WO2016031067A1 - はんだ材料、はんだ継手及びはんだ材料の製造方法 - Google Patents

はんだ材料、はんだ継手及びはんだ材料の製造方法 Download PDF

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Publication number
WO2016031067A1
WO2016031067A1 PCT/JP2014/072803 JP2014072803W WO2016031067A1 WO 2016031067 A1 WO2016031067 A1 WO 2016031067A1 JP 2014072803 W JP2014072803 W JP 2014072803W WO 2016031067 A1 WO2016031067 A1 WO 2016031067A1
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Prior art keywords
solder
less
sno
layer
film
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PCT/JP2014/072803
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English (en)
French (fr)
Inventor
浩由 川▲崎▼
六本木　貴弘
相馬　大輔
佐藤　勇
勇司 川又
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千住金属工業株式会社
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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 EP14900789.0A priority Critical patent/EP3187299B1/en
Priority to KR1020167036699A priority patent/KR101781777B1/ko
Priority to PCT/JP2014/072803 priority patent/WO2016031067A1/ja
Priority to PT149007890T priority patent/PT3187299T/pt
Priority to CN201480080357.3A priority patent/CN106536124B/zh
Priority to US15/327,510 priority patent/US10173287B2/en
Priority to JP2015525662A priority patent/JP5807733B1/ja
Priority to TW104128294A priority patent/TWI543835B/zh
Publication of WO2016031067A1 publication Critical patent/WO2016031067A1/ja

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0244—Powders, particles or spheres; Preforms made therefrom
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B22F1/16—Metallic particles coated with a non-metal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/22—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by the composition or nature of the material
    • B23K35/24—Selection of soldering or welding materials proper
    • B23K35/26—Selection of soldering or welding materials proper with the principal constituent melting at less than 400 degrees C
    • B23K35/262—Sn as the principal constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • 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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    • B23K35/365—Selection of non-metallic compositions of coating materials either alone or conjoint with selection of soldering or welding materials
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    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
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    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/13001—Core members of the bump connector
    • H01L2224/13099—Material
    • H01L2224/131—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof
    • H01L2224/13138—Material with a principal constituent of the material being a metal or a metalloid, e.g. boron [B], silicon [Si], germanium [Ge], arsenic [As], antimony [Sb], tellurium [Te] and polonium [Po], and alloys thereof the principal constituent melting at a temperature of greater than or equal to 950°C and less than 1550°C
    • H01L2224/1316—Iron [Fe] as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/1354—Coating
    • H01L2224/1356—Disposition
    • H01L2224/13561—On the entire surface of the core, i.e. integral coating
    • H—ELECTRICITY
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    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/1354—Coating
    • H01L2224/13575—Plural coating layers
    • H01L2224/1358—Plural coating layers being stacked
    • H01L2224/13582—Two-layer coating
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/1354—Coating
    • H01L2224/13599—Material
    • H01L2224/13686—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2224/00—Indexing scheme for arrangements for connecting or disconnecting semiconductor or solid-state bodies and methods related thereto as covered by H01L24/00
    • H01L2224/01—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
    • H01L2224/10—Bump connectors; Manufacturing methods related thereto
    • H01L2224/12—Structure, shape, material or disposition of the bump connectors prior to the connecting process
    • H01L2224/13—Structure, shape, material or disposition of the bump connectors prior to the connecting process of an individual bump connector
    • H01L2224/1354—Coating
    • H01L2224/13599—Material
    • H01L2224/13686—Material with a principal constituent of the material being a non metallic, non metalloid inorganic material
    • H01L2224/13687—Ceramics, e.g. crystalline carbides, nitrides or oxides
    • 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
    • H01L2924/01—Chemical elements
    • H01L2924/0105—Tin [Sn]
    • 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
    • H01L2924/013—Alloys
    • H01L2924/014—Solder alloys
    • 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
    • H01L2924/053—Oxides composed of metals from groups of the periodic table
    • H01L2924/0544—14th Group

Definitions

  • the present invention relates to a solder material mainly composed of Sn, a solder joint, and a method for manufacturing the solder material.
  • BGA ball grid array
  • An electronic component to which BGA is applied includes, for example, a semiconductor package.
  • a semiconductor package a semiconductor chip having electrodes is sealed with a resin.
  • Solder bumps are formed on the electrodes of the semiconductor chip. This solder bump is formed by joining a solder ball to an electrode of a semiconductor chip.
  • a semiconductor package using BGA is mounted on a printed circuit board by placing the solder bumps on the printed circuit board so that each solder bump contacts the conductive land of the printed circuit board, and the solder bumps and lands melted by heating are joined. Is done.
  • solder ball in order to join the solder ball to the electrode, it is required to suppress the formation of a metal oxide film on the surface of the solder ball. Moreover, when a solder ball is mixed with a flux and used as a solder paste, it is required to suppress an increase in viscosity during storage.
  • Patent Document 1 there is a proportional relationship between the film thickness of the oxide film formed on the solder ball surface and the yellowness. Therefore, a technique has been proposed in which solder balls having a yellowness of a predetermined value or less, that is, an oxide film having a predetermined value or less are used, and the oxide film is destroyed by heating so that bonding is possible (for example, Patent Document 1). reference).
  • Patent Document 1 solder balls having a surface yellowing degree of 10 or less after selection are selected, and the storage state is strictly controlled to prevent solder ball surface yellowing. It is disclosed that a SnO oxide film and a SnO 2 oxide film are formed on the surface of a solder bump formed using this solder ball while suppressing the growth of the SnO oxide film on the surface.
  • JP 2009-248156 A Japanese Patent No. 4084657
  • solder ball mainly composed of Sn, Sn and O 2 in the air react to form a SnO film.
  • this film thickness increases, it becomes difficult to remove with a flux at the time of soldering.
  • oxide film remains on the surface of the solder ball, wettability deteriorates.
  • the oxide film thickness increases, the yellowness increases. In some cases, yellowness is used as an appearance inspection of solder balls. If the increase in the oxide film thickness cannot be suppressed, the possibility that the solder balls are not suitable for use increases.
  • Patent Document 1 the storage state is strictly controlled to suppress the growth of the SnO oxide film on the solder ball surface. Further, in Patent Document 1, the bonding property between the solder and the electrode terminal is improved by paying attention to the fact that the crystalline SnO 2 oxide film is easily damaged by internal deformation accompanying melting of the solder ball. There is no disclosure about suppressing the growth of the oxide film with the composition of the oxide film other than the management of the state. Furthermore, with respect to Patent Document 2, there is no disclosure about suppressing the growth of the SnO oxide film.
  • an object of the present invention is to provide a solder material, a solder joint, and a method for manufacturing a solder material that can suppress the growth of an oxide film, and thereby have good storage properties and wettability.
  • the present inventors have found that the growth of an oxide film can be suppressed by coating a solder layer containing Sn as a main component with a coating layer containing SnO and SnO 2 .
  • the coating layer containing SnO and SnO 2 means an oxide film layer made of tin oxide mainly containing SnO and an oxide film layer made of tin oxide mainly containing SnO 2 . The same applies to the following description.
  • the invention according to claim 1 covers the surface of the solder layer with a solder layer made of a metal material made of an alloy having a Sn content of 40% or more or a metal material having a Sn content of 100%.
  • a solder material comprising a coating layer, wherein the coating layer has an SnO film formed on the outside of the solder layer, an SnO 2 film formed on the outside of the SnO film, and the thickness of the coating layer is greater than 0 nm and not more than 4.5 nm It is.
  • the invention according to claim 2 is the solder material according to claim 1, wherein the yellowness is 5.7 or less.
  • a solder layer made of a metal material made of an alloy having a Sn content of 40% or more or a metal material having a Sn content of 100%, and a coating layer covering the surface of the solder layer
  • the covering layer is a solder material in which a SnO film is formed outside the solder layer, a SnO 2 film is formed outside the SnO film, and the yellowness is 5.7 or less.
  • the solder layer includes Ag of 0% to less than 4%, Cu of 0% to less than 1%, P of 0 ppm to less than 5 ppm, and Ge of 0 ppm to less than 20 ppm.
  • solder layer in the solder layer, (i) at least one element selected from Ni, Co, Fe, and Sb is less than 1% in total so that the Sn content is 40% or more.
  • the solder material according to any one of claims 1 to 4, wherein the solder material contains less than 40% in total or less than 40% of one of In and Bi and less than 20% of the other.
  • the invention according to claim 6 is the solder material according to any one of claims 1 to 5, wherein the emitted ⁇ dose is 0.0200 cph / cm 2 or less.
  • the invention according to claim 7 is the solder material according to any one of claims 1 to 6, which is a sphere having a diameter of 1 to 1000 ⁇ m.
  • the invention according to claim 8 is a solder joint obtained by using the solder material according to any one of claims 1 to 7.
  • the invention according to claim 9 includes a solder layer forming step of forming a solder layer made of a metal material made of an alloy having a Sn content of 40% or more or a metal material having a Sn content of 100%, and a solder layer the SnO film was formed on the outside of, to form a SnO 2 film on the outside of the SnO film, a greater than 4.5nm or less of the coating layer thickness is 0 nm, comprising an oxide film formation step of forming on the surface of the solder layer
  • the invention according to claim 10 is the method for producing a solder material according to claim 9, wherein the yellowness of the surface of the coating layer is formed to be 5.7 or less in the oxide film forming step.
  • the invention according to claim 11 is the method for producing a solder material according to claim 9 or 10, wherein the oxide film forming step irradiates the surface of the solder layer with O 2 —Ar plasma.
  • the reaction between Sn and O 2 in the air is suppressed, and the growth of the SnO film and the SnO 2 film is suppressed.
  • an increase in film thickness can be suppressed, and an increase in film thickness is suppressed, whereby yellowing can be suppressed and yellowness can be suppressed to 5.7 or less.
  • FIG. 1 is a cross-sectional view showing a schematic structure of a solder ball as an example of the solder material of the present embodiment.
  • units (ppm, ppb, and%) relating to the composition of the solder material represent ratios (mass ppm, mass ppb, and mass%) relative to mass unless otherwise specified.
  • the solder ball 1A of the present embodiment includes a solder layer 2 and a coating layer 3 that covers the solder layer 2.
  • the solder layer 2 is spherical, and is made of an alloy material in which Ag is 0% or more and less than 4%, Cu is 0% or more and less than 1%, and the Sn content is 40% or more.
  • the oxidation resistance is improved by adding a predetermined amount of P or Ge.
  • the oxidation resistance can be improved without adding them.
  • the addition of less than 5 ppm P and less than 20 ppm Ge does not impair the effects of the present invention.
  • P or Ge does not have to be added, and if added, the addition amount of P is less than 5 ppm and the addition amount of Ge is less than 20 ppm. Therefore, the addition amount of P is 0 ppm or more and less than 5 ppm, and the addition amount of Ge is 0 ppm or more and less than 20 ppm.
  • the solder layer 2 contains at least one element selected from Ni, Co, Fe, and Sb so that the Sn content is 40% or more as a whole, or less than 1%, or less than 1% of each, And, at least one element selected from In and Bi is contained in total of less than 40%, or one of In and Bi is less than 40% and the other is less than 20%.
  • At least one element selected from Ni, Co, Fe, and Sb is contained less than 1% or less than 1% in total, or at least one element selected from In and Bi is added as a whole Less than 40%, or one of In and Bi is less than 40% and the other is less than 20%.
  • solder layer 2 may be made of a metal material having a Sn content of 100%. Note that the ⁇ dose emitted from the solder layer 2 is preferably 0.0200 cph / cm 2 or less.
  • the SnO film 3a is formed outside the solder layer 2
  • the SnO 2 film 3b is formed outside the SnO film 3a.
  • the solder ball 1A preferably has a diameter of 1 to 1000 ⁇ m.
  • the thickness of the covering layer 3 is preferably greater than 0 nm (meaning that 0 nm is not included) and 4.5 nm or less. When the thickness of the coating layer 3 exceeds 4.5 nm, it becomes difficult to remove the coating layer 3 with a flux during soldering, and the wettability is deteriorated.
  • the yellowness b * of the solder ball 1A is preferably 5.7 or less.
  • yellowness may be used. This is because high yellowness means that the film thickness of SnO is thick, so that solder balls whose yellowness exceeds a predetermined value can be excluded as being unsuitable for use.
  • the lightness and yellowness are measured using a Konica Minolta CM-3500d2600d spectrophotometer, using a D65 light source and a 10-degree field of view according to JIS Z 8722 “Color measurement method: reflection and transmission object color”. was determined from the color values (L * , a * , b * ).
  • the color values (L * , a * , b * ) are defined in JIS Z 8729 “Color Display Method—L * a * b * Color System and L * U * V * Color System”. It is as follows.
  • the shape of the solder material is spherical in this example, but may be other shapes such as a cylindrical shape or a quadrangular prism shape.
  • the ⁇ dose emitted from the solder ball 1A is also preferably 0.0200 cph / cm 2 or less.
  • 2A, 2B, and 2C are cross-sectional views schematically showing a method for manufacturing a solder ball as an example of the solder material of the present embodiment.
  • solder layer forming step As shown in FIG. 2A, a spherical solder layer 2 made of the above-described metal material made of an alloy having a Sn content of 40% or more, or a metal material having a Sn content of 100%. Is formed.
  • the solder layer forming step uses a dropping method in which a molten metal material is dropped to be cured in a spherical shape.
  • an SnO 2 film 3b is formed on the surface of the SnO film 3a generated when the surface of the solder layer 2 is exposed to air, as shown in FIG. 2C.
  • a conventionally known method can be used.
  • an evaporation method, a sputtering method, a plasma irradiation method, and the like can be given.
  • the oxide film forming step is realized by a plasma irradiation method using a known atmospheric pressure plasma apparatus.
  • the plasma irradiation method high-concentration O 2 —Ar plasma is irradiated before molten metal is dropped and cured.
  • the solder ball 1A in which the coating layer 3 is formed on the surface of the solder layer 2 having a predetermined diameter is manufactured by the above manufacturing method.
  • the coating layer 3a has a thickness greater than 0 nm and not greater than 4.5 nm.
  • the SnO film 3a is formed outside the solder layer 2, and the SnO 2 film 3b is formed outside the SnO film 3a.
  • the yellowness of the solder ball 1A is 5.66 or less.
  • a metal ball corresponding to the solder layer 2 was formed by a dropping method using a metal material composed of 3% Ag, 0.5% Cu, and the balance Sn.
  • a film corresponding to the coating layer 3 was formed on the metal sphere by a plasma irradiation method to produce the solder ball of the example.
  • the plasma irradiation method high concentration O 2 —Ar plasma was irradiated before the molten metal material was dropped.
  • solder ball having a SnO layer formed on the surface by natural oxidation was generated.
  • Table 1 shows the results of heating the solder balls of Examples and Comparative Examples at 200 ° C. and observing the oxidation behavior with the value of yellowness b * .
  • the solder ball of the comparative example quickly increased in yellowness b *, whereas the solder ball of the example had a solder layer mainly composed of Sn by qualitative analysis by SERA. It was found that the growth of the oxide film thickness was suppressed by forming the SnO layer on the outer side and the SnO 2 layer on the outer side of the SnO layer.
  • the oxide film thicknesses of the solder balls of Example 1 heated at 200 ° C. for 15 minutes and the solder balls of Example 2 heated at 200 ° C. for 30 minutes are defined as FE-AES (electric field).
  • SERA Sequential Electrochemical Analysis: Sequential Electrochemical Reduction
  • SnO and SnO 2 the components of the formed oxide film are Sn oxides (SnO and SnO 2 ).
  • Quantitative analysis was performed with FE-AES.
  • the analysis values with SERA are easy to disperse and qualitative analysis is possible, but to discuss specific oxide film thickness as quantitative analysis, FE-AES analysis This is because it is easier to show a constant value.
  • the thickness of the oxide film was measured with the following apparatus and conditions. Incidentally, the oxide film thickness measurements were determined by the terms of SiO 2.
  • Measuring device ULVAC-PHI, INC. Scanning FE Auger Electron Spectroscopy Analyzer Measuring conditions: Beam Voltage: 10 kV, Sample current: 10 nA (The sputtering depth measurement method using an Ar ion gun is based on ISO / TR 15969. .)
  • Table 2 shows the measurement results of oxide film thickness and yellowness.
  • the oxide film thickness is suppressed to 5 nm or less, and the film thickness of the coating layer is preferably 4.5 nm or less. Moreover, it turns out that the yellowness is suppressed to 10 or less, and it turns out that it is preferable to set it as 5.7 or less from the result of Table 2.
  • the solder ball of each example has a film thickness of 4.5 nm or less, the solder ball of example 1 has a film thickness of 2.6 nm, and the solder ball of example 2 has a film thickness of 4.1 nm.
  • the solder ball No. 3 has a film thickness of 1.5 nm.
  • solder balls of each example have a yellowness of 5.7 or less, the solder balls of example 1 have a yellowness of 4.60, and the solder balls of example 2 have a yellowness of 5.77.
  • the solder ball of Example 3 has a yellowness of 3.90.
  • the solder ball of each comparative example has a film thickness of 10 nm or more and a yellowness of 10 or less.
  • the solder ball of comparative example 1 has a yellowness of 10.21, and the solder ball of comparative example 2 has The yellowness is 13.15.
  • solder material according to the present invention can be used for a solder joint of an electronic component by being electrically joined to an electrode with a solder paste.

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  • Organic Chemistry (AREA)
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Abstract

酸化膜の成長を抑制できるようにしたはんだ材料を提供する。 はんだ材料であるはんだボール１Ａは、はんだ層２と、はんだ層２を被覆する被覆層３で構成される。はんだ層２は球状であり、Ｓｎの含有量が４０％以上の合金からなる金属材料で構成される。または、はんだ層２は、Ｓｎの含有量が１００％である金属材料で構成される。被覆層３は、はんだ層２の外側にＳｎＯ膜３ａが形成され、ＳｎＯ膜３ａの外側にＳｎＯ2膜３ｂが形成される。被覆層３の厚さは、０ｎｍより大きく４．５ｎｍ以下であることが好ましい。また、はんだボール１Ａの黄色度は、５．７以下であることが好ましい。

Description

はんだ材料、はんだ継手及びはんだ材料の製造方法
　本発明は、Ｓｎを主成分としたはんだ材料、はんだ継手及びはんだ材料の製造方法に関する。
　近年、小型情報機器の発達により、搭載される電子部品では急速な小型化が進行している。電子部品は、小型化の要求により接続端子の狭小化や実装面積の縮小化に対応するため、裏面に電極が設置されたボールグリッドアレイ（以下、「ＢＧＡ」と称する）が適用されている。
　ＢＧＡを適用した電子部品には、例えば半導体パッケージがある。半導体パッケージでは、電極を有する半導体チップが樹脂で封止されている。半導体チップの電極には、はんだバンプが形成されている。このはんだバンプは、はんだボールを半導体チップの電極に接合することによって形成されている。ＢＧＡを適用した半導体パッケージは、各はんだバンプがプリント基板の導電性ランドに接触するように、プリント基板上に置かれ、加熱により溶融したはんだバンプとランドとが接合することにより、プリント基板に搭載される。
　さて、はんだボールを電極に接合するためには、はんだボールの表面に金属酸化膜が形成されることを抑制することが求められる。また、はんだボールがフラックスと混合されてソルダペーストとして使用される場合、保管時の粘度上昇を抑制することが求められる。
　ここで、はんだボール表面に形成される酸化膜の膜厚と黄色度には比例関係がある。
そこで、黄色度が所定値以下、すなわち、酸化膜が所定値以下のはんだボールを使用し、加熱によって酸化膜を破壊して、接合できるようにした技術が提案されている（例えば、特許文献１参照）。この特許文献１においては、先ず、製造後に表面の黄化度が１０以下となるはんだボールを選別し、保管状態を厳密に管理することにより、はんだボール表面の黄化を防止、すなわち、はんだボール表面のＳｎＯ酸化膜の成長を抑制すると共に、このはんだボールを用いて形成されたはんだバンプの表面に、ＳｎＯ酸化膜及びＳｎＯ2酸化膜が形成されることが開示されている。
　また、はんだボールの表面に、所定値の酸化膜を形成して、粘度上昇を抑制できるようにした技術が提案されている（例えば、特許文献２参照）。この特許文献２においては、はんだ粒子表面にＳｎＯまたはＳｎＯ2を主成分とする酸化錫からなる酸化被膜を形成し、フラックスと混合・撹拌して製造されるはんだペースト作製後の経過的粘土上昇を抑制することが開示されている。
特開２００９－２４８１５６号公報 特許第４０８４６５７号公報
　Ｓｎを主成分としたはんだボールでは、Ｓｎと空気中のＯ２が反応してＳｎＯの膜が形成される。この膜厚が増加すると、はんだ付け時にフラックスでの除去が困難になる、はんだボールの表面に酸化膜が残っていると、濡れ性が悪くなる。また、酸化膜厚が増加すると、黄色度が上昇する。はんだボールの外観検査として、黄色度を利用する場合があり、酸化膜厚の増加を抑制できないと、はんだボールが使用に適さないと判断される可能性が高くなる。
　特許文献１では、保管状態を厳密に管理することにより、はんだボール表面のＳｎＯ酸化膜の成長を抑制するようにしている。また、特許文献１では、結晶質であるＳｎＯ2酸化膜が、はんだボールの溶融に伴う内部変形で破損し易いことに着目して、はんだと電極端子の接合性を向上させているが、保管状態の管理以外に、酸化膜の組成で酸化膜の成長を抑制することについての開示は一切ない。更に、特許文献２に関しては、ＳｎＯ酸化膜の成長を抑制することについての開示は一切ない。
　そこで、本発明は、酸化膜の成長を抑制できるようにし、これにより、保管性及び濡れ性の良好なるはんだ材料、はんだ継手及びはんだ材料の製造方法を提供することを目的とする。
　本発明者らは、Ｓｎを主成分とするはんだ層を、ＳｎＯ及びＳｎＯ2を有する被覆層で被覆することで、酸化膜の成長を抑制できることを見出した。なお、ＳｎＯ及びＳｎＯ2を有する被覆層とは、ＳｎＯを主成分とする酸化錫からなる酸化被膜層、及び、ＳｎＯ2を主成分とする酸化錫からなる酸化被膜層を意味する。以下の説明においても同様である。
　そこで、請求項１に記載の発明は、Ｓｎの含有量が４０％以上の合金からなる金属材料またはＳｎの含有量が１００％である金属材料からなるはんだ層と、はんだ層の表面を被覆する被覆層を備え、被覆層は、はんだ層の外側にＳｎＯ膜が形成され、ＳｎＯ膜の外側にＳｎＯ2膜が形成され、被覆層の厚さは、０ｎｍより大きく４．５ｎｍ以下であるはんだ材料である。
　請求項２に記載の発明は、黄色度が５．７以下である請求項１に記載のはんだ材料である。
　請求項３に記載の発明は、Ｓｎの含有量が４０％以上の合金からなる金属材料またはＳｎの含有量が１００％である金属材料からなるはんだ層と、はんだ層の表面を被覆する被覆層を備え、被覆層は、はんだ層の外側にＳｎＯ膜が形成され、ＳｎＯ膜の外側にＳｎＯ2膜が形成され、黄色度が５．７以下であるはんだ材料である。
　請求項４に記載の発明は、はんだ層は、Ａｇを０％以上４％未満、Ｃｕを０％以上１％未満、Ｐを０ｐｐｍ以上５ｐｐｍ未満、Ｇｅを０ｐｐｍ以上２０ｐｐｍ未満で含む請求項１～請求項３のいずれか１項に記載のはんだ材料である。
　請求項５に記載の発明は、はんだ層は、Ｓｎの含有量が４０％以上となるように、（i）Ｎｉ、Ｃｏ、Ｆｅ、Ｓｂから選ばれる少なくとも１つの元素を、全体で１％未満あるいはそれぞれを１％未満含有し、及び、Ｉｎ、Ｂｉから選ばれる少なくとも１つ以上の元素を、全体で４０％未満あるいはＩｎ、Ｂｉの一方を４０％未満、他方を２０％未満含有し、あるいは、（ii）Ｎｉ、Ｃｏ、Ｆｅ、Ｓｂから選ばれる少なくとも１つの元素を、全体で１％未満あるいはそれぞれを１％未満含有するか、または、Ｉｎ、Ｂｉから選ばれる少なくとも１つ以上の元素を、全体で４０％未満あるいはＩｎ、Ｂｉの一方を４０％未満、他方を２０％未満含有した請求項１～請求項４のいずれか１項に記載のはんだ材料である。
　請求項６に記載の発明は、放射されるα線量が０．０２００ｃｐｈ/ｃｍ2以下である請求項１～請求項５のいずれか１項に記載のはんだ材料である。
　請求項７に記載の発明は、直径が１～１０００μmの球体である請求項１～請求項６のいずれか１項に記載のはんだ材料である。
　請求項８に記載の発明は、請求項１～７のいずれか１項に記載のはんだ材料を使用して得たはんだ継手である。
　請求項９に記載の発明は、Ｓｎの含有量が４０％以上の合金からなる金属材料またはＳｎの含有量が１００％である金属材料からなるはんだ層を形成するはんだ層形成工程と、はんだ層の外側にＳｎＯ膜を形成し、ＳｎＯ膜の外側にＳｎＯ2膜を形成して、厚さが０ｎｍより大きく４．５ｎｍ以下の被覆層を、はんだ層の表面に形成する酸化膜形成工程を含むはんだ材料の製造方法である。
　請求項１０に記載の発明は、酸化膜形成工程で、被覆層表面の黄色度が5.7以下に形成される請求項９に記載のはんだ材料の製造方法である。
　請求項１１に記載の発明は、酸化膜形成工程は、はんだ層の表面にＯ2-Arプラズマを照射する請求項９または請求項１０に記載のはんだ材料の製造方法である。
　本発明では、はんだ層を被覆する被覆層において、ＳｎＯ膜の外側にＳｎＯ2膜が形成されると、Ｓｎと空気中のＯ2との反応が抑制され、ＳｎＯ膜及びＳｎＯ2膜成長が抑制され、膜厚の増加を抑制することができる、また、膜厚の増加が抑制されることで、黄変が抑制され、黄色度を５．７以下に抑制することができる。これにより、保管性及び濡れ性の良好なるはんだ材料、及び、このはんだ材料を使用したはんだ継手を提供できる。
本実施の形態のはんだ材料の一例としてのはんだボールの模式的な構造を示す断面図である。 本実施の形態のはんだ材料の一例としてのはんだボールの製造方法を模式的に示した断面図である。 本実施の形態のはんだ材料の一例としてのはんだボールの製造方法を模式的に示した断面図である。 本実施の形態のはんだ材料の一例としてのはんだボールの製造方法を模式的に示した断面図である。
　以下、本発明のはんだ材料、はんだ継手及びはんだ材料の製造方法について説明する。
　＜はんだ材料の構成例＞
　図１は、本実施の形態のはんだ材料の一例としてのはんだボールの模式的な構造を示す断面図である。なお、本明細書において、はんだ材料の組成に関する単位（ｐｐｍ、ｐｐｂ、及び％）は、特に指定しない限り質量に対する割合（質量ｐｐｍ、質量ｐｐｂ、及び質量％）を表す。
　本実施の形態のはんだボール１Ａは、はんだ層２と、はんだ層２を被覆する被覆層３で構成される。はんだ層２は球状であり、Ａｇを０％以上４％未満、Ｃｕを０％以上１％未満、Ｓｎの含有量が４０％以上の合金材料で構成される。一般に、所定量のＰあるいはＧｅを添加することで耐酸化性が向上するが、本発明ではこれらを添加することなく耐酸化性を向上させることができる。但し、Ｐを５ｐｐｍ未満、Ｇｅを２０ｐｐｍ未満添加しても本発明の効果を損なうことはない。そこで、ＰあるいはＧｅは、添加しなくても良いし、添加するのであれば、Ｐの添加量は５ｐｐｍ未満、Ｇｅの添加量は２０ｐｐｍ未満とする。従って、Ｐの添加量を０ｐｐｍ以上５ｐｐｍ未満、Ｇｅの添加量を０ｐｐｍ以上２０ｐｐｍ未満とする。
　また、はんだ層２は、Ｓｎの含有量が４０％以上となるように、Ｎｉ、Ｃｏ、Ｆｅ、Ｓｂから選ばれる少なくとも１つの元素を、全体で１％未満あるいはそれぞれを１％未満含有し、及び、Ｉｎ、Ｂｉから選ばれる少なくとも１つ以上の元素を、全体で４０％未満あるいはＩｎ、Ｂｉの一方を４０％未満、他方を２０％未満含有する。
　あるいは、Ｎｉ、Ｃｏ、Ｆｅ、Ｓｂから選ばれる少なくとも１つの元素を、全体で１％未満あるいはそれぞれを１％未満含有するか、または、Ｉｎ、Ｂｉから選ばれる少なくとも１つ以上の元素を、全体で４０％未満あるいはＩｎ、Ｂｉの一方を４０％未満、他方を２０％未満含有する。
　更に、はんだ層２は、Ｓｎの含有量が１００％である金属材料で構成されるものでも良い。なお、はんだ層２から放射されるα線量が０．０２００ｃｐｈ/ｃｍ2以下であることが好ましい。
　被覆層３は、はんだ層２の外側にＳｎＯ膜３ａが形成され、ＳｎＯ膜３ａの外側にＳｎＯ2膜３ｂが形成される。はんだボール１Ａが空気に触れることで、はんだ層２の表面に形成されるＳｎＯの層は、時間の経過と共に膜厚が厚くなる。また、膜厚が厚くなると、はんだボール１Ａの表面が黄変する。
　これに対し、ＳｎＯ膜３ａの外側にＳｎＯ2膜３ｂが形成されると、Ｓｎと空気中のＯ2との反応が抑制され、ＳｎＯ膜３ａ及びＳｎＯ2膜３ｂ自体の成長が抑制され、結果として膜厚の増加が抑制される。また、膜厚の増加が抑制されることで、黄変が抑制され、はんだ層２を構成する金属材料が持つ色に近い所定の白銀色が保持される。
　はんだボール１Ａは、直径が１～１０００μｍであることが好ましい。また、被覆層３の厚さは、０ｎｍより大きく（０ｎｍは含まないことを意味する）４．５ｎｍ以下であることが好ましい。被覆層３の厚さが４．５ｎｍを超えると、はんだ付け時にフラックスで被覆層３の除去が困難になり、濡れ性が悪化する。
　また、はんだボール１Ａの黄色度ｂ＊は、５．７以下であることが好ましい。製造、保存されたはんだボール１Ａを管理する際に、黄色度を利用する場合がある。これは、黄色度が高いということは、ＳｎＯの膜厚が厚いということであり、黄色度が所定値を超えるはんだボールは、使用に適さないものとして除外できるようにするためである。
　明度及び黄色度は、コニカミノルタ製ＣＭ－３５００ｄ２６００ｄ型分光測色計を使用して、Ｄ６５光源、１０度視野でＪＩＳ　Ｚ　８７２２「色の測定方法―反射及び透過物体色」に準じて分光透過率を測定して、色彩値（Ｌ＊、ａ＊、ｂ＊　）から求めた。
　なお、色彩値（Ｌ＊、ａ＊、ｂ＊　）は、ＪＩＳ　Ｚ　８７２９「色の表示方法―Ｌ＊ａ＊ｂ＊表色系及びＬ＊Ｕ＊Ｖ＊表色系」に規定されているとおりである。
　なお、はんだ材料の形状は、本例では球状としたが、円筒状、四角柱状等、他の形状でもよい。また、はんだボール１Ａから放射されるα線量も０．０２００ｃｐｈ/ｃｍ2以下であることが好ましい。
　＜はんだ材料の製造方法例＞
　図２Ａ、図２Ｂ及び図２Ｃは、本実施の形態のはんだ材料の一例としてのはんだボールの製造方法を模式的に示した断面図である。
　はんだ層形成工程では、図２Ａに示すように、上述したＳｎの含有量が４０％以上の合金からなる金属材料、または、Ｓｎの含有量が１００％である金属材料で、球状のはんだ層２が形成される。はんだ層形成工程は、本例では、溶融した金属材料を滴下して球状に硬化させる滴下法が用いられる。
　酸化膜形成工程では、図２Ｂに示すように、はんだ層２の表面が空気に触れることで生成されるＳｎＯ膜３ａの表面に、図２Ｃに示すように、ＳｎＯ2膜３ｂが形成される。酸化膜を形成する方法としては、従来公知の方法を用いることができる。例えば、蒸着法、スパッタリング法、プラズマ照射法などがあげられる。本例では、酸化膜形成工程を公知の大気圧プラズマ装置を用いてプラズマ照射法で実現する。プラズマ照射法は、溶融した金属が滴下されて硬化するまでの間に、高濃度のＯ2-Ａｒプラズマが照射される。
　以上の製造方法により、所定の直径を有したはんだ層２の表面に被覆層３が形成されたはんだボール１Ａが製造される。被覆層３aは、厚さが0ｎｍより大きく4.5ｎｍ以下であり、はんだ層２の外側にＳｎＯ膜３ａが形成され、ＳｎＯ膜３ａの外側にＳｎＯ2膜３ｂが形成される。また、はんだボール１Ａの黄色度は5.66以下である。
　＜実施例＞
　Ａｇが3％、Ｃｕが0.5％、残部がＳｎからなる金属材料で、滴下法によりはんだ層２に相当する金属球を作成した。この金属球に、プラズマ照射法で被覆層３に相当する被膜を形成して実施例のはんだボールを生成した。プラズマ照射法は、溶融した金属材料が滴下するまでの間に高濃度のＯ2-Ａｒプラズマを照射した。
　比較例として、自然酸化により表面にＳｎＯの層が形成されたはんだボールを生成した。
　実施例と比較例のはんだボールを２００℃で加熱して、酸化挙動を黄色度ｂ＊の値で観察した結果を表１に示す。
Figure JPOXMLDOC01-appb-T000001
　表１に示すように、比較例のはんだボールは速やかに黄色度b*の値が上昇したのに対して、実施例のはんだボールは、ＳＥＲＡによる定性分析により、Ｓｎを主成分としたはんだ層の外側にＳｎＯの層が形成され、ＳｎＯの層の外側にＳｎＯ2の層が形成されることで、酸化膜厚の成長が抑制されているのが判った。
　また、参考までに比較例において酸化工程と加熱試験工程を分離するために、２００℃で１分間の加熱を行い、その後、冷却した後に再度加熱を行ってみたが、工程分離前と同様に速やかに黄色度b*の値が上昇した。
　次に、上述した実施例のはんだボールとして、２００℃で１５分間加熱した実施例１のはんだボールと、２００℃で３０分間加熱した実施例２のはんだボールの酸化膜厚をＦＥ－ＡＥＳ（電界放射型オージェ電子分光法）にて定量分析し、かつ、形成された酸化膜の成分がＳｎの酸化物（ＳｎＯ及びＳｎＯ2）であることの確認をＳＥＲＡ（Ｓｅｑｕｅｎｔｉａｌ Ｅｌｅｃｔｒｏｃｈｅｍｉｃａｌ Ｒｅｄｕｃｔｉｏｎ Ａｎａｌｙｓｉｓ：連続電気化学還元法）により定性分析した。
　なお、定量分析をＦＥ－ＡＥＳで実施したのは、ＳＥＲＡでの分析値は分散しやすく、定性分析は可能であるが、具体的な酸化膜厚を定量分析として議論するにはＦＥ－ＡＥＳ分析の方が一定値を示しやすいためである。酸化膜の膜厚は、以下の装置及び条件で測定された。なお、酸化膜厚測定値はＳｉＯ２換算により求めた。
　測定装置：ＵＬＶＡＣ－ＰＨＩ，ＩＮＣ製　走査型ＦＥオージェ電子分光分析装置
　測定条件：Ｂｅａｍ　Ｖｏｌｔａｇｅ：１０ｋＶ，　試料電流：１０ｎＡ（Ａｒイオン銃を用いたスパッタ深さの測定方法は、ＩＳＯ／ＴＲ　１５９６９に準拠。）
　表２に酸化膜厚と黄色度の測定結果を示す。
Figure JPOXMLDOC01-appb-T000002
　表２に示すように、酸化膜厚は５ｎｍ以下に抑えられていることが判り、被覆層の膜厚は、４．５ｎｍ以下とすることが好ましいことが判る。また、黄色度は１０以下に押さえられていることが判り、表２の結果から、５．７以下とすることが好ましいことが判る。
　次に、上述した実施例と比較例のはんだボールで、膜厚、黄色度を変えたものを作成して、保管性と濡れ性を検証した。
　各実施例のはんだボールは、膜厚が４．５ｎｍ以下であり、実施例１のはんだボールは、膜厚が２．６ｎｍ、実施例２のはんだボールは、膜厚が４．１ｎｍ、実施例３のはんだボールは、膜厚が１．５ｎｍである。
　また、各実施例のはんだボールは、黄色度が５．７以下であり、実施例１のはんだボールは、黄色度が４．６０、実施例２のはんだボールは、黄色度が５．７７、実施例３のはんだボールは、黄色度が３．９０である。
　一方、各比較例のはんだボールは、膜厚が１０ｎｍ以上であり、また、黄色度が１０以下であり、比較例１のはんだボールは、黄色度が１０．２１、比較例２のはんだボールは、黄色度が１３．１５である。
　検証結果を表３に示す
Figure JPOXMLDOC01-appb-T000003
　表３に示すように、実施例１から実施例３のはんだボールでは、保管性及び濡れ性のいずれも、所定の条件を満たして、一方、各比較例のはんだボールは、保管性及び濡れ性のいずれも、所定の条件を満たさなかった、
　よって、被覆層の厚さが０ｎｍより大きく４．５ｎｍ以下、黄色度ｂ＊が５．７以下のはんだボールでは、保管性及び濡れ性とも向上することが判った。
　なお、本発明に係るはんだ材料は、はんだペーストで電極に電気的に接合されることにより、電子部品のはんだ継手に用いることができる。
１Ａ・・・はんだボール
２・・・はんだ層
３・・・被膜層
３ａ・・・ＳｎＯ膜
３ｂ・・・ＳｎＯ2膜

Claims (11)

  1. 　Ｓｎの含有量が４０％以上の合金からなる金属材料またはＳｎの含有量が１００％である金属材料からなるはんだ層と、
    　前記はんだ層の表面を被覆する被覆層を備え、
    　前記被覆層は、前記はんだ層の外側にＳｎＯ膜が形成され、前記ＳｎＯ膜の外側にＳｎＯ2膜が形成され、前記被覆層の厚さは、０ｎｍより大きく４．５ｎｍ以下である
    　ことを特徴とするはんだ材料。
  2. 　黄色度が５．７以下である
    　ことを特徴とする請求項１に記載のはんだ材料。
  3. 　Ｓｎの含有量が４０％以上の合金からなる金属材料またはＳｎの含有量が１００％である金属材料からなるはんだ層と、
    　前記はんだ層の表面を被覆する被覆層を備え、
    　前記被覆層は、前記はんだ層の外側にＳｎＯ膜が形成され、前記ＳｎＯ膜の外側にＳｎＯ2膜が形成され、
    　黄色度が５．７以下である
    　ことを特徴とするはんだ材料。
  4. 　前記はんだ層は、Ａｇを０％以上４％未満、Ｃｕを０％以上１％未満、Ｐを０ｐｐｍ以上５ｐｐｍ未満、Ｇｅを０ｐｐｍ以上２０ｐｐｍ未満で含む
    　ことを特徴とする請求項１～請求項３のいずれか１項に記載のはんだ材料。
  5. 　前記はんだ層は、Ｓｎの含有量が４０％以上となるように、
    　（i）Ｎｉ、Ｃｏ、Ｆｅ、Ｓｂから選ばれる少なくとも１つの元素を、全体で１％未満あるいはそれぞれを１％未満含有し、及び、Ｉｎ、Ｂｉから選ばれる少なくとも１つ以上の元素を、全体で４０％未満あるいはＩｎ、Ｂｉの一方を４０％未満、他方を２０％未満含有し、
    　あるいは、
    　（ii）Ｎｉ、Ｃｏ、Ｆｅ、Ｓｂから選ばれる少なくとも１つの元素を、全体で１％未満あるいはそれぞれを１％未満含有するか、または、Ｉｎ、Ｂｉから選ばれる少なくとも１つ以上の元素を、全体で４０％未満あるいはＩｎ、Ｂｉの一方を４０％未満、他方を２０％未満含有した
    　ことを特徴とする請求項１～請求項４のいずれか１項に記載のはんだ材料。
  6. 　放射されるα線量が０．０２００ｃｐｈ/ｃｍ2以下である
    　ことを特徴とする請求項１～請求項５のいずれか１項に記載のはんだ材料。
  7. 　直径が１～１０００μmの球体である
    　ことを特徴とする請求項１～請求項６のいずれか1項に記載のはんだ材料。
  8. 　請求項１～７のいずれか１項に記載のはんだ材料を使用して得た
    　ことを特徴とするはんだ継手。
  9. 　Ｓｎの含有量が４０％以上の合金からなる金属材料またはＳｎの含有量が１００％である金属材料からなるはんだ層を形成するはんだ層形成工程と、
    　前記はんだ層の外側にＳｎＯ膜を形成し、前記ＳｎＯ膜の外側にＳｎＯ2膜を形成して、厚さが０ｎｍより大きく４．５ｎｍ以下の被覆層を、前記はんだ層の表面に形成する酸化膜形成工程を含む
    　ことを特徴とするはんだ材料の製造方法。
  10. 　前記酸化膜形成工程で、前記被覆層表面の黄色度が５．７以下に形成される
    　ことを特徴とする請求項９に記載のはんだ材料の製造方法。
  11. 　前記酸化膜形成工程は、前記はんだ層の表面にＯ2-Ａｒプラズマを照射する
    　ことを特徴とする請求項９または請求項１０に記載のはんだ材料の製造方法。
PCT/JP2014/072803 2014-08-29 2014-08-29 はんだ材料、はんだ継手及びはんだ材料の製造方法 WO2016031067A1 (ja)

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PT149007890T PT3187299T (pt) 2014-08-29 2014-08-29 Material de solda, uso de material de solda e método de produção para material de solda
CN201480080357.3A CN106536124B (zh) 2014-08-29 2014-08-29 软钎料材料、焊料接头及软钎料材料的制造方法
US15/327,510 US10173287B2 (en) 2014-08-29 2014-08-29 Solder material, solder joint, and method of manufacturing the solder material
JP2015525662A JP5807733B1 (ja) 2014-08-29 2014-08-29 はんだ材料、はんだ継手及びはんだ材料の製造方法
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