TW201814086A - Metal body and method for producing metal body - Google Patents
Metal body and method for producing metal body Download PDFInfo
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- TW201814086A TW201814086A TW106130786A TW106130786A TW201814086A TW 201814086 A TW201814086 A TW 201814086A TW 106130786 A TW106130786 A TW 106130786A TW 106130786 A TW106130786 A TW 106130786A TW 201814086 A TW201814086 A TW 201814086A
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- 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
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- 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
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- 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
- C25D5/20—Electroplating using ultrasonics, vibrations
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- 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
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- 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
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R43/00—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors
- H01R43/16—Apparatus or processes specially adapted for manufacturing, assembling, maintaining, or repairing of line connectors or current collectors or for joining electric conductors for manufacturing contact members, e.g. by punching and by bending
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Abstract
Description
本發明係有關於表面鍍覆的金屬體及金屬體的製造方法。 The present invention relates to a surface-plated metal body and a method for manufacturing the metal body.
以往，使用以具有導電性的鍍覆材料將表面鍍覆的金屬體作為電子裝置的安裝部件等。近年來，因為考量到環境，變成使用不含鉛的錫系鍍覆材料作為此鍍覆材料。然而，已知使用不含鉛的鍍覆材料進行鍍覆時，會從鍍覆部分產生晶鬚。 Conventionally, a metal body having a surface plated with a conductive plating material is used as a mounting member of an electronic device or the like. In recent years, due to environmental considerations, a tin-based plating material containing no lead has been used as the plating material. However, it is known that when plating is performed using a lead-free plating material, whiskers are generated from the plating portion.
晶鬚被認為是在鍍覆製程或後續的處理製程中因為在金屬鍍覆層產生之應力的釋放現象而產生，由於錫原子被擠到金屬鍍覆層外，進而成長為單晶。當晶鬚產生且成長時，會阻礙電路的連接，導致短路。因此，在專利文獻1，公開了在錫鍍覆處理後沒有出現晶鬚的階段，將鍍覆部分在溶液中照射超音波，藉此抑制晶鬚的產生的方法。 Whiskers are thought to be generated during the plating process or subsequent processing processes due to the release of stress generated in the metal plating layer. As the tin atoms are squeezed out of the metal plating layer, they grow into single crystals. When whiskers are generated and grow, they can hinder the connection of the circuit and cause a short circuit. Therefore, Patent Document 1 discloses a method of suppressing the generation of whiskers by irradiating the plated portion with a ultrasonic wave at a stage where no whiskers appear after the tin plating treatment.
[先前技術文獻] [Prior technical literature]
[專利文獻] [Patent Literature]
[專利文獻1]特許第4986141號公報 [Patent Document 1] Japanese Patent No. 4986141
然而，即使是專利文獻1所記載的方法，也由於金屬鍍覆層的表面的結晶粒徑大，在金屬鍍覆層的表面所產生的應力不能充分地減少，因此不能夠完全地抑制晶鬚之成長。 However, even in the method described in Patent Document 1, the crystal grain size on the surface of the metal plating layer is large, and the stress generated on the surface of the metal plating layer cannot be sufficiently reduced, so the whiskers cannot be completely suppressed. Growth.
本發明係為了解決上述課題之發明，其目的在於提供抑制金屬鍍覆層的晶鬚之成長的金屬體，及抑制晶鬚之成長的金屬體的製造方法。 This invention is an invention for solving the said subject, It aims at providing the metal body which suppresses the growth of the whisker of a metal plating layer, and the manufacturing method of the metal body which suppresses the growth of a whisker.
為了解決上述課題，本發明所採用的技術手段，如下。 In order to solve the above problems, the technical means adopted by the present invention are as follows.
(1)一種金屬體，其特徵在於：包括基材和披覆基材的金屬鍍覆層，金屬鍍覆層由含有95質量%以上的Sn之Sn系合金或Sn單體所構成，金屬鍍覆層的表面的平均結晶粒徑為1.2μm以上、1.8μm以下。 (1) A metal body comprising a metal plating layer including a base material and a coating base material, the metal plating layer being composed of an Sn-based alloy or Sn monomer containing 95% by mass or more of Sn, and metal plating The average crystal grain size on the surface of the coating is 1.2 μm or more and 1.8 μm or less.
(2)上述(1)所記載的金屬體，其特徵在於：基材在以金屬鍍覆層披覆之前，先以阻障(barrier)層披覆。 (2) The metal body according to the above (1), wherein the base material is coated with a barrier layer before being coated with a metal plating layer.
(3)上述(2)所記載的金屬體，其特徵在於：阻障層由Ni所構成。 (3) The metal body according to the above (2), wherein the barrier layer is made of Ni.
(4)一種金屬體的製造方法，對由含有95質量%以上的Sn之Sn系合金或Sn單體所構成的中性浴的金屬鍍覆液，照射超過0kHz、未滿160kHz的頻率之超音波的同時，以金屬鍍覆層披覆基材。 (4) A method for producing a metal body, irradiating a metal plating solution of a neutral bath composed of Sn-based alloy or Sn monomer containing 95% by mass or more of a frequency exceeding 0 kHz and less than 160 kHz. At the same time as the sonic wave, the substrate is coated with a metal plating layer.
(5)一種金屬體的製造方法，對由含有95質量%以上的Sn之Sn系合金或Sn單體所構成的中性浴的金屬鍍覆液，照射35kHz以上、100kHz以下的頻率之超音波的同時， 以金屬鍍覆層披覆基材。 (5) A method for producing a metal body, irradiating an ultrasonic wave having a frequency of 35 kHz to 100 kHz to a metal plating solution of a neutral bath composed of Sn-based alloy or Sn monomer containing 95% by mass or more of Sn. At the same time, the substrate is coated with a metal plating layer.
(6)上述(4)或(5)所記載的金屬體的製造方法，其中在金屬鍍覆液之中，沿著金屬鍍覆液的振動方向，搖動基材的同時，對中性浴的金屬鍍覆液照射超音波。 (6) The method for manufacturing a metal body according to the above (4) or (5), wherein the base material is shaken in the metal plating solution along the vibration direction of the metal plating solution while Ultrasonic waves are irradiated by the metal plating solution.
根據本發明之金屬體及金屬體的製造方法，對金屬鍍覆液照射超音波的同時，基材被金屬鍍覆液披覆，因此金屬鍍覆層的表面的平均結晶粒徑變小，能夠抑制晶鬚之成長。 According to the metal body and the manufacturing method of the metal body of the present invention, while the metal plating solution is irradiated with ultrasonic waves, the substrate is covered with the metal plating solution. Therefore, the average crystal grain size of the surface of the metal plating layer can be reduced, and the Inhibit the growth of whiskers.
1、11~14‧‧‧金屬體 1.11 ~ 14‧‧‧metal body
1A‧‧‧基材 1A‧‧‧ substrate
1b‧‧‧陰極板 1b‧‧‧ cathode plate
1c‧‧‧阻障層 1c‧‧‧Barrier layer
2‧‧‧超音波照射裝置 2‧‧‧ Ultrasonic irradiation device
3‧‧‧搖動裝置 3‧‧‧ Shake device
4‧‧‧容器 4‧‧‧ container
5A‧‧‧陽極板 5A‧‧‧Anode plate
6‧‧‧超音波振動部 6‧‧‧ Ultrasonic vibration unit
11a‧‧‧放大照片 11a‧‧‧ Enlarge picture
11d~14d‧‧‧金屬鍍覆層 11d ~ 14d‧‧‧metal plating
21‧‧‧超音波槽 21‧‧‧ Ultrasonic Slot
21A‧‧‧水 21A‧‧‧Water
41‧‧‧金屬鍍覆液 41‧‧‧Metal plating solution
a1‧‧‧直線 a1‧‧‧Straight
L1~L4‧‧‧最大晶鬚長度 L1 ~ L4‧‧‧Max whisker length
第1圖係繪示出在根據本發明之金屬體1的製造中所使用的超音波照射裝置2的部分剖面和搖動裝置3的結構範例的平面示意圖。 FIG. 1 is a schematic plan view showing a partial cross-section of an ultrasonic irradiation device 2 used in the manufacture of a metal body 1 according to the present invention and a structural example of a shaking device 3.
第2圖係繪示出根據本發明之金屬體1的結構範例的剖面圖。 FIG. 2 is a cross-sectional view showing a structural example of the metal body 1 according to the present invention.
第3圖係將金屬體11的表面放大的照片。 FIG. 3 is a photograph in which the surface of the metal body 11 is enlarged.
第4圖係金屬體11的表面的放大照片11a。 FIG. 4 is an enlarged photograph 11 a of the surface of the metal body 11.
第5圖係將金屬體12的表面放大的照片。 FIG. 5 is an enlarged photograph of the surface of the metal body 12.
第6圖係將金屬體13的表面放大的照片。 FIG. 6 is an enlarged photograph of the surface of the metal body 13.
第7圖係將金屬體14的表面放大的照片。 FIG. 7 is an enlarged photograph of the surface of the metal body 14.
第8圖係超音波輸出與金屬體1的最大晶鬚長度的關係圖。 Fig. 8 is a graph showing the relationship between the ultrasonic output and the maximum whisker length of the metal body 1.
第9圖係超音波輸出與金屬體1的金屬鍍覆層1d的平均結晶粒徑的關係圖。 FIG. 9 is a graph showing the relationship between the ultrasonic output and the average crystal grain size of the metal plating layer 1 d of the metal body 1.
以下，參照附圖對根據本發明之金屬體及該金屬體的製造方法進行說明。 Hereinafter, a metal body and a method for manufacturing the metal body according to the present invention will be described with reference to the drawings.
如第1圖所示，在本實施形態中，使用超音波照射裝置2和搖動裝置3，透過電鍍在基材1A上披覆金屬鍍覆液41，進而製造出金屬體1。超音波照射裝置2和搖動裝置3可以使用現有的。 As shown in FIG. 1, in this embodiment, the base body 1A is coated with a metal plating solution 41 by electroplating using the ultrasonic irradiation device 2 and the shaking device 3 to produce a metal body 1. The ultrasonic irradiation device 2 and the shaking device 3 may use existing ones.
超音波照射裝置2，例如，包括超音波槽21和超音波振動部6。超音波槽21內充滿水21A。容器4透過未繪示的固定部件固定在超音波槽21之中，金屬鍍覆液41加入容器4之中。陽極板5A懸掛在金屬鍍覆液41內。超音波振動部6設置有多個彈簧，能夠使得超音波槽21內以預定的頻率振動。 The ultrasonic irradiation device 2 includes, for example, an ultrasonic groove 21 and an ultrasonic vibration unit 6. The ultrasonic tank 21 is filled with water 21A. The container 4 is fixed in the ultrasonic tank 21 through a fixing member (not shown), and the metal plating solution 41 is added to the container 4. The anode plate 5A is suspended in a metal plating solution 41. The ultrasonic vibration unit 6 is provided with a plurality of springs, and can cause the inside of the ultrasonic groove 21 to vibrate at a predetermined frequency.
在本實施形態中，作為基材1A，以使用在陰極板1b的表面預先披覆有阻障層1c的基材為佳。陰極板1b使用Cu、42合金(alloy)等。阻障層1c係為了避免Cu與Sn的固體反應而設置，阻障層1c使用Ni、NiP等。此外，也可以省略阻障層1c。陽極板5A使用Sn單體或SnBi等的Sn合金等。 In this embodiment, as the base material 1A, it is preferable to use a base material in which a barrier layer 1c is previously coated on the surface of the cathode plate 1b. The cathode plate 1b is made of Cu, 42 alloy, or the like. The barrier layer 1c is provided in order to avoid a solid reaction between Cu and Sn, and the barrier layer 1c is made of Ni, NiP, or the like. In addition, the barrier layer 1c may be omitted. The anode plate 5A is made of Sn alone or Sn alloy such as SnBi.
作為金屬鍍覆液41，使用由含有95質量%以上的Sn之Sn系合金或Sn單體所構成的中性浴的金屬鍍覆液。在金屬鍍覆液41含有Sn系合金的情況下，除了Sn之外，還混合選自Ag、Cu、Au、Ni、Bi、Sb、Pd、Co、Ge、Zn等金屬中一種以上的金屬。 As the metal plating solution 41, a metal plating solution of a neutral bath composed of an Sn-based alloy or Sn monomer containing 95% by mass or more of Sn is used. When the metal plating solution 41 contains an Sn-based alloy, in addition to Sn, one or more metals selected from metals such as Ag, Cu, Au, Ni, Bi, Sb, Pd, Co, Ge, and Zn are mixed.
基材1A安裝在搖動裝置3的搖動位置的前端。如圖中的箭頭所示，搖動裝置3使得基材1A在金屬鍍覆液41 內搖動。 The base material 1A is mounted at the front end of the swing position of the swing device 3. As shown by the arrow in the figure, the shaking device 3 causes the substrate 1A to shake in the metal plating solution 41.
藉由使超音波振動部6振動，超音波通過水21A而照射到容器4內的中性浴的金屬鍍覆液41(以下稱為「金屬鍍覆液41」)中。超音波照射到金屬鍍覆液41時，在金屬鍍覆液41中形成駐波，隨之發生空蝕(cavitation)。在向金屬鍍覆液41照射超音波的同時對基材1A電鍍，金屬鍍覆液41披覆在基材1A，如第2圖所示，製造出具有金屬鍍覆層1d的金屬體1。 When the ultrasonic vibration unit 6 is vibrated, the ultrasonic wave is irradiated to the metal plating solution 41 (hereinafter referred to as "metal plating solution 41") of the neutral bath in the container 4 through the water 21A. When the ultrasonic wave is irradiated to the metal plating solution 41, a standing wave is formed in the metal plating solution 41, and cavitation occurs accordingly. The substrate 1A is electroplated while irradiating the metal plating solution 41 with ultrasonic waves, and the metal plating solution 41 is coated on the substrate 1A. As shown in FIG. 2, a metal body 1 having a metal plating layer 1d is manufactured.
在向金屬鍍覆液41照射超音波的同時啟動搖動裝置3，搖動裝置3使基材1A沿著金屬鍍覆液41的振動方向，即金屬鍍覆液41的駐波的行進方向，來回地搖動。藉由在金屬鍍覆液41之中沿著金屬鍍覆液41的振動方向搖動基材1A，隨之在向金屬鍍覆液41照射超音波的同時，對基材1A進行電鍍，基材1A的表面與在金屬鍍覆液41內形成的駐波均勻地接觸，金屬鍍覆液41均一地披覆於基材1A上，進而製造出具有金屬鍍覆層1d的金屬體1。 When the metal plating solution 41 is irradiated with ultrasonic waves, the shaking device 3 is activated, and the shaking device 3 causes the substrate 1A to follow the vibration direction of the metal plating solution 41, that is, the traveling direction of the standing wave of the metal plating solution 41. Shake. The substrate 1A is shaken in the metal plating solution 41 along the vibration direction of the metal plating solution 41, and the substrate 1A is electroplated while the metal plating solution 41 is irradiated with ultrasonic waves. The substrate 1A is then plated. The surface is uniformly contacted with the standing wave formed in the metal plating solution 41, and the metal plating solution 41 is uniformly coated on the substrate 1A, thereby producing a metal body 1 having a metal plating layer 1d.
由於超音波照射所發生的空蝕，抑制披覆基材1A的金屬鍍覆層1d的表面的結晶粒之成長，縮小結晶粒徑。金屬鍍覆層1d的表面的結晶粒徑變小，則可以充分地減少在金屬鍍覆層1d的表面所產生的應力，能夠抑制晶鬚之成長。因此，藉由在向金屬鍍覆液41照射超音波的同時，將金屬鍍覆液41披覆於基材1A，能夠形成抑制晶鬚之成長的金屬鍍覆層1d形成於基材1A的表面。在本實施形態中，由於對金屬鍍覆液41照射超過0kHz、未滿160kHz之超音波，金屬鍍覆層1d 的表面的平均結晶粒徑為1.2μm以上、1.8μm以下，因此製造出抑制晶鬚之成長的金屬體1。 Cavitation corrosion caused by ultrasonic irradiation suppresses the growth of crystal grains on the surface of the metal plating layer 1d covering the substrate 1A, and reduces the crystal grain size. When the crystal grain size on the surface of the metal plating layer 1d is reduced, the stress generated on the surface of the metal plating layer 1d can be sufficiently reduced, and the growth of whiskers can be suppressed. Therefore, by applying ultrasonic waves to the metal plating solution 41 and coating the metal plating solution 41 on the substrate 1A, a metal plating layer 1d capable of suppressing the growth of whiskers can be formed on the surface of the substrate 1A. . In this embodiment, since the metal plating solution 41 is irradiated with an ultrasonic wave exceeding 0 kHz and less than 160 kHz, the average crystal grain size of the surface of the metal plating layer 1d is 1.2 μm or more and 1.8 μm or less. Must-grow metal body 1.
[實施例] [Example]
以下，在實施例中揭示將本發明應用於金屬體1的情況下的具體範例，但本發明不限於以下的具體範例。 Hereinafter, specific examples in the case where the present invention is applied to the metal body 1 are disclosed in the embodiments, but the present invention is not limited to the following specific examples.
如第1、2圖所示，基材1A在製備作為陰極板1b的30mm×30mm的Cu板的表面上披覆了作為阻障層1c的Ni。基材1A的電流密度為0.7A/dm2。製備出4片這樣的基材1A。金屬鍍覆液41使用Sn-235(Dipsol股份公司製造)。超音波槽21內的水21A保持在25℃。陽極板5A使用30mm×30mm的Sn板。 As shown in FIGS. 1 and 2, the substrate 1A is coated with Ni as a barrier layer 1 c on the surface of a 30 mm × 30 mm Cu plate prepared as a cathode plate 1 b. The current density of the substrate 1A was 0.7 A / dm 2 . Four such substrates 1A were prepared. As the metal plating solution 41, Sn-235 (manufactured by Dipsol Co., Ltd.) was used. The water 21A in the ultrasonic tank 21 was maintained at 25 ° C. As the anode plate 5A, a 30 mm × 30 mm Sn plate was used.
將基材1A安裝在搖動裝置3上使其搖動，隨之用超音波照射裝置2對金屬鍍覆液41照射超音波的同時，將每片基材1A各自電鍍20分42秒。對每片基材1A改變超音波輸出，分別設定為無照射、35kHz、100kHz、160kHz。 The substrate 1A is mounted on the shaking device 3 and shaken, and the ultrasonic wave is irradiated to the metal plating solution 41 with the ultrasonic irradiation device 2 while electroplating each substrate 1A for 20 minutes and 42 seconds. The ultrasonic output was changed for each substrate 1A, and was set to no irradiation, 35 kHz, 100 kHz, and 160 kHz, respectively.
將無照射而電鍍的金屬體11、照射35kHz的超音波而電鍍的金屬體12、照射100kHz的超音波而電鍍的金屬體13及照射160kHz的超音波而電鍍的金屬體14在空氣中放置12小時之後，根據JEITA RC-5241所規定的「電子裝置用連接器(connector)的晶鬚試驗方法」，測量金屬體11~14的金屬鍍覆層11d~14d所產生的晶鬚的長度。 A metal body 11 plated without irradiation, a metal body 12 plated with ultrasound at 35 kHz, a metal body plated 13 with ultrasound at 100 kHz, and a metal body 14 plated with ultrasound at 160 kHz are left in the air 12 Hours later, the length of the whiskers generated by the metal plating layers 11d to 14d of the metal bodies 11 to 14 was measured according to the "Whisker Test Method for Connectors for Electronic Devices" prescribed by JEITA RC-5241.
更詳細而言，使用直徑1mm的氧化鋯(zirconia)球，以300g的負重將金屬體11~14壓住240小時。壓完後，對金屬鍍覆層11d~14d的壓痕的周圍部分，使用 Quanta250FEG(FEI製造)的掃描式電子顯微鏡(SEM)，拍攝任意3個位置的放大照片。測量在所拍攝的照片中可看到的晶鬚的長度，觀察在各個金屬鍍覆層11d~14d的晶鬚的長度，將最長晶鬚的長度稱為最大晶鬚長度L1~L4，如第3圖、第5圖~第8圖所示。 More specifically, a metal body 11 to 14 was pressed for 240 hours with a load of 300 g using a zirconia ball having a diameter of 1 mm. After pressing, the surrounding part of the indentation of the metal plating layers 11d to 14d was scanned with a scanning electron microscope (SEM) of a Quanta250FEG (manufactured by FEI), and magnified photographs were taken at any of three positions. Measure the length of the whiskers that can be seen in the photographs taken, observe the length of the whiskers in each of the metal plating layers 11d to 14d, and call the length of the longest whisker the maximum whisker length L1 to L4. Figures 3, 5 to 8 are shown.
如第3圖所示，無照射而電鍍的金屬體11的最大晶鬚長度L1為38.6μm。如第5圖所示，照射35kHz的超音波而電鍍的金屬體12的最大晶鬚長度L2為26.2μm。如第6圖所示，照射100kHz的超音波而電鍍的金屬體13的最大晶鬚長度L3為12.9μm。如第7圖所示，照射160kHz的超音波而電鍍的金屬體14的最大晶鬚長度L4為39.9μm。 As shown in FIG. 3, the maximum whisker length L1 of the metal body 11 plated without irradiation is 38.6 μm. As shown in FIG. 5, the maximum whisker length L2 of the plated metal body 12 irradiated with ultrasonic waves of 35 kHz is 26.2 μm. As shown in FIG. 6, the maximum whisker length L3 of the plated metal body 13 irradiated with ultrasonic waves of 100 kHz is 12.9 μm. As shown in FIG. 7, the maximum whisker length L4 of the plated metal body 14 irradiated with an ultrasonic wave of 160 kHz is 39.9 μm.
如第8圖所示，相較於無照射時的最大晶鬚長度L1，照射35kHz、100kHz的超音波時的最大晶鬚長度L2、L3變短。然而，照射160kHz的超音波時，最大晶鬚長度L4與無照射時的最大晶鬚長度L1相同程度地變長。從此結果來看可以說，用超過0kHz、未滿160kHz之超音波照射，能夠抑制晶鬚之成長。特別地，超音波輸出可說是，以超過0kHz、120kHz以下為佳，以35kHz以上、100kHz以下為較佳。 As shown in FIG. 8, the maximum whisker lengths L2 and L3 when the ultrasonic waves of 35 kHz and 100 kHz are irradiated are shorter than the maximum whisker length L1 when no irradiation is performed. However, when the ultrasonic wave of 160 kHz is irradiated, the maximum whisker length L4 becomes as long as the maximum whisker length L1 without irradiation. From this result, it can be said that the growth of whiskers can be suppressed by irradiation with ultrasonic waves exceeding 0 kHz and less than 160 kHz. In particular, it can be said that the ultrasonic output is more than 0 kHz and 120 kHz, and more preferably 35 kHz and 100 kHz.
接著，從金屬體11~14拍攝的每3張放大照片，測量金屬體11~14的金屬鍍覆層11d~14d的表面的平均結晶粒徑。如第4圖所示，其為將金屬體11的金屬鍍覆層11d放大的3張照片中的1張，以放大照片11a為例來說明金屬鍍覆層11d的平均結晶粒徑的測量方法。首先，在放大照片11a上畫出任意的直線a1，測量直線a1的長度。接著，計算與直線 a1交叉的金屬鍍覆層11d的晶粒數量。將直線a1的長度除以計算出的晶粒數量，得到在放大照片11a中的平均結晶粒徑。在放大照片11a中的平均結晶粒徑為2.07μm。 Next, the average crystal grain size on the surfaces of the metal plating layers 11d to 14d of the metal bodies 11 to 14 was measured from every three enlarged photographs taken of the metal bodies 11 to 14. As shown in FIG. 4, this is one of three photographs in which the metal plating layer 11 d of the metal body 11 is enlarged. The enlarged photograph 11 a is taken as an example to explain the measurement method of the average crystal grain size of the metal plating layer 11 d. . First, an arbitrary straight line a1 is drawn on the enlarged photograph 11a, and the length of the straight line a1 is measured. Next, the number of crystal grains of the metal plating layer 11d crossing the straight line a1 is calculated. The length of the straight line a1 is divided by the calculated number of crystal grains to obtain the average crystal grain size in the enlarged photograph 11a. The average crystal grain size in the enlarged photograph 11a was 2.07 μm.
同樣地，在將金屬體11放大的其餘2張照片及將金屬體12~14放大的每3張照片中，也任意地畫出直線並測量其長度，計算與直線交叉的各個金屬體的金屬鍍覆層的晶粒數量，算出平均結晶粒徑。 Similarly, in the remaining two photos in which the metal body 11 is enlarged and in each of the three photos in which the metal bodies 12 to 14 are enlarged, a straight line is arbitrarily drawn and the length is measured, and the metal of each metal body crossing the straight line is calculated The number of crystal grains in the plated layer was calculated as the average crystal grain size.
雖然未繪示出，但是從將金屬體11放大的其餘2張照片分別算出，金屬鍍覆層11d的平均結晶粒徑分別為2.19μm、1.86μm。從金屬體12的3張放大照片分別算出，金屬鍍覆層12d的平均結晶粒徑為1.55μm、1.55μm、1.38μm。從金屬體13的3張放大照片分別算出，金屬鍍覆層13d的平均結晶粒徑為1.62μm、1.55μm、1.69μm。從金屬體14的3張放大照片分別算出，金屬鍍覆層14d的平均結晶粒徑為2.19μm、2.33μm、2.33μm。 Although not shown, the average crystal grain size of the metal plated layer 11d was calculated from the remaining two photographs in which the metal body 11 was enlarged, and were 2.19 μm and 1.86 μm, respectively. From the three enlarged photographs of the metal body 12, the average crystal grain size of the metal plating layer 12d was calculated to be 1.55 μm, 1.55 μm, and 1.38 μm. From the three enlarged photographs of the metal body 13, the average crystal grain size of the metal plating layer 13d was calculated to be 1.62 μm, 1.55 μm, and 1.69 μm. From the three enlarged photographs of the metal body 14, the average crystal grain size of the metal plating layer 14d was calculated to be 2.19 μm, 2.33 μm, and 2.33 μm.
更進一步，從每3張放大照片的平均結晶粒徑，分別算出金屬體11~14的金屬鍍覆層11d~14d的平均結晶粒徑。金屬鍍覆層11d~14d各自的平均結晶粒徑如第9圖所示。 Furthermore, the average crystal grain size of the metal plating layers 11d to 14d of the metal bodies 11 to 14 was calculated from the average crystal grain size of each of the three enlarged photographs. The average crystal grain size of each of the metal plating layers 11d to 14d is shown in FIG. 9.
金屬體11的金屬鍍覆層11d的平均結晶粒徑為2.04μm，金屬體12的金屬鍍覆層12d的平均結晶粒徑為1.49μm，金屬體13的金屬鍍覆層13d的平均結晶粒徑為1.62μm，金屬體14的金屬鍍覆層14d的平均結晶粒徑為2.28μm。 The average crystal grain size of the metal plating layer 11d of the metal body 11 is 2.04 μm, the average crystal grain size of the metal plating layer 12d of the metal body 12 is 1.49 μm, and the average crystal grain diameter of the metal plating layer 13d of the metal body 13 It was 1.62 μm, and the average crystal grain size of the metal plating layer 14 d of the metal body 14 was 2.28 μm.
從此結果可知，相較於無照射時，照射35kHz、 100kHz的超音波時，平均結晶粒徑變小。然而，照射160kHz的超音波時，平均結晶粒徑與無照射時相同程度地變大。從此結果來看可以說，照射超過0kHz、未滿160kHz之超音波時，能夠使得金屬體1的金屬鍍覆層1d的平均結晶粒徑變小。超音波輸出可說是，以超過0kHz、120kHz以下為佳，以35kHz以上、100kHz以下為較佳。 From this result, it can be seen that the average crystal grain size becomes smaller when the ultrasonic waves of 35 kHz and 100 kHz are irradiated than when there is no irradiation. However, when an ultrasonic wave of 160 kHz is irradiated, the average crystal grain size becomes as large as that when no irradiation is performed. From this result, it can be said that the average crystal grain size of the metal plating layer 1d of the metal body 1 can be made smaller when the ultrasonic waves are irradiated above 0 kHz and below 160 kHz. It can be said that the ultrasonic output is more than 0 kHz and 120 kHz, and more preferably 35 kHz and 100 kHz.
如第8、9圖所示，可以說平均結晶粒徑的尺寸和最大晶鬚長度之間存在相關性。更詳細而言，可以說金屬鍍覆層1d的表面的平均結晶粒徑小之金屬體1，最大晶鬚長度短，而金屬鍍覆層1d的表面的平均結晶粒徑大之金屬體1，最大晶鬚長度長。可以認為這是因為，平均結晶粒徑小則應力分散，進而抑制晶鬚之成長且縮短晶鬚的緣故。可以說，金屬鍍覆層1d的表面的平均結晶粒徑為1.2μm以上、1.8μm以下的金屬體1，能夠抑制晶鬚之成長。特別地，金屬鍍覆層1d的表面的平均結晶粒徑可說是，以1.49μm以上、1.62μm以下為較佳。 As shown in Figures 8 and 9, it can be said that there is a correlation between the size of the average crystal grain size and the maximum whisker length. More specifically, it can be said that the metal body 1 having a small average crystal grain size on the surface of the metal plating layer 1d has a short maximum whisker length, and the metal body 1 having a large average crystal grain size on the surface of the metal plating layer 1d. The maximum whisker length is long. This is considered to be because the stress is dispersed when the average crystal grain size is small, thereby suppressing the growth of the whiskers and shortening the whiskers. It can be said that the metal body 1 having an average crystal grain size on the surface of the metal plating layer 1d of 1.2 μm or more and 1.8 μm or less can suppress the growth of whiskers. In particular, the average crystal grain size on the surface of the metal plating layer 1d is preferably 1.49 μm or more and 1.62 μm or less.
在本實施形態中，超音波振動部6為設置在超音波槽21的下方的結構，但並不限於此。超音波振動部6也可以設置在超音波槽21的側面或上方，也可以設置在多個位置。 In the present embodiment, the ultrasonic vibration unit 6 has a structure provided below the ultrasonic groove 21, but it is not limited to this. The ultrasonic vibration unit 6 may be provided on the side or above the ultrasonic groove 21 or may be provided at a plurality of positions.
在本實施形態中，為了對金屬鍍覆液41均勻地照射超音波而在超音波槽21加入水21A，但是只要能夠傳遞駐波的液體即可，並不限定於此。除了水21A之外，例如也可以加入乳化液，也可以省略水21A而對金屬鍍覆液41直接施加超音波振動。再者，在本實施形態中，使用超音波照射裝置2且以搖動裝置3將基材1A搖動的同時進行鍍覆，但並不限定 於此。例如，也可以使用未繪示的滾鍍(barrel plating)裝置等的鍍覆裝置，將基材1A放置於鍍覆裝置內使其旋轉，並在對金屬鍍覆液41照射超音波的同時鍍覆基材1A。 In the present embodiment, water 21A is added to the ultrasonic tank 21 in order to uniformly irradiate the metal plating liquid 41 with ultrasonic waves, but it is not limited to this as long as it is a liquid capable of transmitting standing waves. In addition to water 21A, for example, an emulsion may be added, or water 21A may be omitted, and ultrasonic vibration may be directly applied to the metal plating solution 41. Furthermore, in this embodiment, plating is performed while the base material 1A is shaken by using the ultrasonic irradiation device 2 and the shaking device 3, but it is not limited to this. For example, a plating device such as a barrel plating device (not shown) may be used. The substrate 1A is placed in the plating device and rotated, and the metal plating solution 41 is irradiated with ultrasonic waves while plating. Cover substrate 1A.
在本實施形態中，基材1A使用Cu陰極板1b的表面披覆有作為阻障層1c的Ni之基材，陽極板5A使用Sn，但不限定於此。雖然為了在金屬鍍覆時避免Cu與Sn的固體反應而將阻障層1c披覆於基材1A，然而也可以省略阻障層1c。再者，也可以使用NiP等的Ni合金作為阻障層1c。陰極板1b也可以使用42合金來代替Cu板，其尺寸或形狀也不限於上述範例，可以是任何尺寸或形狀。陽極板5A，除了Sn之外也可以使用SnBi等的Sn合金。 In this embodiment, the base material 1A is a base material on which the surface of the Cu cathode plate 1b is coated with Ni as the barrier layer 1c, and the anode plate 5A is made of Sn, but it is not limited to this. Although the barrier layer 1c is coated on the substrate 1A in order to avoid a solid reaction between Cu and Sn during metal plating, the barrier layer 1c may be omitted. In addition, a Ni alloy such as NiP may be used as the barrier layer 1c. The cathode plate 1b may also use 42 alloy instead of the Cu plate, and its size or shape is not limited to the above examples, and may be any size or shape. For the anode plate 5A, an Sn alloy such as SnBi may be used in addition to Sn.
在本實施形態中，使用Sn單體作為中性浴的金屬鍍覆液，但不限定於此。除了Sn之外，還混合選自Ag、Cu、Au、Ni、Bi、Sb、Pd、Co、Ge、Zn等金屬中一種以上的金屬，也可以包括含有95質量%以上的Sn之Sn系合金。 In this embodiment, Sn metal is used as the metal plating solution for the neutral bath, but it is not limited to this. In addition to Sn, one or more metals selected from metals such as Ag, Cu, Au, Ni, Bi, Sb, Pd, Co, Ge, and Zn may be mixed, and an Sn-based alloy containing 95% by mass or more of Sn may also be included .
[產業利用性] [Industrial availability]
本發明適用於表面鍍覆的金屬體，該金屬體作為連接器、晶片(chip)部件、導線架(lead frame)、功率元件(power device)、基板等的電子裝置的安裝部件來使用。 The present invention is applicable to a surface-plated metal body that is used as a mounting member of an electronic device such as a connector, a chip component, a lead frame, a power device, a substrate, and the like.
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