly preferably 3 It is 0.0% or less.
- Cu Cu is an element that can suppress Cu erosion and enhance precipitation by Cu 6 Sn 5.
- the lower limit of the Cu content is 0.20% or more, preferably 0.3% or more, more preferably 0.4% or more, and particularly preferably 0.5% or more.
- the upper limit of the Cu content is 0.85% or less, preferably 0.80% or less, more preferably 0.75% or less, and further preferably 0.70% or less.
- Ni is an element that can control the liquidus temperature of the solder alloy and suppress Ni erosion. If the Ni content is less than 0.005%, the effect of adding Ni is difficult to be exhibited.
- the lower limit of the Ni content is 0.005% or more, preferably 0.01% or more, more preferably 0.02% or more, still more preferably 0.025% or more, and even more preferably. It is 0.03% or more, particularly preferably 0.04% or more, and most preferably 0.05% or more.
- the upper limit of the Ni content is 0.090% or less, preferably 0.080% or less, more preferably 0.075% or less, and further preferably 0.070% or less.
- Ge Ge is an element that can suppress unfusion and Ni eating.
- tin oxide is formed on the surface of the molten solder. Tin oxide is strong and hard to break.
- Ge added to the solder alloy reacts with O in the atmosphere to form a hard and brittle oxide film on the surface of the molten solder. Since this oxide film is brittle, it is easily destroyed by the convection of the molten solder itself or the external force applied from the chip when the chip is placed. Therefore, the formation of the Sn oxide film is hindered and the oxide film is not retained on the surface of the molten solder. Contrary to the Sn oxide film, the solder balls and the solder powder in the paste Fusion is promoted.
- Ge is an element that can be dissolved in Ni (Cu, Ni) 6 Sn 5 formed at the bonding interface to suppress Ni erosion. Since (Cu, Ni) 6 Sn 5 is formed at the bonding interface, Ge distorts the crystal structure of this compound, so that the movement of Ni in the compound is suppressed and the movement of Ni to the solder alloy is suppressed. Be hindered. When Ge is not contained, the crystal structure of (Cu, Ni) 6 Sn 5 is maintained in an aligned state, so that Ni at the bonding interface diffuses into the solder alloy, causing Ni erosion. ..
- the lower limit of the Ge content is 0.0005% or more, preferably 0.002% or more, more preferably 0.003% or more, further preferably 0.0035% or more, and particularly preferably 0. It is more than .004%.
- the upper limit of the Ge content is 0.0090% or less, preferably 0.0082% or less, more preferably 0.0080% or less, still more preferably 0.0075% or less, and even more preferably. It is 0.0060% or less, particularly preferably 0.0050% or less, and most preferably 0.0045% or less.
- the present invention contains at least one selected from the group consisting of Mn, Pd, P, Au, Pt, Cr, Fe, Co, V, Mo, and Nb, each containing up to 0.01%.
- the solder alloy may contain one or more of Mn, Pd, P, Au, Pt, Cr, Fe, Co, V, Mo, and Nb as optional elements, up to 0.01% each. These elements can improve mechanical properties.
- Sn The rest of the solder alloy according to the present invention is Sn.
- unavoidable impurities may be contained. Even if it contains unavoidable impurities, it does not affect the above-mentioned effects. Specific examples of unavoidable impurities include As and Cd.
- the present invention is lead-free and antimony-free, it does not exclude the inclusion of Pb and Sb as unavoidable impurities. If In is contained, the wettability deteriorates, so it is better not to contain it. Further, Mn does not have to be contained because it is oxidized during the production of the solder alloy and it is difficult to produce the solder alloy.
- Equation (1) The present invention satisfies the following equation (1). 0.003 ⁇ (Ag + Cu + Ni) ⁇ Ge ⁇ 0.023 (1) formula In the above formula (1), Ag, Cu, Ni, and Ge are the contents (mass%) of the alloy composition, respectively.
- the lower limit of the equation (1) needs to exceed 0.003, preferably 0.004 or more, more preferably 0.005 or more, still more preferably 0.006 or more, and particularly preferably 0. It is 007 or more, and most preferably 0.008 or more.
- the upper limit of the formula (1) needs to be less than 0.023, preferably 0.022 or less, more preferably 0.021 or less, still more preferably 0.020 or less, and even more preferably. It is 0.019% or less, particularly preferably 0.018 or less, most preferably 0.016 or less, 0.014% or less, 0.013% or less, 0.011% or less, 0.009%. It may be as follows.
- Equation (2) The present invention satisfies the following equation (2). (Sn / Cu) x (Ni x Ge) / (Ni + Ge) ⁇ 0.89 (2) formula
- Cu, Ni, Ge, and Sn are the contents (mass%) of the alloy composition, respectively. Is.
- Sn—Ag—Cu—Ni—Ge solder alloy according to the present invention it is necessary to consider the balance of Cu, Ni, Ge, and Sn contents in order to achieve both improvement in share strength.
- the occurrence of Ni erosion can be suppressed.
- the movement of Ni to the solder alloy may be hindered.
- (Cu, Ni) 6 Sn 5 is formed at the bonding interface, and that the crystal structure of the compound is distorted and the diffusion of Ni is suppressed by further blending Ge that dissolves in Ni in a well-balanced manner. NS.
- the upper limit of the formula (2) is less than 0.89, preferably 0.88 or less, more preferably 0.84 or less, still more preferably 0.83 or less, still more preferably 0.81. It is less than or equal to, particularly preferably 0.80 or less, most preferably 0.79 or less, and may be 0.73 or less.
- the lower limit of the formula (2) is not particularly limited, but is preferably more than 0.25, more preferably 0.32 or more, and further preferably 0.32 or more, from the viewpoint of suppressing Ni erosion and sufficiently improving the share strength. Is 0.34 or more, still more preferably 0.36 or more, particularly preferably 0.37 or more, most preferably 0.44 or more, 0.49 or more, 0.57 or more, 0. It may be .63 or more and 0.71 or more.
- the solder alloy according to the present invention needs to satisfy the equations (1) and (2) at the same time in order to suppress unfusion and improve the share strength at the same time. As a result, it is possible to suppress Ni eating.
- the solder alloy according to the present invention is preferable in that if ⁇ T is within a predetermined range, the solid-liquid coexistence region is narrowed and the increase in viscosity of the molten solder can be suppressed.
- the range of ⁇ T is preferably 100 ° C. or lower, more preferably 70 ° C. or lower, and even more preferably 40 ° C. or lower.
- solder ball The lead-free and antimony-free solder alloy according to the present invention is most suitable for the form of the solder ball used for BGA.
- the sphericity of the solder ball is preferably 0.90 or more, more preferably 0.95 or more, and most preferably 0.99 or more.
- the sphericity is obtained by various methods such as the least squares center method (LSC method), the minimum region center method (MZC method), the maximum inscribed center method (MIC method), and the minimum circumscribed center method (MCC method). ..
- the sphericity of the solder ball is measured using a CNC image measuring system (Ultra Quick Vision ULTRA QV350-PRO measuring device manufactured by Mitutoyo Co., Ltd.) using the minimum region center method (MZC method).
- the sphericity represents a deviation from the sphere, for example, an arithmetic mean value calculated when the diameter of each of 500 balls is divided by the major axis, and the value is set to 1.00, which is the upper limit. The closer it is, the closer it is to a true sphere.
- the solder balls according to the present invention are used for forming bumps on electrodes and substrates of semiconductor packages such as BGA (ball grid array).
- the diameter of the solder ball according to the present invention is preferably in the range of 1 to 1000 ⁇ m, more preferably 50 ⁇ m or more and 300 ⁇ m.
- the solder ball can be manufactured by a general solder ball manufacturing method.
- the diameter in the present invention means the diameter measured by the ULTRA QV350-PRO measuring device manufactured by Mitutoyo. 4. Solder fitting
- solder joint according to the present invention is suitable for being used for connecting an IC chip and its substrate (interposer) in a semiconductor package, or for connecting a semiconductor package and a printed wiring board.
- the "solder joint" according to the present invention is connected by using the above-mentioned solder alloy according to the present invention, and means a connection portion between an IC chip and a substrate, and a connection portion between electrodes or a die and a substrate. Including the connection part of.
- the joining method using the solder alloy according to the present invention may be carried out according to a conventional method using, for example, a reflow method.
- the heating temperature may be appropriately adjusted according to the heat resistance of the chip and the liquidus temperature of the solder alloy.
- the temperature is preferably about 240 ° C. from the viewpoint of suppressing thermal damage to the chip to a low level.
- the melting temperature of the solder alloy may be approximately 20 ° C. higher than the liquidus temperature.
- the structure can be further made finer by considering the cooling rate at the time of solidification. For example, the solder joint is cooled at a cooling rate of 2 to 3 ° C./s or more.
- Other joining conditions can be appropriately adjusted according to the alloy composition of the solder alloy.
- the solder alloy according to the present invention can be produced as a low ⁇ -dose alloy by using a low- ⁇ -dose material as a raw material thereof.
- a low ⁇ -dose alloy can suppress soft errors when used for forming solder bumps around a memory.
- solder alloy Sn-3.0Ag-0.5Cu consisting of 3.0% Ag, 0.5% Cu and the balance Sn.
- a diameter of 300 ⁇ m was placed in an environment of 125 ° C. and 100% humidity RH for 24 hours in the same manner as the small piece member.
- the solder of the example or the comparative example Flux was applied on a sample made of an alloy, and a predetermined number of solder balls were placed. In this example, the number of solder balls was 9, and 5 of each were prepared. Then, after reflow, unfused solder was applied. The number of balls was counted to calculate the rate of occurrence of fusion defects.
- Unfused means a state in which the small pieces and the solder balls are not joined.
- the number of unfused solder balls was 0 or less, it was evaluated as “ ⁇ ”, when it was more than 0 and 10 or less, it was evaluated as “ ⁇ ”, and when it was more than 10, it was evaluated as “x”.
- the soldering conditions are as follows: Flux (manufactured by Senju Metal Industry Co., Ltd .: WF-6400) is applied onto the electrodes, and a profile with a peak temperature of 245 ° C and a cooling rate of 2 ° C / s is used as a reflow device (manufactured by Senju Metal Industry Co., Ltd .: It was carried out using SNR-615). The prepared sample was subjected to a shear strength test under a shear strength measuring device (Made by Nordson Dage: SERIES 4000HS) under the condition of a shear rate of 1000 mm / s.
- a preform having a Ni-eating plate thickness of 250 ⁇ m and having an alloy composition shown in Table 1 was mounted on a Cu lead frame. After that, an IC chip having a back metal on the substrate bonding surface side of a 5 mm ⁇ 5 mm ⁇ 200 ⁇ m t silicon chip was mounted on the solder alloy.
- the back metal is formed by sequentially laminating a 0.05 ⁇ m Ti layer and a 0.20 ⁇ m Ni layer as a barrier layer. The mounting orientation was such that the Ni layer abuts on the solder alloy in the IC chip equipped with this back metal.
- the substrate on which the solder alloy and the IC chip were mounted was heated in a reflow oven so that the peak temperature was 240 ° C., and die bonding was performed. Then, the cross section of the obtained lead frame was magnified 30,000 times on the SEM monitor, and the average value of the film thickness of the Ni layer was calculated at any 10 locations. The results are shown in Table 1.
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- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
Abstract
Description
これらの知見により得られた本発明は次の通りである。
0.006 ≦ (Ag+Cu+Ni)×Ge < 0.023 (1)式
(Sn/Cu)×(Ni×Ge)/(Ni+Ge) < 0.89 (2)式
上記(1)式および上記(2)式中、Ag、Cu、Ni、Ge、およびSnは、各々合金組成の含有量(質量%)である。
(2)質量%で、0.1~4.5%のAgと、0.20~0.85%のCuと、0.005~0.090%のNiと、0.0005~0.0090%のGeと、残部がSnからなる合金組成を有し、合金組成は下記(1)式および下記(2)式を満たすことを特徴する鉛フリーかつアンチモンフリーのはんだ合金。
0.003 < (Ag+Cu+Ni)×Ge < 0.023 (1)式
0.57 ≦(Sn/Cu)×(Ni×Ge)/(Ni+Ge) < 0.89 (2)式
上記(1)式および上記(2)式中、Ag、Cu、Ni、Ge、およびSnは、各々前記合金組成の含有量(質量%)である。
(4)合金組成は、質量%で、Mn、Pd、P、Au、Pt、Cr、Fe、Co、V、Mo、およびNbからなる群から選択される1種以上を、各々0.01%を上限として含有する、上記(1)~上記(3)のいずれか1項に記載の鉛フリーかつアンチモンフリーのはんだ合金。
(6)平均粒径が1~1000μmである、上記(5)に記載のはんだボール。
(7)真球度が0.95以上である、上記(5)または上記(6)に記載のはんだボール。
(8)真球度が0.99以上である、上記(5)または上記(6)に記載のはんだボール。
(10)上記(1)~上記(4)のいずれか1項に記載の鉛フリーかつアンチモンフリーのはんだ合金を用いてなるはんだ継手。
(1) 0.1~4.5%のAg
Agは結晶粒界で微細なAg3Snを析出させることによりはんだ合金の強度を向上させる元素である。Ag含有量が0.1%未満であるとAgの添加効果が十分に発揮されない。Ag含有量の下限は0.1%以上であり、好ましくは0.5%以上であり、より好ましくは1.0%以上であり、さらに好ましくは1.2%以上であり、特に好ましくは2.0%以上であり、最も好ましくは2.5%以上である。一方、Ag含有量が多すぎると、粗大なAg3Snが析出してしまい、強度が劣化する。Ag含有量の上限は4.5%以下であり、好ましくは4.0%以下であり、より好ましくは3.5%以下であり、さらに好ましくは3.2%以下であり、特に好ましくは3.0%以下である。
Cuは、Cu食われを抑制するとともにCu6Sn5による析出強化を図ることができる元素である。Cu含有量が0.20%未満であると、Cu6Sn5の析出量が少なく脆いSnNi化合物が析出するためにはんだ合金自体が脆くなる。Cu含有量の下限は0.20%以上であり、好ましくは0.3%以上であり、さらに好ましくは0.4%以上であり、特に好ましくは0.5%以上である。一方、Cu含有量が0.85%を超えるとはんだ合金の液相線温度が高く溶融し難い。Cu含有量の上限は0.85%以下であり、好ましくは0.80%以下であり、より好ましくは0.75%以下であり、さらに好ましくは0.70%以下である。
Niは、Cuと同様にはんだ合金の液相線温度を制御するとともにNi食われを抑制することができる元素である。Ni含有量が0.005%未満であるとNiの添加効果が発揮され難い。Ni含有量の下限は0.005%以上であり、好ましくは0.01%以上であり、より好ましくは0.02%以上であり、さらに好ましくは0.025%以上であり、さらにより好ましくは0.03%以上であり、特に好ましくは0.04%以上であり、最も好ましくは0.05%以上である。一方、Ni含有量が0.090%を超えるとはんだ合金の液相線温度が高く溶融し難い。Ni含有量の上限は0.090%以下であり、好ましくは0.080%以下であり、より好ましくは0.075%以下であり、さらに好ましくは0.070%以下である。
Geは、未融合およびNi食われを抑制することができる元素である。Geを含有しない場合には、酸化錫が溶融はんだの表面に形成される。酸化錫は強固であり破壊し難い。一方、はんだ合金中に添加されたGeは、雰囲気中のOと反応し、溶融はんだの表面に硬くて脆い酸化膜を形成する。この酸化膜は脆いために溶融はんだ自体の対流や、チップを載置した際にチップから加わる外力により容易に破壊される。このため、Snの酸化膜の形成が阻害されるとともに溶融はんだの表面に酸化膜が保持されることがなく、Snの酸化膜とは逆に、むしろ、はんだボールとペースト中のはんだ粉末との融合が促進される。
本発明に係るはんだ合金は、Mn、Pd、P、Au、Pt、Cr、Fe、Co、V、Mo、Nbから1種以上を、任意元素として、各々0.01%を上限として含有することができる。これらの元素は機械的特性を改善することができる。
本発明に係るはんだ合金の残部はSnである。前述の元素の他に不可避的不純物を含有してもよい。不可避的不純物を含有する場合であっても、前述の効果に影響することはない。不可避的不純物の具体例としては、AsやCdが挙げられる。また、本発明は鉛フリーかつアンチモンフリーではあるが、不可避的不純物としてのPbやSbの含有を除外するものではない。Inを含むと濡れ性が悪化するので含有しない方がよい。また、Mnははんだ合金の製造時に酸化してしまいはんだ合金を製造することが難しいため、含有しなくてもよい。
本発明は、下記(1)式を満たす。
0.003 < (Ag+Cu+Ni)×Ge < 0.023 (1)式
上記(1)式中、Ag、Cu、Ni、およびGeは、各々合金組成の含有量(質量%)である。
本発明は、下記(2)式を満たす。
(Sn/Cu)×(Ni×Ge)/(Ni+Ge) < 0.89 (2)式
上記(2)式中、Cu、Ni、Ge、およびSnは、各々合金組成の含有量(質量%)である。
本発明に係るSn-Ag-Cu-Ni-Geはんだ合金において、シェア強度の向上を両立するためには、Cu、Ni、Ge、およびSn含有量のバランスを考慮する必要がある。
本発明に係るはんだ合金は、ΔTが所定の範囲内であれば固液共存領域が狭くなり、溶融はんだの粘度上昇を抑えることができる点で好ましい。ΔTの範囲は好ましくは100℃以下、より好ましくは70℃以下、更に好ましくは40℃以下である。
本発明に係る鉛フリーかつアンチモンフリーのはんだ合金は、BGAに用いられるはんだボールの形態に最適である。はんだボールの真球度は0.90以上が好ましく、0.95以上がより好ましく、0.99以上が最も好ましい。真球度は、例えば、最小二乗中心法(LSC法)、最小領域中心法(MZC法)、最大内接中心法(MIC法)、最小外接中心法(MCC法)など種々の方法で求められる。本発明において、はんだボールの真球度は、最小領域中心法(MZC法)を用いるCNC画像測定システム(ミツトヨ社製のウルトラクイックビジョンULTRA QV350-PRO測定装置)を使用して測定する。本発明において、真球度とは真球からのずれを表し、例えば500個の各ボールの直径を長径で割った際に算出される算術平均値であり、値が上限である1.00に近いほど真球に近いことを表す。
4. はんだ継手
本発明に係るはんだ合金を用いた接合方法は、例えばリフロー法を用いて常法に従って行えばよい。加熱温度はチップの耐熱性やはんだ合金の液相線温度に応じて適宜調整してもよい。チップの熱的損傷を低く抑える観点から240℃程度であることが好ましい。フローソルダリングを行う場合のはんだ合金の溶融温度は概ね液相線温度から20℃程度高い温度でよい。また、本発明に係るはんだ合金を用いて接合する場合には、凝固時の冷却速度を考慮した方がさらに組織を微細にすることができる。例えば2~3℃/s以上の冷却速度ではんだ継手を冷却する。この他の接合条件は、はんだ合金の合金組成に応じて適宜調整することができる。
表1に示すはんだ合金について、未融合の有無を検証した。検証方法は、各実施例及び比較例の組成で調合したはんだ合金を鋳造、圧延したものを、打ち抜きして小片状の部材(2mm(縦)×2mm(横)×0.1mm(厚み))を作成した。この小片を所定の大きさの板状に成形し、フラックスを塗布したOSP(水溶性プリフラックス(Organic Solderability Presevation)処理が施されたCu板上に置き、リフローを行った後、表面を洗浄し、温度125℃、湿度100%RHの環境に24時間置いた。さらに、Agが3.0%、Cuが0,5%、残部がSnからなるはんだ合金(Sn-3.0Ag-0.5Cu)を用いて作製したはんだボール(本例の場合、直径300μm)を、小片部材と同様に温度125℃、湿度100%RHの環境に24時間置いた。次に、実施例あるいは比較例のはんだ合金からなる試料上にフラックスを塗布し、はんだボールを所定個数置いた。本例では、はんだボールの数は9個とし、それぞれ5枚用意した。そして、リフローを行った後、未融合のはんだボールの数を計数して、融合不良発生率を算出した。未融合とは、小片とはんだボールが接合していない状態をいう。
未融合のはんだボールが0個以下の場合には「◎」とし、0個超え10個以下の場合には「〇」とし、10個超えの場合には「×」と評価した。
表1の各はんだ合金を作製して、はんだの溶融温度を測定した。測定方法は、固相線温度はJIS Z3198-1に準じて行った。液相線温度は、JIS Z3198-1を採用せずに、JIS Z3198-1の固相線温度の測定方法と同様のDSCによる方法で実施した。測定した液相線温度と固相線温度の差であるΔT(K)を求め、ΔT(K)が100K以下を「〇」、100K超を「×」とした。
表1に示すはんだ組成からなる直径0.6mmのはんだボールを作製した。このはんだボールを用いて基板の厚みが1.2mm、電極の大きさが直径0.5mm(Cu-OSP)の基板にはんだ付けを行った。
板厚が250μmであり表1に示す合金組成からなるプリフォームをCu製リードフレームに搭載した。その後、5mm×5mm×200μmtのシリコンチップの基板接合面側にバックメタルを備えるICチップをはんだ合金上に搭載した。バックメタルは、バリア層として0.05μmのTi層、0.20μmのNi層を順次積層したものである。搭載の向きは、このバックメタルを備えるICチップにおいて、Ni層がはんだ合金と当接するような向きとした。はんだ合金およびICチップを搭載した基板を、ピーク温度が240℃となるようにリフロー炉で加熱し、ダイボンディングを行った。
そして、得られたリードフレームの断面について、SEMのモニター上で30000倍に拡大し、任意の10か所について、Ni層の膜厚の平均値を算出した。
結果を表1に示す。
Claims (10)
- 質量%で、0.1~4.5%のAgと、0.20~0.85%のCuと、0.005~0.090%のNiと、0.0005~0.0090%のGeと、残部がSnからなる合金組成を有し、前記合金組成は下記(1)式および下記(2)式を満たすことを特徴する鉛フリーかつアンチモンフリーのはんだ合金。
0.006 ≦ (Ag+Cu+Ni)×Ge < 0.023 (1)式
(Sn/Cu)×(Ni×Ge)/(Ni+Ge) < 0.89 (2)式
上記(1)式および上記(2)式中、Ag、Cu、Ni、Ge、およびSnは、各々前記合金組成の含有量(質量%)である。 - 質量%で、0.1~4.5%のAgと、0.20~0.85%のCuと、0.005~0.090%のNiと、0.0005~0.0090%のGeと、残部がSnからなる合金組成を有し、前記合金組成は下記(1)式および下記(2)式を満たすことを特徴する鉛フリーかつアンチモンフリーのはんだ合金。
0.003 < (Ag+Cu+Ni)×Ge < 0.023 (1)式
0.57 ≦(Sn/Cu)×(Ni×Ge)/(Ni+Ge) < 0.89 (2)式
上記(1)式および上記(2)式中、Ag、Cu、Ni、Ge、およびSnは、各々前記合金組成の含有量(質量%)である。 - 前記合金組成は、質量%で、0.0005~0.0045%のGeを含有する、請求項1または2に記載の鉛フリーかつアンチモンフリーのはんだ合金。
- 前記合金組成は、質量%で、Mn、Pd、P、Au、Pt、Cr、Fe、Co、V、Mo、およびNbからなる群から選択される1種以上を、各々0.01%を上限として含有する、請求項1~3のいずれか1項に記載の鉛フリーかつアンチモンフリーのはんだ合金。
- 請求項1~4のいずれか1項に記載の鉛フリーかつアンチモンフリーのはんだ合金からなるはんだボール。
- 平均粒径が1~1000μmである、請求項5に記載のはんだボール。
- 真球度が0.95以上である、請求項5または6に記載のはんだボール。
- 真球度が0.99以上である、請求項5または6に記載のはんだボール。
- 請求項5~8のいずれか1項に記載のはんだボールを用いて形成されたBall Grid Array。
- 請求項1~4のいずれか1項に記載の鉛フリーかつアンチモンフリーのはんだ合金を用いてなるはんだ継手。
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CN115927908A (zh) * | 2021-08-27 | 2023-04-07 | 千住金属工业株式会社 | 软钎料合金和钎焊接头 |
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MX2022009912A (es) | 2022-09-09 |
TWI765570B (zh) | 2022-05-21 |
JP2021126704A (ja) | 2021-09-02 |
JP6928284B1 (ja) | 2021-09-01 |
TW202138576A (zh) | 2021-10-16 |
JP7025679B2 (ja) | 2022-02-25 |
EP4105349A1 (en) | 2022-12-21 |
JP2021126685A (ja) | 2021-09-02 |
TW202219287A (zh) | 2022-05-16 |
TWI781050B (zh) | 2022-10-11 |
CN115397605A (zh) | 2022-11-25 |
KR102543580B1 (ko) | 2023-06-15 |
US20230060857A1 (en) | 2023-03-02 |
BR112022016141A2 (pt) | 2022-10-04 |
KR20220129112A (ko) | 2022-09-22 |
MX2023008513A (es) | 2024-01-02 |
CN115397605B (zh) | 2024-04-30 |
EP4105349A4 (en) | 2023-09-06 |
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