WO2004030428A1 - はんだ被覆ボールおよびその製造方法、ならびに半導体接続構造の形成方法 - Google Patents
はんだ被覆ボールおよびその製造方法、ならびに半導体接続構造の形成方法 Download PDFInfo
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- WO2004030428A1 WO2004030428A1 PCT/JP2003/012183 JP0312183W WO2004030428A1 WO 2004030428 A1 WO2004030428 A1 WO 2004030428A1 JP 0312183 W JP0312183 W JP 0312183W WO 2004030428 A1 WO2004030428 A1 WO 2004030428A1
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- solder
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- solder layer
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- H—ELECTRICITY
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- 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
- H05K3/341—Surface mounted components
- H05K3/3431—Leadless components
- H05K3/3436—Leadless components having an array of bottom contacts, e.g. pad grid array or ball grid array components
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- H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
- H01L23/498—Leads, i.e. metallisations or lead-frames on insulating substrates, e.g. chip carriers
- H01L23/49811—Additional leads joined to the metallisation on the insulating substrate, e.g. pins, bumps, wires, flat leads
- H01L23/49816—Spherical bumps on the substrate for external connection, e.g. ball grid arrays [BGA]
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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
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- 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
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Definitions
- the present invention relates to a solder-coated pole used as an input / output terminal of a semiconductor device such as a BGA, a method of manufacturing the same, and the like.
- the BGA (Ba11Grid Array) has a solder-coated pole 50 bonded to the lower surface of the LSI chip via an interposer 62. It is an LSI package.
- the solder-covered poles 50 are arranged in a grid array on one surface of the inner poser 62 and are input / output terminals of the package.
- the solder-coated pole 50 is, for example, a microsphere having a diameter of about 0.1 to 1.0 mm.
- the solder coating pole is heated and melted and joined to the interposer pad. There is a problem that gaps (voids) are formed. Poisoning may cause poor connection or misalignment between the interposer and the soldered pole, thus degrading BGA reliability.
- the applicant of the present invention has found that the cause of the above voids is hydrogen gas absorbed in the solder layer formed by electrolytic plating, and that the generation of voids can be suppressed by reducing the amount of generated hydrogen gas.
- the applicant of the present invention controlled the ion concentration of lead and tin in the plating solution and the current density when performing electroplating, so that hydrogen gas occluded in the solder layer was controlled.
- a method for reducing the amount of voids by reducing the amount is disclosed (for example, Japanese Patent Application Laid-Open No. 10-270636 (pages 2 and 3)).
- lead-containing solder has been replaced by lead-free solder (Pb-free solder).
- Pb-free solder for example, Sn—Ag-based solder or Sn—Ag—Cu-based solder is used. Disclosure of the invention
- a solder-coated pole having an Sn-Ag-based solder layer is prepared using the electrolytic plating method, and is heated and melted. Has occurred.
- this poiid is different from the lead-tin-tin system. It was generated by factors other than hydrogen gas, and was found to be a problem specific to the Sn-Ag system.
- the present invention has been made in view of the above-mentioned points, and has an Sn—Ag-based solder layer in which generation of voids during heating and melting is suppressed, a method of manufacturing the same, and a semiconductor connection structure. It is an object of the present invention to provide a method for forming a film.
- the solder-coated pole of the present invention has a pole-shaped core, and a solder layer including Sn and Ag provided so as to surround the core, and the amount of moisture contained in the solder layer is in a standard state.
- the amount of water vapor is 1001 Zg or less, thereby solving the above problem.
- the solder layer may include an alloy of Sn and Ag.
- the solder layer includes: a first metal layer provided to surround the core; and a second metal layer provided to surround the first metal layer.
- One of the metal layer and the second metal layer may include Sn, and the other may include Ag.
- the core is formed of Cu, Al, or resin. It is preferable that the mass percentage of Ag in the solder layer is 0.5% or more and 4.0% or less.
- the solder layer preferably contains Cu, Sn, and Ag.
- the mass percentage of Ag in the solder layer is 3.5% .
- the method of manufacturing a solder-coated pole of the present invention comprises the steps of preparing a pole-shaped core and electrolytic plating. Forming a plating layer containing Sn and Ag so as to surround the core, heating the core on which the plating layer is formed, and keeping the plating layer in a molten state for a predetermined time; The And the step of solidifying the molten plating layer to form a solder layer, thereby solving the above-mentioned problems.
- the step of forming the plating layer may include a step of forming an alloy plating layer containing Sn and Ag.
- the step of forming the plating layer may further include a step of forming a plating layer containing Ag.
- the step of forming the plating layer includes: forming a first plating layer containing Sn so as to surround the core; and forming a second plating layer containing Ag so as to surround the core. And the step of carrying out.
- the solder layer may include Cu, Sn, and Ag.
- the solder layer preferably has a mass percentage of Ag of 0.5% or more and 4.0% or less.
- the solder layer preferably has a mass percentage of Ag of 3.5%.
- solder-coated pole of the present invention is preferably manufactured by the method described above.
- the method for producing a solder-coated pole according to the present invention includes a step of preparing a pole-shaped core and a step of forming a solder layer containing Sn and Ag so as to surround the core.
- the process of forming tris (3-hydroxypropyl) phosphine is 10 to 25 g / l, organic sulfonic acid Sn 15 to 25 g / 1, organic sulfonic acid A g 0.3 to 1.5. g / l, organic sulfonic acid 50 to 100 g / 1, and a first solder layer containing an alloy of Sn and Ag by electrolytic plating using a plating solution containing ammonia Including the step of Ag of the first solder layer.
- the mass percentage is 0.5% or more and 2.5% or less, which solves the above problem.
- the plating solution further contains thiourea of 3 to 12 gZ1.
- the step of forming the solder layer may further include a step of forming a second solder layer containing Ag.
- the second solder layer may be formed by an electrolytic plating method, an evaporation method, or a colloid method.
- the second solder layer is formed by an electrolytic plating method and has a thickness of 0.5 m or less.
- the mass percentage of Ag in the solder layer is preferably 3.0% or more and 4.0% or less.
- the first solder layer has a thickness of not less than 3 / m and not more than 50 m.
- the core is preferably formed of C11, Al, or a resin.
- the mass percentage of Ag in the solder layer is 3.5%.
- the core preferably has a diameter of not less than 0.05 mm and not more than 1 mm.
- solder-coated pole of the present invention is preferably manufactured by the method described above.
- a method for forming a semiconductor connection structure includes the steps of preparing a solder-coated pole manufactured using the method described above, and preparing a substrate on which a pad formed of a conductive material is disposed. Heating the solder-coated pole with the solder-coated pole placed on the pad; By doing so, the method includes a step of bringing the solder layer into a molten state and a step of solidifying the solder layer in the molten state, whereby the above problem is solved.
- the solder-coated pole of the present invention is a solder-coated ball having a pole-shaped core and a solder layer including Sn and Ag provided so as to surround the core, wherein the solder layer comprises: A first solder layer formed from an alloy of Sn and Ag, wherein the mass percentage of Ag in the first solder layer is 0.5% or more and 2.5% or less; and The amount of water contained in the solder layer is 100 lZg or less in the standard amount of water vapor, thereby solving the above problem.
- the solder layer may further include a second solder layer provided so as to surround the first solder layer.
- the second solder layer preferably contains Ag and has a thickness of 0.5 or less.
- the mass percentage of Ag in the solder layer is 3.0% or more and 4.0% or less.
- the first solder layer preferably has a thickness of 3 m or more and 50 / zrn or less.
- the core is preferably formed of Cu, Al, or resin.
- the mass percentage of Ag in the solder layer is 3.5%.
- the core preferably has a diameter of not less than 0.05 mm and not more than 1 mm.
- the semiconductor device of the present invention preferably includes the above-mentioned solder-coated pole.
- 1 (a) and 1 (b) are cross-sectional views of the solder-coated poles of Embodiments 1 and 2 of the present invention.
- FIGS. 2 (a) and 2 (b) are a perspective view and a sectional view of a BGA using the solder-coated poles of Embodiments 1 and 2 of the present invention, respectively.
- FIGS. 3A and 3B are diagrams illustrating an example of a method for forming a semiconductor connection structure according to the present invention.
- FIGS. 4 (a), (b) and (c) are diagrams for explaining a method of confirming a void.
- FIGS. 5 (a) and 5 (b) show the results of the photographing of Example 1 and Comparative Example 1, respectively.
- the inventors of the present invention conducted heating.
- the gas released from the solder layer during melting was analyzed.
- the main component of the released gas was found to be water vapor.
- the inventors of the present application have obtained the following findings based on this fact.
- Water vapor which is the main component of the released gas, is the water trapped in the solder layer when the solder layer was formed by the electroplating method, which was vaporized during heating and melting. During heating and melting, steam was released from the solder layer, resulting in the formation of voids. Furthermore, the cause of the trapping of moisture (a component that generates water vapor by heating) in the solder layer is mainly due to the Ag component contained in the solder layer. of This is probably due to the formation of hydrolysis products (eg, Ag (OH)).
- hydrolysis products eg, Ag (OH)
- FIG. 1 shows a cross-sectional view of a solder-coated pole 50 according to Embodiment 1 of the present invention.
- the solder-coated ball 50 has a pole-shaped core 2 and a solder layer 4 including Sn and Ag provided so as to surround the core 2.
- the solder layer 4 may be formed as a single layer as shown in FIG. 1 (a) or may be formed as a multilayer as shown in FIG. 1 (b).
- the amount of water contained is controlled so as to be 100 1 / g or less in a standard state of water vapor.
- the amount of water contained in the solder layer 4 is controlled to be sufficiently low as described above, the formation of the void when the solder layer 4 is heated and melted can be sufficiently suppressed.
- problems such as a decrease in bonding strength and displacement of the solder coating pole 50 are caused. It has been experimentally confirmed that it can be sufficiently suppressed.
- the water content is defined as follows using a thermal desorption gas analyzer (TDS: Therma 1 Desorption Spectrometer (EMD-WA100S manufactured by Electronic Science Co., Ltd.)). It is measured by the method described. And placed under an atmosphere venting of the solder coating poles below 2 X 1 0- 6 P a, to warm to room temperature or et 6 0 0 ° C at a rate of 0. 5 sec. The mass of the gas generated during this time is measured for each component using a quadrupole mass spectrometer. Using the gas component having a mass number of 18 as water, determine the total amount and convert it to the standard volume. This is the quality of solder layer 4.
- TDS Thermal desorption gas analyzer
- EMD-WA100S Therma 1 Desorption Spectrometer
- the mass of the solder layer 4 was obtained by subtracting the mass of the core 2 from the mass of the solder-coated pole 50.
- the mass of the solder layer 4 is an average value of a sample on the order of 100 pieces.
- the masses of the solder-coated pole 50 and the core 2 on the order of 100 pieces were measured using a precision balance.
- FIG. 2 shows an example of a BGA having a solder-covered pole 50.
- FIGS. 2A and 2B are a perspective view and a cross-sectional view of BGA 70, respectively.
- the BGA 70 is bonded to the interposer 62, the semiconductor chip 64 mounted on one side of the interposer 62, and the other side.
- a plurality of solder-coated poles 50 are arranged in a lattice pattern on the surface of the interposer 62 as shown in FIG.
- the semiconductor chip 64 is sealed with a resin 66.
- the semiconductor chip 64 is electrically connected to the solder coating pole 50 via a metal wire 68 and a wiring 69 formed in the interposer 62.
- the solder-coated pole 50 of the present embodiment can sufficiently suppress the formation of voids when heated and melted, so that when the solder-coated pole 50 is fixed to the interposer 62, BGA reliability can be improved because connection failure and misalignment of the BGA can be suppressed.
- solder layer 4 in which the water content is controlled so as to be equal to or less than 100 ⁇ 1 / g in the standard water vapor amount will be specifically described.
- the solder layer 4 is composed of a single plating layer containing an alloy of Sn and Ag, as shown in FIG.
- the solder layer 4 may have a multilayer structure composed of a plurality of metal layers as shown in FIG. 1 (b). That is, the solder layer 4 is composed of a first metal layer 6 provided so as to surround the core 2 and a second metal layer 8 provided so as to surround the first metal layer 6. .
- One of the first metal layer 6 and the second metal layer 8 is a layer containing Sn, and the other is a layer containing Ag.
- the composition of the solder layer 4 can be controlled by controlling the thickness of each layer constituting the solder layer 4.
- the thicknesses of the first metal layer 6 and the second metal layer 8 are determined based on the desired solder composition ratio.
- the layer containing Sn and the layer containing Ag may be disposed on either the first metal layer 6 or the second metal layer 8, but the one having excellent oxidation resistance is placed on the outside ( It is preferable to form it on the second metal layer 8). Therefore, for example, when the solder layer 4 is formed of the Sn layer and the Ag layer, it is preferable that the Ag layer be the second metal layer 8.
- the mass percentage of Ag in the solder layer 4 is appropriately determined depending on the desired composition of the solder, but typically, the mass percentage of Ag is 0.5% or more and 4.0% or less. Preferably, there is.
- the core 2 is formed of, for example, Cu.
- Cu is diffused from the core 2 to the solder layer 4 during heating, and the Cu and Sn and Ag contained in the solder layer 4 constitute the solder. Material. That is, Sn-Ag-Cu-based solder can be obtained.
- the core 2 is formed of Cu, it is desirable to set the mass percentage of Ag contained in the solder layer 4 to about 2 to 4%, more preferably about 3.5%. If the mass percentage of Ag contained in the solder layer 4 is the above value, heating will cause a ternary eutectic reaction of Sn_Ag—Cu, resulting in a single melting point (about 2 16 ° C) Is obtained. In addition, this melting point (about 2 16 ° C
- solder layer has a eutectic composition.
- the fluidity is high and the workability is excellent.
- the composition and structure of the solidified solder are high, the mechanical strength is high, and the shear strength, tensile strength, and impact resistance are high. Therefore, it is preferable to use a solder layer having a eutectic composition.
- the material of the core 2 is not limited to Cu.
- the core 2 may be formed of, for example, a metal such as A1, or may be formed of a resin.
- a metal layer such as Ni is formed on the surface of the core 2 by, for example, an electroless plating method, and the solder layer 4 is formed thereon by, for example, an electrolytic plating method. This is preferred.
- the first method is to dehydrate the plating layer by heating and melting.
- a pole-shaped core 2 is prepared.
- a plating layer containing Sn and Ag is formed so as to surround the core 2 using an electrolytic plating method.
- the plating layer is formed, for example, by electrolytic plating of an alloy of Sn and Ag.
- the plating layer is electrolytically plated with an alloy of Sn and Ag.
- Ag may be further formed by electrolytic plating (forming the second plating layer).
- it may be formed by electrolytically depositing Sn (forming a first plating layer) and then electrolytically depositing Ag (forming a second plating layer). Good.
- the core 2 on which the plating layer (single layer or multilayer) is formed is heated to keep the plating layer in a molten state for a predetermined time.
- This heating and melting is performed by placing the solder-coated port 50 on a surface with low solder wettability (for example, on a stainless steel or ceramic substrate) and in an inert atmosphere such as Ar set at atmospheric pressure.
- the heating is performed at a predetermined temperature for a predetermined time.
- the heating temperature is set to a temperature that is several 10 ° C. higher than the melting point of the material constituting the solder layer 4 finally.
- the core 2 is formed of Cu
- the plating layer is formed of an alloy of Sn and Ag, and the mass percentage of Ag contained in the plating layer is set to about 3.5% (solder layer 4
- the material is composed of a melting point (ternary eutectic point) of 2 16 ° C) and heated to about 240 ° C.
- a preferred range for a given time is from 10 minutes to 30 minutes.
- the solder layer 4 has a multilayer structure composed of a metal layer of Sn layer and Ag layer, and the Ag layer is a method other than the electrolytic plating method.
- the Ag layer is a method other than the electrolytic plating method.
- the Ag layer is formed by a method other than the electrolytic plating method.
- a solder-coated pole 50 is produced in which the amount of water contained in the solder layer 4 is controlled to be equal to or less than the above value.
- a connection structure in which a solder coated pole can be used is collectively called a semiconductor connection structure.
- This semiconductor connection structure is formed by a method described below.
- a solder-covered pole 50 and a desired substrate 20 to which the solder-covered pole 50 is to be joined are prepared.
- the substrate 20 is, for example, an interposer of a BGA (FIG. 2) or a CSP, and a pad 18 made of a conductive material is provided on a main surface of the substrate 20: a pad 18 Is composed of a laminate of a Cu layer 12, a Ni plating layer 14, and an Au plating layer 16, for example.
- the solder-coated pole 50 placed on the pad 18 the solder-coated pole 50 is heated to melt the solder layer 4 as shown in FIG. 3 (b).
- the solder layer in the molten state is indicated by 4A in FIG. 3 (b).
- solder layer 4A in the molten state is cooled and solidified, and is joined to the pad 18.
- a semiconductor connection structure is formed.
- the bonding strength of the solder-covered pole 50 to the substrate 20 is high, and problems such as displacement are unlikely to occur. Therefore, a highly reliable semiconductor connection structure is provided.
- the solder pole of the present embodiment is preferably manufactured by using an electroplating method, but the electroplating method is not limited to the method described below, and a known method can be used.
- an alkanesulfonic acid bath for example, Japanese Patent Application Laid-Open No. H08-131185, Japanese Patent Application Laid-Open No. H12-34559
- darconic acid-iodide bath for example, see Japanese Patent Application Laid-Open No. H10-36995
- tartaric acid bath for example, surface technology
- the solder layer 4 is formed of a single alloy layer of Sn and Ag.
- a method of manufacturing the solder-coated pole 50 of the first embodiment will be described.
- a 0.8 mm-diameter spherical copper core is pretreated with a 17.5% HC 1 aqueous solution at room temperature for 1 minute.
- B Rinse it with pure water at room temperature (immersion for 1 minute, running water for 1 minute).
- C Soak in organic acid for 30 seconds at room temperature.
- D Plating solution containing tin methanesulfonate (24 gZl as Sn), silver methanesulfonate (1.4 g / l as Ag), and sulfonic acid, hydroxycarboxylic acid, organic phosphorus compound, and thiourea (3 0 ° C) using, plated at a current density of 0.
- solder-coated pole of Example 1 (3.5% by mass of Ag) was produced.
- the solder layer 4 is composed of two layers: an Sn plating layer 6 and an Ag vapor deposition layer 8.
- an Sn plating layer 6 and an Ag vapor deposition layer 8.
- a spherical copper core having a diameter of 0.5 mm is pretreated with a 17.5% aqueous solution of HC 1 at room temperature for 1 minute.
- B Rinse it with pure water at room temperature (immersion for 1 minute, running water for 1 minute).
- C Immerse in organic acid at room temperature for 30 seconds.
- D using methanesulfonic tin dark liquid containing (6 0 gZ l as S n) (4 0 ° C ), and plated at a current density of 0. 3 OA / dm 2, S n plating layer ( To form a thickness of 34.2 m).
- E Wash it with pure water at room temperature (immersion for 1 minute, running water for 1 minute).
- Steps (a) to (e) are processed in a barrel container. Then, taking out the solder-coated pole from the barrel container and dried for 10 minutes at cleaned with pure water in (f) at room temperature (immersed for 2 minutes, 2 minutes running water), (i) 6 0 D C. Then, the pressure was reduced to (g) pressure 1 X 1 0 _ 4 P a , by introducing A r as an inert gas, under conditions of pressure 1 X 1 0- 2 P a, by ion plating An Ag film (0.8 m thick) is formed. (H) Wash with pure water at room temperature (immersion for 2 minutes, running water for 2 minutes), and (i) dry at 60 ° C for 10 minutes. As described above, the solder-coated pole of Example 2 (3.7% by mass of Ag) was produced.
- the solder layer 4 is composed of two layers: an Sn plating layer 6 and an Ag plating layer 8.
- an Sn plating layer 6 an Ag plating layer 8.
- Steps (a) to (g) are processed in a barrel vessel. Thereafter, the solder-coated pole is taken out of the barrel container, (h) washed with pure water at room temperature (immersion for 2 minutes, running water for 2 minutes), and (i) dried with 60 for 10 minutes. As described above, the solder-coated pole 50 of Example 3 (mass percentage of Ag: 3.6%) was produced. Since the thickness of the Ag plating layer of the solder-coated pole 50 of Example 3 was relatively thin, the amount of water contained in the solder layer could be sufficiently reduced without dehydration by heating and melting.
- the amount of water can be sufficiently reduced.
- solder-coated poles of Comparative Examples 1 to 3 were produced.
- the solder layer 4 was composed of a single alloy layer of Sn and Ag, and was not dehydrated by heating and melting.
- the solder-coated pole of Comparative Example 1 was manufactured using the same method as in Example 1 except that dehydration by heating and melting was not performed.
- the solder-coated pole of Comparative Example 2 was manufactured in the same manner as in Comparative Example 1, except that a spherical copper core having a diameter of 0.5 mm was used.
- the mass percentage of Ag of the solder-coated pole of Comparative Example 2 was 3.7%.
- the solder-coated pole of Comparative Example 3 was manufactured in the same manner as in Comparative Example 1 except that a spherical copper core having a diameter of 0.3 mm was used and the thickness of the plating layer was set to 10 m. I have.
- the mass percentage of Ag of the solder-coated pole of Comparative Example 3 was 3.6%.
- solder-coated poles of the example and the comparative example the amount of water contained in each of the solder-coated poles was measured.
- each solder-coated pole was heated and melted, the number of voids generated and the maximum diameter were measured, and photographs were taken.
- a bonding experiment was performed. The maximum diameter and the number of voids were measured as follows. First, as shown in FIG. 4 (a), solder-coated poles were arranged on a Cu substrate 30 having a main surface on which a flux 32 was arranged. Next, as shown in Fig. 4 (b), 250. By heating for 10 seconds with C, the solder layer 4 was melted (molten solder 4 A). Next, as shown in FIG.
- the joining experiment was performed as follows. 100 solder-coated poles were placed on the Cu substrate 30 as shown in FIG. 4 (a). Next, as shown in FIG. 4 (b), the solder layer 4 was heated and melted, then cooled and solidified, and joined to the substrate 30. The heating and melting were performed by allowing the substrate 30 on which the above-described solder-coated poles were arranged to stand still for 250 seconds at 250 ° (with the inside being replaced by a nitrogen atmosphere). Then, it was taken out of the oven and allowed to cool to room temperature.
- Table 1 shows the water content, the number of voids and the maximum diameter of the voids in Examples 1 to 3 and Comparative Examples 1 to 3, and the number of drops in the joining experiment. (table 1 )
- solder-coated poles of Examples 1 to 3 all had a water content of 100 1 / g or less, whereas the solder-coated poles of Comparative Examples 1 to 3 were all It exceeded 1801 / g, and was 180 to 190 lZg. Note that the solder-coated pole of Example 1 had a moisture content of 1901 Zg (corresponding to Comparative Example 1) before heat-melting and dehydration, but changed to 301 / g after heat-melting and dehydration. .
- the solder-coated pole according to the second embodiment has a water content in the solder layer 4 containing Sn and Ag of 100 ⁇ 1Z as a standard amount of water vapor, similarly to the solder-coated pole of the first embodiment. It is controlled to be less than or equal to g. Therefore, similarly to Embodiment 1, the formation of voids when the solder layer 4 is heated and melted can be sufficiently suppressed.
- the amount of water contained in the solder layer 4 is controlled to be equal to or less than the above value, sufficient problems such as a decrease in bonding strength and displacement of the solder coating pole 50 can be sufficiently obtained. It was confirmed experimentally that it could be suppressed.
- the main feature of the second embodiment is that the solder layer includes a solder layer made of an alloy of Sn and Ag formed by an electrolytic plating method using a predetermined plating solution.
- solder-covered pole 50 of the second embodiment will be described with reference to FIGS. 1 (a) and (b).
- FIG. 1 shows that the solder layer included in the solder-coated pole of Embodiment 2 includes at least a solder layer formed of an alloy of Sn and Ag.
- It may be formed of a single layer as shown in (a), or may be formed of multiple layers as shown in FIG. 1 (b).
- solder-coated pole 50 is connected to the core 2 and the solder layer 4 formed from an alloy of Sn and Ag, as shown in FIG. Is provided.
- the solder-coated pole 50 is provided so as to surround the first metal layer 6 and the first metal layer 6, as shown in FIG. 1 (b).
- a solder layer (4) composed of a second metal layer (8) is provided.
- the first metal layer 6 is a solder layer formed of, for example, an alloy of Sn and Ag
- the second metal layer 8 is a solder layer formed of, for example, Ag. It is.
- the first metal layer 6 and the second metal layer 8 are referred to as a first solder layer 6 and a second solder layer 8, respectively.
- the solder layer 4 was substantially composed of the alloy of Sn and Ag shown in Fig. 1 (a). The same solder as in the case can be realized at least in the joined state.
- the composition of the solder layer 4 can be controlled by controlling the thickness of each layer constituting the solder layer 4.
- a pole-shaped core 2 is prepared.
- a solder layer 4 made of an alloy of Sn and Ag is formed so as to surround the core 2 by using an electrolytic plating method.
- the plating solution contains tris (3-hydroxypropyl) phosphine 10 to 25 g / l, organic sulfonic acid Sn 15 to 25 g Z1, and organic sulfonic acid A g of 0.3 to 1.5. g / 1, a solution containing 50 to 100 g / l of organic sulfonic acid and ammonia. Ammonia is added to adjust the pH of the solution.
- PH is preferably adjusted to 3.5 to 5.0.
- the organic sulfonate Sn, the organic sulfonic acid Ag, and the organic sulfonic acid include methanesulfonic acid Sn, maleic sulfonic acid Ag, and methanesulfonic acid, which are described in Examples below. used. More preferably, the plating solution further contains thiourea 3 to 12 g "1. For details of the plating solution, see Japanese Patent Application Laid-Open No. 2000-34559. It is described in Japanese Patent Publication No. 3 Using the above plating solution, the solder layer 4 is formed so that the Ag mass percentage is in the range of 2.5% or less.
- the electroplating is preferably carried out by controlling the current density to 0.1 to 0.6 AZdm 2 and the temperature of the plating solution to 20 to 30.
- a solder-covered ball 50 is produced in which the amount of water contained in the solder layer 4 is controlled to be 100 1 / g or less in terms of water vapor in a standard state.
- the amount of moisture contained in the solder layer 4 can be sufficiently reduced without special treatment.
- the solder layer 4 may have a multilayer structure as shown in FIG. 1 (b).
- the Ag mass percentage of the solder layer 4 is larger than 2.5%, the crystal structure becomes finer when the solder layer 4 is melted. Therefore, the bonding strength of the solder-coated pole 50 can be increased.
- the solder-coated pole 50 having a multilayered solder layer is manufactured by forming the first solder layer 6 using the above-described electrolytic plating method, and then forming the second solder layer 8 containing Ag. You.
- the first solder layer 6 preferably has a Ag mass percentage of 0.5% or more. If the Ag mass percentage of the first solder layer 6 is set to 0.5% or more, the surface roughness of the first solder layer 6 can be sufficiently reduced, so that the adhesion to the second solder layer 8 can be improved. Can be higher.
- the second solder layer 8 made of Ag is formed by, for example, an electrolytic plating method, a vapor deposition method, or a colloid method.
- the thickness of the second solder layer 8 is set to 0.5 m or less.
- electrolytic plating The reason why moisture is trapped in the solder layer formed by the method is mainly that
- the second solder layer 8 is formed by a method other than the electrolytic plating method, it is not necessary to set the thickness to 0.5 m or less, but if the thickness is set to the above value or less, the melting is performed. Occasionally, the solder layer tends to have a uniform composition, thereby suppressing the formation of abnormal grains.
- the Ag mass percentage of the solder layer 4 exceeds 2.5%, and the amount of water contained in the solder layer 4 is 1001 / g or less in terms of water vapor in a standard state.
- a solder-coated pole 50 controlled in a predetermined manner.
- the thicknesses of the first solder layer 6 and the second solder layer 8 are determined based on a target solder composition ratio.
- the solder-coated pole 50 shown in FIG. 1 (b) has a structure in which the first solder layer 6 is an Ag layer and the second solder layer 8 is an alloy layer of Sn and Ag. Although it is good, it is preferable to form the one having excellent oxidation resistance on the outside (the second solder layer 8).
- the alloy layer of Sn and Ag contains various composition grains, when the alloy layer of Sn and Ag is used as the second solder layer 8, the If left in the air for a long period of time, oxidation of the surface tends to proceed, resulting in deformation due to corrosion, reduced wettability during soldering, and reduced bonding strength. Therefore, it is preferable that the first solder layer 6 be an alloy layer of Sn and Ag, and the second solder layer 8 be an Ag layer.
- the mass percentage of Ag in the solder layer 4 is preferably 3.0% or more and 4.0% or less. Mass of Ag contained in solder layer 4 If the fraction is about 3.5%, heating causes a binary eutectic reaction of Sn—Ag, resulting in a single melting point (about 221 ° C). As will be described later, setting the components of the solder layer to the eutectic composition has various advantages such as a sufficiently high bonding strength. Also, if the mass percentage of Ag exceeds 4.0%, coarse Ag 3 Sn plate-like primary crystals (or needle-like primary crystals) are crystallized by heating, and cracks are formed in the solder layer. Therefore, the mass percentage of Ag is preferably 4.0% or less (“Trump-free soldering technology, the key to environmentally friendly mounting” by Katsuaki Suganuma, published by the Industrial Research Institute, (2001) January 20))).
- the core 2 is formed of, for example, Cu.
- Cu diffuses from the core 2 to the solder layer 4 during heating, and the Cu and Sn and Ag contained in the solder layer 4 constitute the solder. Material. That is, Sn-Ag-Cu-based solder is obtained.
- the mass percentage of Ag contained in the solder layer 4 may be set to 2.0% or more and 4.0% or less, more preferably, about 3.5%. desirable. If the mass percentage of Ag contained in the solder layer 4 is the above value, heating causes a ternary eutectic reaction of Sn—Ag—Cu, resulting in a single melting point (about 2 16) Is obtained. This melting point (about 2 16 ° C) is lower than the melting point of the binary eutectic of Sn-Ag (about 2 21 ° C). The melting point was the onset temperature (melting start temperature) of the DTA curve measured at a heating rate of 2 ° C / min.
- solder layer has a eutectic composition.
- the fluidity is high and the workability is excellent.
- the composition and structure of the solidified solder are high, the mechanical strength is high, and the shear strength, tensile strength, and impact resistance are high. High in nature. Therefore, it is preferable to use a solder layer having a eutectic composition.
- the material of the core 2 is not limited to Cu.
- the core 2 may be formed of, for example, a metal such as A1, or may be formed of a resin.
- a metal layer such as Ni is formed on the surface of the core 2 by, for example, electroless plating, and the solder layer 4 is formed thereon by, for example, electrolytic plating. Is preferred.
- the diameter of the core 2 is typically in the range from 0.05 mm to 1 mm. When the size of the core 2 is in the above range, the strength at the time of joining can be sufficiently increased. Also, it can be bonded to a substrate or the like at a sufficiently high density.
- the thickness of the solder layer 4 or 6 formed of an alloy with Sn ⁇ Ag is typically 3 m or more and 50 m or less.
- the solder coating pole 50 of the second embodiment is used for input / output terminals such as BGA (see FIG. 2) and CSP.
- BGA see FIG. 2
- CSP input / output terminals
- the use of the solder-coated pole 50 sufficiently suppresses the formation of voids when the solder-coated pole 50 is melted by heating, so that the connection failure when fixing the solder-coated pole 50 to the interposer 62 and the position Since the deviation can be suppressed, the reliability of the BGA can be improved.
- the bonding strength of the solder-coated pole 50 to the substrate 20 is high, and problems such as misalignment hardly occur.
- a semiconductor connection structure having a high level can be provided. This semiconductor connection structure is manufactured by using the same method as that described in Embodiment 1 with reference to FIG.
- the solder layer 4 is formed of a single alloy layer of Sn and Ag.
- a method for manufacturing the solder-coated pole 50 of the fourth embodiment will be described.
- a spherical copper core 2 having a diameter of 0.85 mm is prepared. Also, 15 g 1 of tris (3-hydroxypropyl) phosphine, Sn of methanesulfonic acid (24 gZl as Sn), Ag of methanesulfonic acid (0.7 gZl as Ag), methanesulfonic acid Prepare a solution containing 60 gZ1 and 5 g / 1 thiourea, and adjust the pH to 4.0 by adding ammonium salt.
- plating was performed at a current density of 0.3 OA / dm 2 and a bath temperature of 30 ° C using Sn as the anode electrode, and an alloy plating layer of Sn and Ag (thickness 3 5 m) 4 is formed on the surface of the copper core 2.
- the electroplating process is processed in a barrel vessel.
- the solder-coated pole of Example 4 (the mass percentage of Ag of the solder layer 4 was 1.8%) was produced.
- the solder coating pole 50 of the fifth embodiment has the solder layer 4 made of a single alloy layer of Sn and Ag.
- a method of manufacturing the solder-coated pole 50 of the fifth embodiment will be described.
- a spherical copper core 2 having a diameter of 0.60 mm is prepared. 20 g / l of tris (3-hydroxypropyl) phosphine, Sn of methanesulfonic acid (24 g / l as Sn), Ag of methanesulfonic acid (0.95 g / l of Ag), 70 g / 1 methanesulfonic acid, and Prepare a solution containing thiourea 5 gZ 1, add ammonia salt, adjust the pH to pH 4.0, and prepare a drip solution.
- plating is performed at a current density of 0.3 OA / dm 2 and a bath temperature of 20 with Sn as the anode electrode.
- An alloy plating layer of Sn and Ag (20 m thick) 4 is formed on the surface of the copper core 2.
- the electrolytic plating step is performed in a barrel container.
- the solder layer 4 is composed of an alloy layer 6 of 311 and 88 and an Ag layer 8.
- a method for manufacturing the solder-coated pole 50 of the sixth embodiment will be described.
- a spherical copper core 2 having a diameter of 0.50 mm is prepared. Also, 13 gZl of tris (3-hydroxypropyl) phosphine, Sn of methanesulfonic acid (24 gZl as Sn), Ag of methanesulfonic acid (0.4 gZl as Ag), and methane Prepare a solution containing 50 g Z 1 of sulfonic acid, and adjust the pH to 4.0 by adding ammonia.
- plating was performed at a current density of 0.30 AZ dm 2 and a bath temperature of 30 ° C using Sn as the anode electrode.
- An alloy layer of Sn and Ag (10 m thick) 6 is formed on the surface of the copper core 2.
- the mass percentage of Ag in the alloy layer 6 is 1.0%.
- the above-mentioned alloy layer is formed by electrolytic plating using a silver iodide plating bath.
- An Ag layer (thickness 0.17 ⁇ 11) 8 is formed on 6.
- the electroplating process is performed in a barrel vessel.
- the solder-coated pole of Example 6 was produced.
- the solder layer 4 of this solder-coated pole is composed of an alloy layer 6 of Sn and Ag and an Ag layer 8, and the mass percentage of Ag in the solder layer 4 is 3.5%.
- solder-coated poles of Comparative Examples 4 to 6 described below were prepared.
- the solder-coated pole of Comparative Example 4 differs from that of Example 4 in performing electrolytic plating using the following plating solution.
- the liquid used in Comparative Example 4 was methanesulfonic acid Sn (20 gZl as Sn), Ag methanesulfonate (0.3 g / l Ag), and methanesulfonic acid (100 g / 1 ), And the PH has been adjusted to less than 1.0.
- Example 4 Using the above-mentioned plating solution, plating was performed under the same conditions as in Example 4 except that the bath temperature was set to 25 ° C. Formed on the surface. By the above method, the solder-coated pole of Comparative Example 4 (1.8% by mass of Ag) was produced.
- the solder-coated pole of Comparative Example 5 differs from that of Example 5 in performing electrolytic plating using the following plating solution.
- the plating solutions used in Comparative Example 5 were sulfuric acid Sn (17 gZl as Sn), Ag sulfate (0.
- Example 5 Using the above-mentioned plating solution, plating was performed under the same conditions as in Example 5 except that the bath temperature was set to 25 ° C, and the plating layer of the alloy of Sn and Ag (thickness: 20 zm) was Formed on the surface of the core.
- the bath temperature was set to 25 ° C
- the plating layer of the alloy of Sn and Ag (thickness: 20 zm) was Formed on the surface of the core.
- a solder-coated pole of Comparative Example 5 (Ag mass percentage: 2.4%) was produced.
- the solder-coated pole of Comparative Example 6 differs from that of Example 6 in that the following plating solution is used for plating an alloy of Sn and Ag.
- the solution used in Comparative Example 6 was methanesulfonic acid Sn (18 g / l as Sn), methanesulfonic acid Ag (0.2 g / l as Ag), and methanesulfonic acid (10%). 0 g / 1) 1 "1 is adjusted to less than 1.0.
- plating was carried out under the same conditions as in Example 6 except that the bath temperature was set at 25 ° C. Formed on the surface.
- the mass percentage of Ag in the alloy-coated layer is 1.0%.
- Example 6 using the same silver iodide plating bath as in Example 6, an Ag layer (0.17 zm in thickness) is formed on the above-mentioned alloy-coated layer.
- the solder-coated pole of Comparative Example 6 was produced.
- the solder layer of this solder-coated pole is composed of an alloyed layer of Sn and Ag and an Ag layer, and the mass percentage of Ag in the solder layer is 3.5%.
- solder-coated poles of the example and the comparative example the amount of water contained in each of the solder-coated poles was measured.
- each solder-coated pole was heated and melted, and the number of generated voids and the maximum diameter were measured.
- bonding experiments were performed. The maximum diameter and the number of voids were measured as follows. First, as shown in FIG. 4 (a), solder-coated poles were arranged on a Cu substrate 30 having a main surface on which a flux 32 was arranged. Next, as shown in FIG. 4B, the solder layer 4 was melted by heating at 250 ° C. for 10 seconds (molten solder 4A). Next, as shown in FIG.
- the joining experiment was performed as follows. 100 solder-coated poles were placed on the Cu substrate 30 as shown in FIG. 4 (a). Next, as shown in FIG. 4 (b), the solder layer 4 was heated and melted, then cooled and solidified, and joined to the substrate 30. The heating and melting were performed by allowing the substrate 30 on which the above-mentioned solder-coated poles were arranged to stand for 10 seconds in an oven in which the inside was replaced with a nitrogen atmosphere (250 °) for 10 seconds. Removed from oven and allowed to cool to room temperature.
- Table 2 shows the water content, the number of voids and the maximum diameter of the voids of Examples 4 to 6 and Comparative Examples 4 to 6, and the number of drops in the joining experiment. (Table 2)
- solder-coated poles of Examples 4 to 6 all had a water content of 100 ⁇ 1 / g or less, whereas the solder-coated poles of Comparative Examples 4 to 6 all had Was also 200 1 / g.
- solder-coated pole having an Sn-Ag-based solder layer in which the generation of voids during heating and melting is suppressed, and a method of manufacturing the same are provided.
- the solder-coated pole of the present invention is suitably used for input / output terminals such as BGA and CSP.
Landscapes
- Engineering & Computer Science (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Computer Hardware Design (AREA)
- Power Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Electric Connection Of Electric Components To Printed Circuits (AREA)
- Powder Metallurgy (AREA)
- Wire Bonding (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Description
Claims
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP03798471A EP1551211B1 (en) | 2002-09-27 | 2003-09-24 | Solder-coated ball and method for manufacture thereof, and method for forming semiconductor interconnecting structure |
AU2003266588A AU2003266588A1 (en) | 2002-09-27 | 2003-09-24 | Solder-coated ball and method for manufacture thereof, and method for forming semiconductor interconnecting structure |
US10/529,172 US7265046B2 (en) | 2002-09-27 | 2003-09-24 | Method of making a solder ball |
DE60325620T DE60325620D1 (de) | 2002-09-27 | 2003-09-24 | Lotbeschichtete kugel und verfahren zu ihrer herstellung und verfahren zur bildung einer halbleiterverbindungsstruktur |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2002283301A JP4175857B2 (ja) | 2002-09-27 | 2002-09-27 | はんだ被覆ボールの製造方法 |
JP2002-283301 | 2002-09-27 | ||
JP2002-291187 | 2002-10-03 | ||
JP2002291187A JP4175858B2 (ja) | 2002-10-03 | 2002-10-03 | はんだ被覆ボールの製造方法 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2004030428A1 true WO2004030428A1 (ja) | 2004-04-08 |
Family
ID=32044636
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2003/012183 WO2004030428A1 (ja) | 2002-09-27 | 2003-09-24 | はんだ被覆ボールおよびその製造方法、ならびに半導体接続構造の形成方法 |
Country Status (7)
Country | Link |
---|---|
US (1) | US7265046B2 (ja) |
EP (1) | EP1551211B1 (ja) |
KR (1) | KR20050042060A (ja) |
CN (1) | CN100405883C (ja) |
AU (1) | AU2003266588A1 (ja) |
DE (1) | DE60325620D1 (ja) |
WO (1) | WO2004030428A1 (ja) |
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EP1900471A1 (en) * | 2005-05-27 | 2008-03-19 | Neomax Materials Co., Ltd. | Silver-coated ball and method for manufacturing same |
WO2014207897A1 (ja) * | 2013-06-28 | 2014-12-31 | 千住金属工業株式会社 | はんだ材料及びはんだ継手 |
CN108430689A (zh) * | 2015-12-01 | 2018-08-21 | 三菱综合材料株式会社 | 焊料粉末及使用该粉末的焊接用浆料的制备方法 |
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---|---|---|---|---|
EP1900471A1 (en) * | 2005-05-27 | 2008-03-19 | Neomax Materials Co., Ltd. | Silver-coated ball and method for manufacturing same |
EP1900471A4 (en) * | 2005-05-27 | 2010-06-02 | Neomax Materials Co Ltd | SILVER COATED BALL AND MANUFACTURING METHOD THEREFOR |
US8039107B2 (en) | 2005-05-27 | 2011-10-18 | Neomax Materials Co., Ltd. | Silver-coated ball and method for manufacturing same |
US20110318484A1 (en) * | 2005-05-27 | 2011-12-29 | Neomax Materials Co., Ltd. | Silver-coated ball and method for manufacturing same |
WO2014207897A1 (ja) * | 2013-06-28 | 2014-12-31 | 千住金属工業株式会社 | はんだ材料及びはんだ継手 |
CN108430689A (zh) * | 2015-12-01 | 2018-08-21 | 三菱综合材料株式会社 | 焊料粉末及使用该粉末的焊接用浆料的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
US7265046B2 (en) | 2007-09-04 |
DE60325620D1 (de) | 2009-02-12 |
EP1551211A4 (en) | 2005-12-07 |
CN1572129A (zh) | 2005-01-26 |
US20060055054A1 (en) | 2006-03-16 |
KR20050042060A (ko) | 2005-05-04 |
CN100405883C (zh) | 2008-07-23 |
EP1551211A1 (en) | 2005-07-06 |
AU2003266588A1 (en) | 2004-04-19 |
EP1551211B1 (en) | 2008-12-31 |
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