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WO2010119489A1 - Élément conducteur et son procédé de fabrication - Google Patents

Élément conducteur et son procédé de fabrication Download PDF

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Publication number
WO2010119489A1
WO2010119489A1 PCT/JP2009/003280 JP2009003280W WO2010119489A1 WO 2010119489 A1 WO2010119489 A1 WO 2010119489A1 JP 2009003280 W JP2009003280 W JP 2009003280W WO 2010119489 A1 WO2010119489 A1 WO 2010119489A1
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WO
WIPO (PCT)
Prior art keywords
layer
plating
conductive member
alloy
intermetallic compound
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2009/003280
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English (en)
Japanese (ja)
Inventor
櫻井健
石川誠一
久保田賢治
玉川隆士
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Mitsubishi Shindoh Co Ltd
Original Assignee
Mitsubishi Shindoh Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from JP2009115289A external-priority patent/JP5442316B2/ja
Priority claimed from JP2009127085A external-priority patent/JP4372835B1/ja
Application filed by Mitsubishi Shindoh Co Ltd filed Critical Mitsubishi Shindoh Co Ltd
Priority to CN200980158742.4A priority Critical patent/CN102395713B/zh
Publication of WO2010119489A1 publication Critical patent/WO2010119489A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
    • H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
    • H01R13/02—Contact members
    • H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/10—Electroplating with more than one layer of the same or of different metals
    • C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/48—After-treatment of electroplated surfaces
    • C25D5/50—After-treatment of electroplated surfaces by heat-treatment
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
    • C25D5/60—Electroplating characterised by the structure or texture of the layers
    • C25D5/615—Microstructure of the layers, e.g. mixed structure
    • C25D5/617—Crystalline layers
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated

Definitions

  • the present invention relates to a conductive member used for an electrical connection connector, a fuse, or the like, in which a plurality of plating layers are formed on the surface of a substrate made of Cu or Cu alloy, and a method for manufacturing the same.
  • This application includes Japanese Patent Application No. 2009-98043 filed in Japan on April 14, 2009, Japanese Patent Application No. 2009-115289 filed in Japan on May 12, 2009, and May 26, 2009. Claim priority based on Japanese Patent Application No. 2009-127085 filed in Japan, the contents of which are incorporated herein.
  • Sn-based metal plating is applied to the surface of a Cu-based substrate made of Cu or a Cu alloy for the purpose of improving electrical connection characteristics. Many of them have been used. Examples of such conductive members include those described in Patent Document 1 to Patent Document 4.
  • the conductive members described in Patent Document 1 to Patent Document 3 are subjected to a reflow treatment by heating after forming Ni, Cu, Sn on the surface of a substrate made of Cu or Cu alloy in order to form a three-layered plating layer. Thus, an Sn layer is formed on the outermost surface layer, and a Cu—Sn intermetallic compound layer (for example, Cu 6 Sn 5 ) is formed between the Ni layer and the Sn layer.
  • the technique described in Patent Document 4 is a technique in which a base plating layer is made of, for example, Ni—Fe, Fe, or the like, and Cu and Sn are sequentially plated thereon to perform a reflow process.
  • such a conductive member is continuously manufactured as a copper strip, but with a limited line length by using an inorganic acid and an insoluble anode on the surface of a wide thin plate such as this copper strip.
  • the relative flow rate between the copper strip and the plating solution in each plating bath is increased to increase the current density, thereby shortening the time required to obtain the desired properties of plating. This is very important.
  • the reflow treatment after plating is a major factor, which greatly affects the performance during use as a conductive member.
  • the characteristics of the surface layer formed after the reflow treatment and the intermediate alloy layer which is the lower layer greatly contribute to the connector insertion / removability.
  • Patent Document 5 a current density of 50 A / dm 2 or more and a temperature of 30 to 70 ° C. are used in an insoluble anode in a tin plating sulfuric acid bath for high current density used for the production of electroplated tin and thin tin-plated steel sheet.
  • a method of tin plating is disclosed.
  • Patent Document 6 a Ni or Ni alloy layer is formed on the surface of copper or a copper alloy, a Sn or Sn alloy layer is formed on the outermost surface, and the Ni or Ni alloy layer and the Sn or Sn alloy layer are formed.
  • At least one intermediate layer containing Cu and Sn as a main component or an intermediate layer containing Cu, Ni and Sn as a main component is formed between the at least one intermediate layer, and the Cu content is 50 wt. %, And the Ni content is 50% by weight or less, and the Cu content is 50% by weight, projected in the direction perpendicular to each layer formed on the surface of the copper or copper alloy.
  • a plated copper or copper alloy characterized in that the average crystal grain size of the layer having the following and Ni content of 50% by weight or less is 0.5 to 3.0 ⁇ m.
  • Ni or Ni alloy As a manufacturing method, Ni or Ni alloy, Cu plating is applied on the surface of copper or copper alloy, Sn or Sn alloy plating is applied to the outermost surface layer, then at least one reflow treatment is performed, and a heating temperature is set. Is 400 to 900 ° C., the time from the melting of the Sn or Sn alloy layer to the solidification is 0.05 to 60 seconds.
  • the connectors when used for connectors, as the circuit density increases, the connectors also become multipolar, and the insertion force at the time of assembling the automobile wiring is increasing. Therefore, a conductive member that can reduce the insertion / extraction force is required. ing. Furthermore, the use as a fuse is found about the electrically conductive member which plated the Sn type metal on the surface of such Cu type base material, and the favorable fusing characteristic as a fuse is calculated
  • the invention described in Patent Document 5 is a production method of tin-plated steel sheets such as tinplate, in a sulfuric acid bath using an insoluble anode, at a temperature of 30 to 70 ° C., and a current density of 50 A / dm 2 or more.
  • the steel strip is tin-plated at a relative speed of the steel strip and the electrolyte of 160 m / min or more.
  • Ni or Ni alloy Cu plating is applied on the surface of copper or a copper alloy, and Sn or Sn alloy plating is applied to the outermost surface layer. Is 400 to 900 ° C., and the time from when the Sn or Sn alloy layer melts to solidification is 0.05 to 60 seconds, the Cu content is 50% by weight or less and the Ni content is One intermediate layer having an average crystal grain size of 0.5 to 3.0 ⁇ m is formed by 50% by weight or less. This average crystal grain size is greatly related to the pluggability when the conductive member is used as a connector, but appropriate pluggability cannot be obtained only by controlling the average grain size.
  • the present invention has been made in view of such circumstances, and has a stable contact resistance, is difficult to peel off, can reduce and stabilize the insertion / extraction force when used as a connector, and is used as a fuse.
  • a Cu—Sn intermetallic compound layer is formed between a Ni-based underlayer formed on a Cu-based substrate and a Sn-based surface layer forming the surface, and Cu— Sn intermetallic compound layer further made from the the Cu 3 Sn layer disposed on the Ni-based base layer, the Cu 6 Sn 5 layer disposed on the said Cu 3 Sn layer, the Cu 3 Sn
  • the surface roughness of the surface of the Cu-Sn intermetallic compound layer combined with the Sn-based surface layer in combination with the Cu 6 Sn 5 layer is 0.05 to 0.25 ⁇ m in terms of arithmetic average roughness Ra, and
  • the maximum valley depth Rv of the roughness curve is 0.05 to 1.00 ⁇ m
  • the Cu 3 Sn layer covers the Ni-based underlayer, and the area coverage is 60 to 100%. It is characterized by that.
  • the conductive member, Cu-Sn intermetallic compound layer between the Ni-based base layer and the Sn-based surface layer is a two-layer structure of the Cu 3 Sn layer and the Cu 6 Sn 5 layer, the underlying Cu 3
  • the Cu 6 Sn 5 layer is present so that the Sn layer covers the Ni-based underlayer and covers it.
  • the Cu—Sn intermetallic compound layer formed by combining the Cu 3 Sn alloy layer and the Cu 6 Sn 5 layer has a film thickness that is not necessarily uniform and has irregularities, but is a surface in contact with the Sn-based surface layer.
  • the surface roughness is 0.05 to 0.25 ⁇ m in terms of arithmetic average roughness Ra, and 0.05 to 1.00 ⁇ m in terms of the maximum valley depth Rv of the roughness curve.
  • the arithmetic average roughness Ra represents the average size of the irregularities on the surface. If this Ra exceeds 0.25 ⁇ m, large irregularities are formed under the Sn-based surface layer.
  • the insertion / extraction force when used is not preferable. When the unevenness of the Cu—Sn intermetallic compound layer is reduced, the insertion / extraction force during use of the connector is reduced, but it is preferable that Ra is less than 0.05 ⁇ m because the unevenness of the Cu—Sn intermetallic compound layer is almost eliminated. This is not preferable because the Cu—Sn intermetallic compound layer becomes extremely brittle and peeling of the film easily occurs during bending.
  • Ra is averaged, even if there is a large valley, it is averaged and hardly appears in the numerical value. If there is such a large valley, Sn diffuses from the valley to the Ni-based underlayer at a high temperature, and there is a risk that defects will occur in the Ni-based underlayer.
  • the contact resistance is increased. Further, at this time, Kirkendall voids are likely to be generated due to diffusion of Cu from the defect portion of the Ni-based underlayer. Therefore, if Ra is in the above-mentioned range and the maximum valley depth Rv of the roughness curve is 1.00 ⁇ m or less, it is possible to prevent the Ni-based underlayer from being damaged.
  • the Rv be less than 0.05 ⁇ m because the Cu—Sn intermetallic compound layer becomes brittle as in the case of Ra.
  • the flexible Sn base is hardened and used in a multipolar connector or the like. It is possible to reduce the insertion / extraction force and to suppress variations thereof.
  • the reason why the area coverage of the Cu 3 Sn layer with respect to the Ni-based underlayer is 60% or more is that when the coverage is low, the Ni atoms in the Ni-based underlayer are Cu 6 Sn at high temperatures from the uncoated portion. This is because the Ni-based underlayer is deficient in five layers and the Cu of the base material diffuses from the deficient portion, resulting in increased contact resistance and generation of Kirkendall voids as in the above case. is there. In order to prevent this increase in contact resistance at high temperatures and the generation of Kirkendall voids and to achieve heat resistance higher than that of the prior art, it is necessary that the Ni-based underlayer is coated at least 60% or more. Further, it is desirable that the area coverage is 80% or more.
  • the Cu 3 Sn layer preferably has an average thickness of 0.01 to 0.5 ⁇ m.
  • This average thickness is an average value when the thickness of the Cu 3 Sn layer portion is measured at a plurality of locations.
  • the average thickness of the Sn-based surface layer is preferably 0.5 to 1.5 ⁇ m.
  • the Sn-based surface layer preferably has an average thickness of 0.5 to 1.5 ⁇ m as a layer forming the surface of the conductive member in order to maintain performance such as heat resistance and insertion / removability as a connector terminal.
  • a Sn—Ag coating layer having an average thickness of 0.05 to 0.5 ⁇ m may be formed on the Sn surface layer.
  • the Sn—Ag coating layer preferably contains 0.1 to 5.0% by weight of Ag.
  • the manufacturing method of the electrically-conductive member of this invention heats, after plating the surface of Cu base material, Ni or Ni alloy, Cu or Cu alloy, Sn or Sn alloy in this order, and forming each plating layer And reflow treatment to produce a conductive member in which a Ni-based underlayer, a Cu—Sn intermetallic compound layer, and a Sn-based surface layer are sequentially formed on the Cu-based substrate,
  • a plating layer made of Cu alloy is formed by electrolytic plating with a current density of 20 to 60 A / dm 2
  • a plating layer made of Sn or Sn alloy is formed by electrolytic plating with a current density of 10 to 30 A / dm 2
  • the average thickness of the plating layer made of Cu or Cu alloy is 0.3 to 0.5 ⁇ m, and the reflow treatment is performed after 1 to 15 minutes have passed since the formation of the plating layer.
  • Cu plating at a high current density increases the grain boundary density and helps to form a uniform alloy layer.
  • the reason why the current density of Cu plating is set to 20 to 60 A / dm 2 is that when the current density is less than 20 A / dm 2 , the reaction activity of the Cu plating crystal is poor, and therefore the effect of forming a smooth intermetallic compound when alloying is performed.
  • the current density exceeds 60 A / dm 2 the smoothness of the Cu plating layer is lowered, and thus a smooth Cu—Sn intermetallic compound layer cannot be formed.
  • the current density of Sn plating was set to 10 to 30 A / dm 2 because when the current density was less than 10 A / dm 2 , the Sn grain boundary density was low, and smooth Cu-Sn intermetallic This is because the effect of forming the compound layer is poor, and on the other hand, if the current density exceeds 30 A / dm 2 , the current efficiency is remarkably lowered, which is undesirable. Also, in order to reduce the unevenness of the Cu—Sn intermetallic compound layer, the thickness of the plating layer made of Cu or Cu alloy as the base is important, and the reflow treatment was performed by forming this slightly thicker. The unevenness of the subsequent Cu—Sn intermetallic compound layer can be reduced.
  • the plating layer made of Cu or Cu alloy is formed to be relatively thick and has a thickness of 0.3 ⁇ m or more, so that the surface roughness of the Cu—Sn intermetallic compound layer after reflow treatment is small and the surface roughness is reduced. An appropriate state can be obtained. Even if it exceeds 0.5 ⁇ m, the effect is saturated.
  • the reflow process may be performed within 15 minutes, preferably within 5 minutes.
  • Ni or Ni alloy, Cu or Cu alloy, Sn or Sn alloy is plated at a higher current density than in the prior art, and Cu and Sn are activated actively during reflow by performing reflow treatment immediately after plating. By reacting, a large amount of Ni-based underlayer is covered with the Cu 3 Sn layer, and a uniform Cu 6 Sn 5 layer is generated.
  • the cooling step by providing a primary cooling step with a low cooling rate, Cu atoms diffuse gently in the Sn grains and grow with a desired intermetallic compound structure.
  • the cooling rate in the primary cooling step exceeds 30 ° C./second, the intermetallic compound cannot grow into a smooth shape due to the effect of rapid cooling, and unevenness increases.
  • the cooling time is less than 2 seconds, the intermetallic compound cannot grow into a smooth shape.
  • the cooling time exceeds 10 seconds, the growth of the Cu 6 Sn 5 layer proceeds excessively and the coverage of the Cu 3 Sn layer decreases. Air cooling is appropriate for this primary cooling step. Then, after the primary cooling step, the secondary cooling step is rapidly cooled to complete the growth of the intermetallic compound layer with a desired structure. When the cooling rate in the secondary cooling step is less than 100 ° C./second, the intermetallic compound further proceeds, and a desired intermetallic compound shape cannot be obtained. Thus, by precisely controlling the electrodeposition conditions and the reflow conditions for plating, a stable Cu—Sn intermetallic compound layer having a two-layer structure with few irregularities can be obtained.
  • the average thickness of the plating layer made of Sn or Sn alloy is preferably 1.5 to 2.0 ⁇ m. This is for ensuring adequate thicknesses of the Cu—Sn intermetallic compound layer and the Sn-based surface layer.
  • the plating layer made of Ni or Ni alloy is preferably formed by electrolytic plating with a current density of 20 to 50 A / dm 2 .
  • the current density of Ni plating 20 A / dm 2 or more the crystal grains are made finer and effectively prevent Ni atoms from diffusing into Sn or intermetallic compounds during reflow or heating after product production.
  • the current density is 50 A / dm 2 or less, the generation of hydrogen on the plating surface during electrolysis is suppressed, and the plating quality is further improved. For this reason, it is desirable that the current density of Ni plating be 20 to 50 A / dm 2 .
  • the oxide film of the Sn-based surface layer after the reflow treatment is removed, and the surface roughness of the Sn-based surface layer is 0.005 to 0 in terms of arithmetic average roughness Ra.
  • a Sn—Ag coating layer may be formed thereon. Since an oxide film is easily formed on the Sn-based surface layer, when the Sn-Ag coating layer is provided on the outermost surface to improve heat resistance and connector insertion / extraction, the surface is smoothed after removing the oxide film. Thus, the unevenness of the Sn—Ag coating layer can be reduced, and the effect of improving heat resistance and insertion / extraction can be effectively exhibited.
  • a copper strip is continuously run while passing through a plurality of plating baths, and Ni or Ni alloy, Cu or Cu alloy, Sn or Sn alloy plating layer is formed on the surface thereof in this order. Then, in the method of manufacturing a conductive member in which a Ni-based underlayer, a Cu—Sn intermetallic compound layer, and a Sn-based surface layer are sequentially formed on the copper strip by heating and reflow treatment.
  • the inventors have found that a plating film having a desired property can be obtained more efficiently by appropriately selecting the current density, bath temperature, and Reynolds number in each plating bath, and in particular, by selecting the Reynolds number optimally.
  • the plating bath it is optimal to use a plating bath mainly composed of an inorganic acid that does not require special wastewater treatment equipment.
  • the Reynolds number is appropriate as an index that represents the turbulent flow value. From the experimental results, it has been found that the theoretical current efficiency value of the plating remains flat above the optimum value, and the appearance defect (plating burn) occurs below the optimum value. (See FIG. 6).
  • the Reynolds number is a dimensionless number determined by the three factors of plating solution viscosity, plating channel diameter, and relative flow velocity between the plating solution and the object to be plated. The optimum value is obtained by appropriately changing the three factors according to the situation. Can be obtained.
  • the Reynolds number is considered to be correlated with the interface (boundary layer) between the object to be plated and the plating solution, unlike the relative speed.
  • the plating efficiency is further increased by providing a means for removing bubbles and sludge generated in a large amount during tin plating.
  • the surface roughness of the intermediate layer can be controlled by examining the reflow conditions.
  • the intermediate layer is basically laminar, and it is important that the unevenness of the intermediate layer itself, that is, the surface roughness be in an optimum numerical range based on the average crystal grain size.
  • the electrolytic plating uses an insoluble anode in a plating bath mainly composed of an inorganic acid, and has an Reynolds number of 1 ⁇ 10 4 to 5 ⁇ 10 5. It is good to do.
  • the surface roughness of the Cu—Sn intermetallic compound layer under the Sn-based surface layer is formed within a predetermined range, so that the insertion / extraction force when used as a connector is reduced and the variation is suppressed.
  • the diffusion of Cu at high temperatures can be prevented, the surface state can be maintained well, the increase in contact resistance can be suppressed, and the peeling of the plating film and the generation of Kirkendall voids can be prevented.
  • the electrical characteristics of the Cu—Sn intermetallic compound layer are stabilized, and excellent fusing characteristics can be exhibited even when used as a fuse.
  • the copper strip plated in the multilayer which has a favorable characteristic at the time of use as an electrically-conductive member can be obtained continuously and efficiently.
  • FIG. 2 is a cross-sectional view showing an embodiment in which a Sn—Ag coating layer is formed on the outermost surface of the conductive member of FIG. 1. It is the temperature profile which made the relationship between the temperature of reflow conditions and time concerning the manufacturing method of this invention a graph. It is a schematic block diagram which shows the example of the manufacturing apparatus used for the manufacturing method of 2nd Embodiment of this invention. It is sectional drawing which shows the positional relationship of the electrode in a plating tank in FIG. 4, and a copper strip. It is a graph which shows the relationship between the Reynolds number during plating processing, and current efficiency.
  • the conductive member 10 As shown in FIG. 1, the conductive member 10 according to the first embodiment includes a Ni-based underlayer 3, a Cu—Sn intermetallic compound layer 4, and a Cu-based substrate 1 with a Fe-based underlayer 2 interposed therebetween.
  • the Sn-based surface layer 5 is formed in this order, and the Cu—Sn intermetallic compound layer 4 further includes a Cu 3 Sn layer 6 and a Cu 6 Sn 5 layer 7.
  • the Cu-based substrate 1 is, for example, a plate-like one made of Cu or a Cu alloy.
  • the material of the Cu alloy is not necessarily limited, but Cu—Zn alloy, Cu—Ni—Si alloy (Corson alloy), Cu—Cr—Zr alloy, Cu—Mg—P alloy, Cu—Fe -P-based alloys and Cu-Sn-P-based alloys are suitable.
  • MSP1, MZC1, MAX251C, MAX375, and MAX126 manufactured by Mitsubishi Shindoh Co., Ltd. are preferably used.
  • the Fe-based underlayer 2 is formed by electrolytic plating of Fe or Fe alloy, and is formed on the surface of the Cu-based substrate 1 with a thickness of 0.1 to 1.0 ⁇ m.
  • an Fe—Ni alloy is used as the Fe alloy.
  • the Ni-based underlayer 3 is formed by electrolytic plating of Ni or a Ni alloy, and is formed on the surface of the Fe-based underlayer 2 with a thickness of, for example, 0.05 to 0.3 ⁇ m. By setting the Ni-based underlayer 3 to a thickness in this range, diffusion at high temperatures is effectively prevented, peeling is less likely to occur, and bending workability is improved.
  • the Cu—Sn intermetallic compound layer 4 is an alloy layer formed by diffusing Cu plated on the Ni-based underlayer 3 and Sn on the surface by reflow treatment.
  • the Cu—Sn intermetallic compound layer 4 is formed to a thickness of 0.05 to 1.8 ⁇ m as a whole, preferably 0.1 ⁇ m or more, and further disposed on the Ni-based underlayer 3.
  • the Cu 3 Sn layer 6 and the Cu 6 Sn 5 layer 7 disposed on the Cu 3 Sn layer 6 are configured.
  • the Cu—Sn intermetallic compound layer 4 as a whole is uneven, and the surface roughness of the surface in contact with the Sn-based surface layer 5 is an arithmetic average roughness Ra of 0.05 to 0.25 ⁇ m.
  • the maximum valley depth Rv of the roughness curve is 0.05 to 1.00 ⁇ m.
  • the reason why the arithmetic average roughness Ra is 0.05 to 0.25 ⁇ m is that when Ra is used as the connector terminal portion 3, it is preferable that Ra is small because the insertion / extraction force is reduced, but Ra is less than 0.05 ⁇ m. Then, the unevenness of the Cu—Sn intermetallic compound layer 4 is almost eliminated and the Cu—Sn intermetallic compound layer 4 becomes extremely fragile, and the film is easily peeled off during bending.
  • the unevenness of the Cu—Sn intermetallic compound layer 4 becomes resistance at the time of insertion / extraction when used as a connector, so that the effect of reducing the insertion / extraction force is poor.
  • the maximum valley depth Rv of the roughness curve when Rv exceeds 1.00 ⁇ m, Sn diffuses from the valley portion to the Ni-based underlayer at a high temperature, and the Ni-based underlayer may be damaged. Due to the defect, Cu of the base material diffuses, the Cu 6 Sn 5 layer reaches the surface, and Cu oxide is formed on the surface, thereby increasing the contact resistance.
  • the Cu 3 Sn layer 6 disposed in the lower layer of the Cu—Sn intermetallic compound layer 4 covers the Ni-based underlayer 3 and has an area coverage of 60 to 100%. If the area coverage is less than 60%, diffusion of Ni atoms in the Ni-based underlayer 3 from the uncoated portion to the Cu 6 Sn 5 layer 7 at a high temperature is promoted, and the Ni-based underlayer 3 There is a risk of loss. More preferably, 80% or more is covered. This area coverage can be confirmed from a scanning ion image (SIM image) of the surface obtained by processing the cross section of the film with a focused ion beam (FIB) and observing with a scanning ion microscope (SIM). it can.
  • SIM image scanning ion image
  • the area coverage is 60% or more with respect to the Ni-based underlayer 3
  • the area coverage is less than 100%, the portion where the Cu 3 Sn layer 6 does not locally exist on the surface of the Ni-based underlayer 3 Even in this case, the Cu 6 Sn 5 layer 7 of the Cu—Sn intermetallic compound layer 4 covers the Ni-based underlayer 3.
  • the Cu 3 Sn layer 6 constituting the lower layer of the Cu—Sn intermetallic compound layer 4 has an average thickness of 0.01 to 0.5 ⁇ m. Since this Cu 3 Sn layer 6 is a layer covering the Ni-based underlayer 3, the average thickness within this range is preferable in order to suppress diffusion of the Ni-based underlayer 3. If the thickness is too thick, the Cu 3 Sn layer 6 changes to a Sn-rich Cu 6 Sn 5 layer 7 at a high temperature, and the Sn-based surface layer 5 is reduced correspondingly, and the contact resistance may be increased. A range up to about 5 ⁇ m is preferred. This average thickness is a portion where the Cu 3 Sn layer 6 exists and is an average value when the thickness is measured at a plurality of locations.
  • the Cu—Sn intermetallic compound layer 4 is an alloy formed by diffusion of Cu plated on the Ni-based underlayer 3 and Sn on the surface, and depending on conditions such as reflow treatment, In some cases, the entire Cu plating layer is diffused to form the Cu—Sn intermetallic compound layer 4, but the Cu plating layer may remain. When this Cu plating layer remains, the Cu plating layer has a thickness of 0.01 to 0.1 ⁇ m, for example. Further, since Ni in the Ni-based underlayer 3 is slightly diffused into the Cu—Sn intermetallic compound layer 4, Ni is slightly mixed in the Cu 6 Sn 5 layer 7.
  • the Sn-based surface layer 5 is formed by performing reflow treatment after electrolytic plating of Sn or Sn alloy. In order to maintain performance such as heat resistance and insertion / removability as a connector terminal, for example, 0.05 to It is formed to a thickness of 1.5 ⁇ m. Further, an Sn—Ag coating layer may be further formed on the Sn-based surface layer 5 to further improve heat resistance and pluggability as a connector.
  • FIG. 2 shows a conductive member 11 in which a Sn—Ag coating layer 8 is formed on the outermost surface of the same conductive member as in FIG.
  • the Sn—Ag coating layer 8 is formed to have a thin thickness of 0.05 to 0.5 ⁇ m, for example, and contains 0.1 to 5.0% by weight of Ag.
  • the Fe-based underlayer 2, Ni-based underlayer 3, Cu—Sn intermetallic compound layer 4, and Sn-based surface layer 5 are formed after the Fe, Ni, Cu, and Sn plating layers are attached by electrolytic plating.
  • the Sn—Ag coating layer 8 is formed by electrolysis on the Sn-based surface layer 5 after the reflow treatment.
  • a method for manufacturing such a conductive member will be described.
  • a Cu-based substrate a Cu or Cu alloy plate material is prepared, and after cleaning the surface by degreasing, pickling, etc., Fe plating, Ni plating, Cu plating, and Sn plating are sequentially performed in this order. .
  • pickling or rinsing is performed between the plating processes.
  • a sulfuric acid bath mainly composed of ferrous sulfate (FeSO 4 ) and ammonium chloride (NH 4 Cl) is used as a plating bath.
  • a plating bath mainly composed of nickel sulfate (NiSO 4 ), ferrous sulfate (FeSO 4 ), and boric acid (H 3 BO 3 ) is used.
  • the plating temperature is 45 to 55 ° C., and the current density is 5 to 25 A / dm 2 .
  • Ni plating conditions include a plating bath, a watt bath mainly composed of nickel sulfate (NiSO 4 ), boric acid (H 3 BO 3 ), nickel sulfamate (Ni (NH 2 SO 3 ) 2 ) and boric acid.
  • a sulfamic acid bath or the like mainly composed of (H 3 BO 3 ) is used.
  • nickel chloride (NiCl 2 ) or the like is added as a salt that easily causes an oxidation reaction.
  • the plating temperature is 45 to 55 ° C., and the current density is 20 to 50 A / dm 2 .
  • a copper sulfate bath mainly composed of copper sulfate (CuSO 4 ) and sulfuric acid (H 2 SO 4 ) is used as a plating bath, and chlorine ions (Cl ⁇ ) are added for leveling. .
  • the plating temperature is 35 to 55 ° C., and the current density is 20 to 60 A / dm 2 .
  • a sulfuric acid bath containing sulfuric acid (H 2 SO 4 ) and stannous sulfate (SnSO 4 ) as main components is used for the plating bath, the plating temperature is 15 to 35 ° C., and the current density is 10 to 30 A / dm 2 .
  • All the plating processes are performed at a higher current density than a general plating technique.
  • the plating solution agitation technology is important.
  • a fresh plating solution can be supplied quickly, and a uniform plating layer can be formed in a short time with a high current density.
  • the flow rate of the plating solution is desirably 0.5 m / second or more on the surface of the treatment plate.
  • an insoluble anode such as a Ti plate coated with iridium oxide (IrO 2 ) having a high anode limit current density is used as the anode. It is desirable.
  • IrO 2 iridium oxide
  • an Fe-based underlayer is formed on the Cu-based substrate.
  • a Ni-based underlayer, a Cu plating layer, and a Sn plating layer are formed in this order.
  • the average thickness of the Cu plating layer is 0.3 to 0.5 ⁇ m
  • the average thickness of the Sn plating layer is 1.5 to 2.0 ⁇ m.
  • the Sn-based surface layer has a heat resistance as a connector terminal as described above. From the viewpoint of insertion / extraction, it is formed to a thickness of 0.5 to 1.5 ⁇ m, and in order to ensure the thickness of this Sn-based surface layer, the Sn plating layer as a base is 1.5 to 2. 0 ⁇ m is required. In order to obtain a Cu—Sn intermetallic compound layer with small irregularities under this Sn plating layer, the Cu plating layer should have a thickness of 0.3 to 0.5 ⁇ m, which is slightly larger than a normal one. preferable.
  • the Sn plating layer is composed of columnar crystals grown in the thickness direction, and when Cu and Sn react in the next reflow process to form an alloy layer, Cu is a grain boundary of Sn columnar crystals. It is considered that an alloy is formed from the grain boundary so as to penetrate into the grain boundary. However, when the Cu plating layer is thick and the amount of Cu is large, along the grain boundary of the columnar crystal along the thickness direction of the Sn plating layer It is considered that the Cu—Sn alloy formed in this way grows while spreading in the plane direction from the grain boundary, so that the convex portion becomes smooth and becomes a Cu—Sn intermetallic compound layer with few irregularities.
  • the reflow process is performed by heating.
  • the reflow process is preferably performed under the temperature profile shown in FIG.
  • the reflow process is a heating process in which the treated material after plating is heated to a peak temperature of 240 to 300 ° C. for 2.9 to 11 seconds at a temperature rising rate of 20 to 75 ° C./second in a heating furnace having a CO reducing atmosphere.
  • a secondary cooling step is a heating process in which the treated material after plating is heated to a peak temperature of 240 to 300 ° C. for 2.9 to 11 seconds at a temperature rising rate of 20 to 75 ° C./second in a heating furnace having a CO reducing atmosphere.
  • the primary cooling step is performed by air cooling
  • the secondary cooling step is performed by water cooling using 10 to 90 ° C. water.
  • the conductive member subjected to the reflow treatment as described above is pickled and electropolished to remove the oxide film of the Sn-based surface layer, and Sn After the surface of the system surface layer is smoothed, a Sn—Ag coating layer containing 0.1 to 5.0% by weight of Ag is formed thereon. Since the Sn-based surface layer is easily oxidized, the surface roughness of the Sn—Ag coating layer is reduced by removing the oxide film and smoothing the surface at that time. The degree of smoothness is preferably about 0.005 to 0.3 ⁇ m in terms of arithmetic average roughness Ra. Then, an Sn—Ag coating layer is formed on the smooth surface by electrolysis with a thickness of 0.05 to 0.5 ⁇ m.
  • FIG. 4 schematically shows an example of a manufacturing apparatus for carrying out the manufacturing method of the second embodiment.
  • the conductive member manufacturing apparatus 31 includes a degreasing / cleaning tank 32, a Ni plating tank 33, a Cu plating tank 34, a Sn plating tank 35, and cleaning tanks 36 to 38 disposed after the plating tanks 33 to 35.
  • the copper strip 51 is plated while being continuously conveyed in the order of the degreasing / cleaning tank 32, the Ni plating tank 33, the Cu plating tank 34, and the Sn plating tank 35.
  • the degreasing / cleaning tank 32 further includes a degreasing tank 32a, a cleaning tank 32b, a pickling tank 32c, and a cleaning tank 32d.
  • a pair of electrode plates 39 are disposed in each of the plating tanks 33 to 35 so as to face both surfaces of a continuously running copper strip material (Cu-based substrate) 51.
  • the copper strip 51 and the plating solution are relative to each other so that the Reynolds number in the flow field of the plating solution formed between each electrode plate 39 and the copper strip 51 is 1 ⁇ 10 4 to 5 ⁇ 10 5.
  • the plating solution is circulated between a circulation tank 40 (only the circulation tank of the Sn plating tank 35 is shown in FIG. 4).
  • the Sn plating tank 35 is provided with a bubble removing means 41.
  • Sludge removal means 42 is also provided. This sludge removal means 42 connects a sludge settling tank to the circulation tank 40, extracts the plating solution from the circulation tank 40 to the sludge settling tank in a fixed amount, and adds a settling agent. The sludge is allowed to settle while returning the upper liquid to the circulation tank 40 again. The settled sludge is subjected to a centrifuge, sent to a refining company, and reused as Sn.
  • a dryer 43 that dries the copper strip material 51 that has passed through the cleaning tank 38 is provided at a downstream position of the Sn plating tank 35.
  • a reflow furnace 44 is provided at a downstream position of the dryer 43.
  • the reflow furnace 44 is provided with an air cooling zone 45 for primary cooling and a water cooling zone 46 for secondary cooling, which will be described later.
  • Reference numeral 47 denotes a dryer that dries the copper strip material 51 that has passed through the water cooling zone 46.
  • Ni plating conditions include a plating bath, a watt bath mainly composed of nickel sulfate (NiSO 4 ), boric acid (H 3 BO 3 ), nickel sulfamate (Ni (NH 2 SO 3 ) 2 ) and boric acid.
  • a sulfamic acid bath or the like mainly composed of (H 3 BO 3 ) is used.
  • NiCl 2 nickel chloride
  • the plating temperature is 45 to 55 ° C.
  • the current density is 20 to 50 A / dm 2
  • the Reynolds number is 1 ⁇ 10 4 to 5 ⁇ 10 5 .
  • a copper sulfate bath mainly composed of copper sulfate (CuSO 4 ) and sulfuric acid (H 2 SO 4 ) is used as a plating bath, and chlorine ions (Cl ⁇ ) are added for leveling. .
  • the plating temperature is 35 to 55 ° C.
  • the current density is 20 to 60 A / dm 2
  • the Reynolds number is 1 ⁇ 10 4 to 5 ⁇ 10 5 .
  • a sulfuric acid bath containing sulfuric acid (H 2 SO 4 ) and stannous sulfate (SnSO 4 ) as main components is used for the plating bath
  • the plating temperature is 15 to 35 ° C.
  • the current density is 10 to 30 A / dm 2 and Reynolds number of 1 ⁇ 10 4 to 5 ⁇ 10 5 .
  • the sulfuric acid bath is provided with a sludge removing device and a foam removing device.
  • Ni plating layer, Cu plating layer, and Sn plating layer are formed in order on a copper strip.
  • the Cu plating layer has an average thickness of 0.3 to 0.5 ⁇ m
  • the Ni plating layer has an average thickness of 0.1 to 2.0 ⁇ m
  • the Sn plating layer has an average thickness of 1.5 to 0.5 ⁇ m. 2.0 ⁇ m.
  • These Cu plating layer and Sn plating layer are converted into a Cu-Sn intermetallic compound layer and a Sn-based surface layer by a reflow process described later.
  • the Sn-based surface layer has heat resistance and insertion / removal as a connector terminal as described above.
  • the Sn plating layer as a base is required to be 1.5 to 2.0 ⁇ m become.
  • the Cu plating layer is usually 0.3 to 0.5 ⁇ m as in the case of the first embodiment.
  • the thickness is preferably slightly larger than the above.
  • This reflow treatment is a heating process in which a treated material after plating is heated to a peak temperature of 240 to 300 ° C. at a temperature rising rate of 20 to 75 ° C./second in a heating furnace having a CO reducing atmosphere, and the peak temperature is reached. Then, a primary cooling step of cooling for 2 to 10 seconds at a cooling rate of 30 ° C./second or less, and a secondary cooling step of cooling for 0.5 to 5 seconds at a cooling rate of 100 to 250 ° C./second after the primary cooling. Process.
  • the primary cooling step is performed by air cooling
  • the secondary cooling step is performed by water cooling using 10 to 90 ° C. water.
  • the reflow process may be performed immediately after the plating process.
  • the reflow process may be performed within 15 minutes, more preferably within 5 minutes.
  • a short standing time after plating does not cause a problem, but in a normal processing line, it is about one minute after construction.
  • the conductive member 50 includes a Ni-based underlayer 3, a Cu—Sn intermetallic compound layer 4, and a Sn-based surface layer 5 formed in this order on the surface of a copper strip 51, and Cu
  • the —Sn intermetallic compound layer 4 is further composed of a Cu 3 Sn layer 6 and a Cu 6 Sn 5 layer 7.
  • the Ni-based underlayer 3 is formed to a thickness of 0.05 ⁇ m or more, for example, and functions as a barrier layer that prevents Cu diffusion at high temperatures.
  • the Cu—Sn intermetallic compound layer 4 as a whole is formed to a thickness of 0.05 to 1.8 ⁇ m, preferably 0.1 ⁇ m or more, and is further disposed on the Ni-based underlayer 3.
  • the Cu—Sn intermetallic compound layer 4 as a whole is uneven, and the surface roughness of the surface in contact with the Sn-based surface layer 5 is an arithmetic average roughness Ra of 0.05 to 0.25 ⁇ m.
  • the maximum valley depth Rv of the roughness curve is 0.05 to 1.00 ⁇ m.
  • the Cu 3 Sn layer 6 disposed in the lower layer of the Cu—Sn intermetallic compound layer 4 covers the Ni-based underlayer 3 and has a function of suppressing its diffusion, and has an area relative to the Ni-based underlayer 3.
  • the coverage is 60 to 100%, and the average thickness is 0.01 to 0.5 ⁇ m.
  • the Cu—Sn intermetallic compound layer 4 is an alloy formed by diffusion of Cu plated on the Ni-based underlayer 3 and Sn on the surface, and depending on conditions such as reflow treatment, In some cases, the entire Cu plating layer is diffused to form the Cu—Sn intermetallic compound layer 4, but the Cu plating layer may remain. Further, since Ni in the Ni-based underlayer 3 is slightly diffused into the Cu—Sn intermetallic compound layer 4, Ni is slightly mixed in the Cu 6 Sn 5 layer 7.
  • the outermost Sn-based surface layer 5 is formed to have a thickness of, for example, 0.5 to 1.5 ⁇ m in order to optimize surface contact resistance, solderability, corrosion resistance, and insertion / extraction force when used as a connector. .
  • the Ni-based underlayer 3 is formed on the surface of the Cu-based substrate (copper strip) 1.
  • the Ni-based underlayer is interposed via the Fe-based underlayer. May be formed.
  • the Fe density is 5 to 25 A / dm 2 as shown in Table 1 or Table 2, and the Reynolds number in the flow field of the plating solution formed between the electrode plate and the copper strip is used. Is 1 ⁇ 10 4 to 5 ⁇ 10 5 electrolytic plating.
  • a water washing step for washing the plating solution from the surface of the treatment material was inserted between these four types of plating steps.
  • an insoluble anode of a Ti plate coated with iridium oxide was sprayed on the Cu alloy plate at a high speed.
  • a reflow treatment was performed on the treated material. This reflow process was performed 1 minute after the last Sn plating process, and the heating process, the primary cooling process, and the secondary cooling process were performed under various conditions. The above test conditions are summarized in Table 9.
  • the cross section of the treated material in this example is the result of energy dispersive X-ray spectroscopic analysis (TEM-EDS analysis) using a transmission electron microscope.
  • TEM-EDS analysis energy dispersive X-ray spectroscopic analysis
  • Cu 6 Sn 5 layers, and Sn-based surface layer, and the minimum thickness of the Cu—Sn intermetallic compound layer was 0.05 ⁇ m or more.
  • the Cu 6 at the interface Sn 5 layer and the Ni-based base layer has discontinuous Cu 3 Sn layer, Ni of Cu 3 Sn layer observed from a scanning ion microscope of a cross section by focused ion beam (FIB-SIM image)
  • the surface coverage with respect to the system underlayer was 60% or more.
  • the Sn-based surface layer was removed, and the surface roughness of the underlying Cu—Sn intermetallic compound layer was measured.
  • pure Sn such as L80 manufactured by Reybold Co., Ltd. is etched and immersed in an etching solution for removing the plating film made of a component that does not corrode the Cu—Sn alloy for 5 minutes.
  • the surface layer is removed, and the underlying Cu—Sn intermetallic compound layer is exposed.
  • the surface roughness was determined by using a scanning confocal infrared laser microscope LEXT OLS-3000-IR manufactured by Olympus Co., Ltd.
  • the contact resistance after 175 ° C. ⁇ 1000 hours, the presence or absence of peeling, and the wear resistance were measured. Further, the coefficient of dynamic friction and the rate of change in resistance value after 175 ° C. ⁇ 1000 hours were also measured.
  • the contact resistance was measured under the condition of sliding with a load of 0.49 N (50 gf) using an electrical contact simulator manufactured by Yamazaki Seiki Co., Ltd. after the sample was left at 175 ° C. for 1000 hours.
  • 90 ° bending (curvature radius R: 0.7 mm) was performed with a load of 9.8 kN, then held in the atmosphere at 160 ° C.
  • the abrasion resistance was determined by a reciprocating wear test specified in JIS H 8503, with a test load of 9.8 N and abrasive paper no. 400, the number of times until the substrate (Cu-based substrate) was exposed was measured, a sample in which plating remained even after 50 times of testing, and a sample in which the substrate was exposed within 50 times were evaluated as x. .
  • the dynamic friction coefficient a plate-shaped male test piece and a hemispherical female test piece having an inner diameter of 1.5 mm are prepared for each sample so as to simulate the contact portion of the male terminal and female terminal of the fitting type connector.
  • the frictional force between the two test pieces was measured to obtain the dynamic friction coefficient.
  • the male test piece 22 is fixed on the horizontal base 21, the hemispherical convex surface of the female test piece 23 is placed on the male test piece 23, and the plated surfaces are brought into contact with each other.
  • the load P of 9N (500 gf) is applied and the male test piece 22 is pressed. With the load P applied, the frictional force F when the male test piece 22 was pulled 10 mm in the horizontal direction indicated by the arrow at a sliding speed of 80 mm / min was measured by the load cell 25.
  • the resistance value change rate is such that each sample is formed to a size of 10 mm (L) ⁇ 1 m (W), its electric resistance value (R) is measured, and the change rate ⁇ R of the resistance value after heating at 175 ° C. ⁇ 1000 hours. / R (%) was measured.
  • the conductive member of this example has a low contact resistance at high temperatures, no occurrence of peeling or Kirkendall voids, and a small coefficient of dynamic friction. Therefore, the insertion / extraction force when using the connector is also small. It can be judged that it is good.
  • the rate of change in resistance value ( ⁇ R / R) is also small and stable, and it can be determined that it is excellent in fusing characteristics when used as a fuse.
  • Sample 5 and Sample 18 were also measured over time during heating at 175 ° C. for 1000 hours. The result is shown in FIG. As shown in FIG. 9, the sample 5 according to the present invention has a slight increase in contact resistance even when exposed to a high temperature for a long time, whereas the sample 18 according to the prior art has a contact resistance after 1000 hours. Increased to 10 m ⁇ or more.
  • the sample 5 of the present invention has a five-layer structure in which the Sn-based surface layer remains due to the heat resistance of the Fe-based underlayer, whereas in the sample 18 of the prior art, the Fe-based underlayer is thin and has a barrier. Since the function as a layer is not sufficient, it is considered that the contact resistance increased due to the Cu oxide covering the surface. In this case, the thickness of the Fe-based underlayer was 0.5 ⁇ m for sample 5 and 0.05 ⁇ m for sample 18.
  • peeling occurs when the standing time after plating becomes longer. This is because Cu crystal grains precipitated at a high current density are enlarged due to a long standing time, and Cu and Sn react spontaneously to form Cu 6 Sn 5, and smooth Cu 6 Sn during reflowing. This is thought to be because the alloying between 5 and Cu 3 Sn is hindered.
  • the Cu—Sn intermetallic compound layer contains It shall also include those in which a slight amount of Ni is mixed.
  • an Fe-based underlayer is interposed between the Ni-based underlayer and the Cu-based substrate, and the presence of this Fe-based underlayer further enhances the Cu diffusion preventing function, and allows bending. Although generation of cracks during processing can be reduced, it is not always essential, and a Ni-based underlayer may be directly formed on a Cu-based substrate.
  • the cross section of the treated material of this example is a Ni-based underlayer, a Cu 3 Sn layer, and Cu 6 on a copper strip. It has a four-layer structure of Sn 5 layers and Sn-based surface layers.
  • the Cu 6 at the interface Sn 5 layer and the Ni-based base layer has discontinuous Cu 3 Sn layer, Ni of Cu 3 Sn layer observed from a scanning ion microscope of a cross section by focused ion beam (FIB-SIM image)
  • the surface coverage with respect to the system underlayer was 60% or more.
  • the Sn-based surface layer is removed by the same method as in the first embodiment, and the surface roughness of the Cu—Sn intermetallic compound layer below is removed using a scanning confocal infrared laser microscope manufactured by Olympus Corporation. The measurement was performed in the same manner as in the first example using LEXT OLS-3000-IR. The above measurement results are summarized in Table 15.
  • the conductive member of this example has a low contact resistance at high temperatures, no peeling or Kirkendall voids, and a small coefficient of dynamic friction. It can be judged that it is good.
  • Comparative Example 30 the generation of sludge was noticeable in Sn plating.
  • the present invention can be applied to a conductive member in which a plurality of plating layers are formed on the surface of a substrate made of Cu or a Cu alloy, and a method for manufacturing the conductive member.

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Abstract

L'invention porte sur un élément conducteur qui présente une résistance de contact stable, qui résiste au décollage, qui manifeste une force d'insertion/enlèvement faible, qui est stable lorsqu'il est utilisé comme connecteur, et qui possède une excellente caractéristique de fusion lorsqu'il est utilisé comme fusible. Une couche de composé intermétallique Cu-Sn (4) est formée entre une sous-couche à base de Ni (3) formée sur une matière de base à base de Cu (1), et une couche de surface à base de Sn (5) qui forme la surface. De plus, la couche de composé intermétallique Cu-Sn (4) comporte une couche de Cu3Sn (6) disposée sur la sous-couche à base de Ni (3) et une couche de Cu6Sn5 (7) qui est disposée sur la couche de Cu3Sn (6). La rugosité de surface de la face de contact entre la couche de surface à base de Sn (5) et la couche de composé intermétallique Cu-Sn (4) combinant la couche de Cu3Sn (6) et la couche de Cu6Sn5 (7) a une rugosité arithmétique moyenne Ra de 0,05 à 0,25 µm, et la profondeur de vallée maximale Rv de la courbe de rugosité est de 0,05 à 1,00 µm. De plus, la couche de Cu3Sn couvre la sous-couche à base de Ni par une couverture de surface de 60 à 100 %.
PCT/JP2009/003280 2009-04-14 2009-07-13 Élément conducteur et son procédé de fabrication Ceased WO2010119489A1 (fr)

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JP2013231223A (ja) * 2012-05-01 2013-11-14 Dowa Metaltech Kk めっき材およびその製造方法
US10530084B2 (en) 2012-06-27 2020-01-07 Jx Nippon Mining & Metals Corporation Metallic material for electronic components and method for producing same, and connector terminals, connectors and electronic components using same
US10594066B2 (en) 2012-06-27 2020-03-17 Jx Nippon Mining & Metals Corporation Metallic material for electronic components and method for producing same, and connector terminals, connectors and electronic components using same
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US9979110B2 (en) * 2012-10-04 2018-05-22 JX Nippin Mining & Metals Corporation Electronic component metal material and method for manufacturing the same
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WO2014129222A1 (fr) * 2013-02-22 2014-08-28 古河電気工業株式会社 Borne, structure de connexion de câblage et procédé de fabrication de borne
JP5547357B1 (ja) * 2013-02-22 2014-07-09 古河電気工業株式会社 端子、電線接続構造体および端子の製造方法
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WO2015045449A1 (fr) * 2013-09-26 2015-04-02 豊田合成 株式会社 Stratifié et son procédé de production
EP4039855A4 (fr) * 2019-09-30 2023-12-06 Mitsubishi Materials Corporation Matériau de borne pour connecteurs
US11905614B2 (en) 2019-09-30 2024-02-20 Mitsubishi Materials Corporation Terminal material for connector
TWI788016B (zh) * 2021-02-22 2022-12-21 日商Ｊｘ金屬股份有限公司 鍍覆材料及電子零件

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CN102395713A (zh) 2012-03-28
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CN102395713B (zh) 2014-07-16

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