TW200521270A - Electrolytic stripping method - Google Patents

Electrolytic stripping method Download PDF

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Publication number
TW200521270A
TW200521270A TW093132149A TW93132149A TW200521270A TW 200521270 A TW200521270 A TW 200521270A TW 093132149 A TW093132149 A TW 093132149A TW 93132149 A TW93132149 A TW 93132149A TW 200521270 A TW200521270 A TW 200521270A
Authority
TW
Taiwan
Prior art keywords
silver
copper
electrolytic stripping
electrolytic
stripping solution
Prior art date
Application number
TW093132149A
Other languages
Chinese (zh)
Other versions
TWI367267B (en
Inventor
Yoko Ogihara
Masao Nakazawa
Original Assignee
Shinko Electric Ind Co
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
Application filed by Shinko Electric Ind Co filed Critical Shinko Electric Ind Co
Publication of TW200521270A publication Critical patent/TW200521270A/en
Application granted granted Critical
Publication of TWI367267B publication Critical patent/TWI367267B/en

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
    • C25F5/00—Electrolytic stripping of metallic layers or coatings
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L23/00—Details of semiconductor or other solid state devices
    • H01L23/48—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor
    • H01L23/488—Arrangements for conducting electric current to or from the solid state body in operation, e.g. leads, terminal arrangements ; Selection of materials therefor consisting of soldered or bonded constructions
    • H01L23/495—Lead-frames or other flat leads
    • H01L23/49579—Lead-frames or other flat leads characterised by the materials of the lead frames or layers thereon
    • H01L23/49582—Metallic layers on lead frames
    • 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
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L2224/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • H01L2224/45001—Core members of the connector
    • H01L2224/45099—Material
    • H01L2224/451—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
    • H01L2224/45138—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
    • H01L2224/45144—Gold (Au) 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
    • H01L2224/42—Wire connectors; Manufacturing methods related thereto
    • H01L2224/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L2224/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • H01L2224/485—Material
    • H01L2224/48505—Material at the bonding interface
    • H01L2224/48599—Principal constituent of the connecting portion of the wire connector being Gold (Au)
    • H01L2224/486—Principal constituent of the connecting portion of the wire connector being Gold (Au) with a principal constituent of the bonding area 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
    • H01L2224/48638—Principal constituent of the connecting portion of the wire connector being Gold (Au) with a principal constituent of the bonding area 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
    • H01L2224/48639—Silver (Ag) 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
    • H01L2224/80—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected
    • H01L2224/85—Methods for connecting semiconductor or other solid state bodies using means for bonding being attached to, or being formed on, the surface to be connected using a wire connector
    • H01L2224/8538—Bonding interfaces outside the semiconductor or solid-state body
    • H01L2224/85399—Material
    • H01L2224/854—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
    • H01L2224/85438—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
    • H01L2224/85439—Silver (Ag) as principal constituent
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L24/00—Arrangements for connecting or disconnecting semiconductor or solid-state bodies; Methods or apparatus related thereto
    • H01L24/01—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
    • H01L24/42—Wire connectors; Manufacturing methods related thereto
    • H01L24/44—Structure, shape, material or disposition of the wire connectors prior to the connecting process
    • H01L24/45—Structure, shape, material or disposition of the wire connectors prior to the connecting process of an individual wire connector
    • 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
    • H01L2924/0001—Technical content checked by a classifier
    • H01L2924/00014—Technical content checked by a classifier the subject-matter covered by the group, the symbol of which is combined with the symbol of this group, being disclosed without further technical details
    • 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
    • H01L2924/01012—Magnesium [Mg]
    • 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
    • H01L2924/01019—Potassium [K]
    • 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
    • H01L2924/01028—Nickel [Ni]

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Power Engineering (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Computer Hardware Design (AREA)
  • Physics & Mathematics (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Lead Frames For Integrated Circuits (AREA)

Abstract

The present invention provides an electrolytic stripping method comprising electrolytically stripping: a copper plating film exposed from a silver plating film that partially covers a copper plating film formed on the entire surface of a member; and leaking silver formed on an exposed portion of the copper plating film and having a smaller thickness than the silver plating film, using the copper plating film as an anode, wherein the electrolytic stripping is carried out using a cyan compound-free electrolytic copper-stripping liquid, and the electrolytic stripping liquid comprises a compound capable of forming, with silver, a complex ion that is more easily dissociated than a complex ion of silver and cyan; and wherein silver and copper are deposited on a cathode which is used as a counter electrode to the anode and which is made of a metal that is chemically stable against the electrolytic stripping liquid.

Description

200521270 九、發明說明： 【發明所屬之技術領域】 本發明關於一種電解剝離方法。更詳細地，本發明關於 一種電解剝離方法，其係剝離：一鍍銅薄膜，其係由一鍍 銀薄膜露出，該鍍銀薄膜係部分地覆蓋形成於構件之整個 表面上之鍍銅薄膜；及滲出銀，形成於鍍銅薄膜的露出部 分上且具有比鍍銀薄膜更小厚度，透過使用鍍銅薄膜及滲 出銀作為陽極之電解剝離。 【先前技術】 於欲用於半導體裝置之導線架中，如圖1所示，於構成 導線架1 0 (由鐵基底合金材料，例如鐵-鎳合金（4 2合金） 製成）之每一内引線1 2的頂部上，於晶粒座1 4之側（此頂 部將於以下簡稱為「頂部」），係形成欲與金線之端部連接 之一結合區1 2 a (金線之其他端部則連接於安裝於晶粒座 14上之半導體元件）。 一鍍銀薄膜形成於此一結合區1 2 a上，並且前述金線之 一端部係連接於結合區1 2 a。 如圖1所示，於形成具有鍍銀薄膜形成於其上之晶粒結 合區1 2 a時，於由鐵基底合金材料製成之導線架1 0之每一 内引線1 2的頂部上，一鍍銅薄膜係透過電鍍電解銅而形成 於導線架1 0的整個周圍上。 如圖2 A所示，將具有此一鍍銅薄膜形成於其上之導線 架1 0放在橡膠製的遮罩板1 8 a與1 8 b之間，依此方式，僅 一部分用以形成結合區1 2 a之鑛銅薄膜1 6於内引線1 2的 5 312XP/發明說明書(補件)/94-02/93132149 200521270 頂部2 0露出，並且進行電鍍電解銀，以形成鍍銀薄膜於露 出的鍍銅薄膜1 6上。 接著，如圖2B所示，於完成電鍵電解銀後，當移走遮 罩板1 8 a和1 8 b時，鍍銀薄膜2 2僅於用以形成内引線1 2 頂部2 0的結合區1 2 a之區域上形成。 之後，將導線架1 0浸潰於電解剝離液中，並且藉電解 剝離（使用導線架1 0作為陽極），去除未被鍍銀薄膜2 2覆 蓋而露出之鍵銅薄膜16。因此，如圖2C所示，含有鍵銅 薄膜1 6及鍍銀薄膜2 2之結合區1 2 a僅於用以形成内引線 1 2頂部2 0的結合區1 2 a之區域上形成。 此刻，於將導線架1 0放在橡膠製的遮罩板1 8 a與1 8 b 之間且形成鍍銀薄膜於露出的鍍銅薄膜1 6上時，具有厚度 小於鍍銀薄膜2 2之厚度的滲出銀2 4因由於遮罩板1 8 a與 1 8 b的應變等等造成電解銀電鍍液滲漏而亦形成於已被遮 罩板1 8 a與1 8 b覆蓋的區域上，如圖2 B所示。此滲出銀 2 4亦透過電解剝離鍍銅薄膜1 6而被移除，並且如圖2 C所 示，鍍銀薄膜2 2僅於用以形成内引線1 2頂部2 0的結合區 1 2 a之區域上形成。 為了電解剝離滲出銀2 4及鍍銅薄膜1 6，而實質上不會 剝離鍍銀薄膜2 2，如以下專利文件1所述，已使用含氰化 合物之電解剝離液。 專利文件1 :日本專利J P 5 9 - 0 3 1 9 0 0 A (第2至3頁）。 如專利文件1所示，藉浸潰導線架1 0 (於其上，鍍銀薄 膜2 2僅形成於内引線1 2的頂部2 0處）於含氰化合物之電 6 312XP/發明說明書(補件)/94-02/93132149 200521270 解剝離液中，並且進行銅之電解剝離（使用此導線架1 〇作 為陽極及不銹鋼板作為陰極），電解剝離滲出銀2 4及鍍銅 薄膜1 6，而實質上不會剝離鍍銀薄膜2 2是可能的。 然而，倘若連續地使用含氰化合物之電解剝離液，則於 電解剝離滲出銀2 4及鍍銅薄膜1 6之過程中，鍍銅薄膜1 6 與滲出銀2 4的剝離速度係於相當短期間内降低。基於此理 由，經常地更換電解剝離液是必要的。 再者，倘若想要自欲交換及處理之含氰化物的電解剝離 液回收銀（為貴金屬），則需要另一特殊的回收步驟。 【發明内容】 因此，本發明之目的係提供一種使用電解剝離液之電解 剝離方法，該電解剝離液係為不含氰化合物之電解剝離 液，並且相對於含氰化合物之電解剝離液，其壽命可大大 地延長。 本發明之其他目的及效果，自以下說明當可明白。 為了達成上述目的，本發明人進行廣泛的研究。結果， 係使用導線架1 0 (如圖2 Β所示，其中鍍銀薄膜2 2僅形成 於内引線1 2的頂部2 0處）作為陽極，同時使用不含氰化合 物之電解剝離液（其含有可形成比銀和氰之絡合物離子更 容易解離之銀和銨的絡合物離子之磷酸三銨進行電解剝 離。同時，鉑製陰極係用為導線架1 0 (作為陽極）之反電 極。結果，發現當電解剝離滲出銀2 4及鍍銅薄膜1 6時， 銀和銅係沉積於陰極上，而實質上不會剝離鍍銀薄膜2 2。 再者，發現依此方式藉著當沉積銀和銅於陰極時進行電 7 312ΧΡ/發明說明書(補件)/94-02/93132149 200521270 解剝離，相較於含氰化合物之電解剝離液，其壽命可延長， 因而造成本發明之實現。 具體而言，本發明係關於一種電解剝離方法，其包含電 解剝離： 一鍍銅薄膜其係由一鍍銀薄膜露出，該鍍銀薄膜係部分 地覆蓋形成於構件之整個表面上之鍍銅薄膜；及 滲出銀，使用該鑛銅薄膜作為陽極，而形成於該鐘銅薄 膜的露出部分上且具有比該鍍銀薄膜更小厚度， 其中該電解剝離係使用不含氰化物之電解銅剝離液進 行，並且該電解剝離液包含一種可與銀形成比銀和氰之絡 合物離子更容易解離的絡合物離子之化合物；且 其中銀和銅係沉積於陰極上，該陰極係用作陽極之反電 極且由對該電解剝離液具化學安定性之金屬製成。 於本發明中，可與銀形成比銀和氰之絡合物離子更容易 解離的絡合物離子之該化合物係為一種可與銀形成具有比 銀和氰之絡合物離子更低絡合物安定性常數之絡合物離 子。 就此化合物而言，可使用至少一種選自由氨水、錄鹽、 酒石酸鹽、磷酸及擰檬酸鹽組成之群之化合物。 再者，由於欲用於本發明之電解剝離液係為用於電解剝 離鍍銅薄膜之電解剝離液，故較佳為電解剝離液含有銅化 合物或芳族硝基化合物作為銅氧化劑，並且係經調整為具 pH為9至1 2。 於此中，銅化合物較佳係為添加至電解剝離液中之衍生 8 312XP/發明說明書(補件)/94-02/93132 ] 49 200521270 自可形成銅敍絡合物之銨源與銅源。 再者，經由以一陰極袋圍繞陰極，藉陰極袋收集銀和銅 顆粒（包含分別沉積於陰極上之銀和銅）是可能的；並且經 由自電解剝離液取出陰極袋，回收銀和銅（含有沉積於陰極 上之銀和銅）是可能的。 順便一提，由鐵基底合金製成之導線架可合宜地用作構 件。 迄今所用之含氰化合物的電解剝離液之壽命為何短暫 之原因可被認為如下。 由於電解剝離液中之氰離子與電解剝離液中之銀離子 形成安定的絡合物離子，故電解剝離液中之銀濃度隨著滲 出銀的電解剝離處理量增加而提高。當電解剝離液中之銀 濃度提高時，滲出銀和鍍銅薄膜的剝離速度降低。 另一方面，於本發明中，電解剝離之進行係使用不含氰 化物之電解銅剝離液（包含一種可與銀形成比銀和氰之絡 合物離子更容易解離的絡合物離子之化合物），同時沉積銀 和銅於用作鍍銅薄膜及滲出銀（作為陽極）之反電極之陰極 上。 因此，根據本發明之電解剝離方法，避免鍍銅薄膜和滲 出銀的剝離速度因電解剝離液中之銀累積而降低是可能 的；相較於含有氰化合物之習知的電解剝離液，大大地延 長其壽命是可能的。 【實施方式】 用於本發明之電解剝離液係為不含氰化合物之電解剝 9 312XP/發明說明書(補件)/94-02/93132149 200521270 離液。就電解剝離液而言，可適當地使用含有銅化合物或 芳族硝基化合物作為銅氧化劑之電解剝離液。 就作為銅氧化劑之銅化合物而言，銅銨絡合物是適合 的。經由添加作為銨源之氨水或銨鹽以及作為銅源之硫酸 銅、碳酸銅、草酸銅或氫氧化銅於電解剝離液中，可形成 此一銅銨絡合物。 於具有經添加銨源及銅源之電解剝離液中所形成之銅 銨絡合物包含[Cu(NH3)2]2+、[Cu(NH3)4]2 +及[Cu(NH3)6]2 +中 之至少一者。 就芳族硝基化合物而言，可適當地使用氯硝基苯曱酸、 2 -氣-4 -硝基苯曱酸、鄰-硝基苯甲酸、間-硝基苯曱酸、對 -硝基苯甲酸、對-硝基苯甲酸乙酯及對-硝基苯曱酸鈉。 含有芳族硝基化合物作為銅氧化劑但加入氰化合物之 電解剝離液，無法被預期具有延長的壽命。 用於本發明電解剝離液中之銅氧化劑的含量通常為1至 100克/升，較佳為5至40克/升。 再者，較佳係調整此一電解剝離液，使得具pH為9至 1 2。藉使用氨水作為欲添加為可形成銅銨絡合物之銨源， 或使用p Η調整劑（例如氫氧化鈉），可達成p Η調整。 於此中，在電解剝離液的pH小於9之例子中，或在電 解剝離液的p Η超過1 2之例子中，鍍銅薄膜的剝離速度有 降低之傾向。 一種可與銀形成比銀和氰之絡合物離子更容易解離的 絡合物離子之化合物係添加於用於本發明之電解銅剝離液 10200521270 IX. Description of the invention: [Technical field to which the invention belongs] The present invention relates to an electrolytic stripping method. In more detail, the present invention relates to an electrolytic peeling method, which is peeling off: a copper-plated film exposed by a silver-plated film that partially covers a copper-plated film formed on the entire surface of a component; And exuded silver, which is formed on the exposed portion of the copper-plated film and has a smaller thickness than the silver-plated film, and is subjected to electrolytic peeling by using the copper-plated film and the exuded silver as an anode. [Prior art] In a lead frame to be used in a semiconductor device, as shown in FIG. 1, each of the lead frames 10 (made of an iron-based alloy material such as an iron-nickel alloy (42 alloy)) is used. The top of the inner lead 12 is on the side of the die seat 14 (this top will be referred to as the "top" hereinafter), forming a bonding region 1 2 a (of the gold wire) to be connected to the end of the gold wire. The other ends are connected to the semiconductor element mounted on the die pad 14). A silver-plated film is formed on the bonding region 12a, and one end portion of the foregoing gold wire is connected to the bonding region 12a. As shown in FIG. 1, when forming a grain bonding region 12a having a silver-plated film formed thereon, on the top of each inner lead 12 of a lead frame 10 made of an iron-based alloy material, A copper-plated film is formed on the entire periphery of the lead frame 10 through electrolytic copper plating. As shown in FIG. 2A, the lead frame 10 having the copper-plated film formed thereon is placed between the rubber mask plates 18a and 18b, and in this way, only a part is used to form The ore copper film 16 in the bonding area 1 2 a 5 of the inner lead 12 2 312XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270 The top 2 0 is exposed and electroplated electrolytic silver is formed to form a silver plated film on The exposed copper-plated film 16 is on. Next, as shown in FIG. 2B, after the key electrolysis silver is completed, when the mask plates 18a and 18b are removed, the silver-plated film 22 is used only to form the bonding area of the inner lead 1 2 and the top 20 1 2 a. After that, the lead frame 10 is immersed in an electrolytic stripping solution, and the key copper film 16 which is not covered by the silver-plated thin film 2 2 is removed by electrolytic stripping (using the lead frame 10 as an anode). Therefore, as shown in FIG. 2C, the bonding region 12a containing the bond copper film 16 and the silver-plated film 22 is formed only on the region of the bonding region 12a for forming the top 20 of the inner lead 12. At this moment, when the lead frame 10 is placed between the rubber mask plates 18 a and 18 b and a silver-plated film is formed on the exposed copper-plated film 16, the thickness is smaller than that of the silver-plated film 22. Exuded silver with a thickness of 2 4 is also formed on the area covered by the mask plates 1 8 a and 1 8 b due to the leakage of the electrolytic silver plating solution due to the strain of the mask plates 1 8 a and 1 8 b. As shown in Figure 2B. The exuded silver 2 4 is also removed by electrolytically peeling the copper-plated film 16, and as shown in FIG. 2 C, the silver-plated film 2 2 is used only to form the bonding area 1 2 a at the top 20 of the inner lead 12. Formed on the area. In order to electrolytically peel the exuded silver 24 and the copper-plated film 16 without substantially peeling the silver-plated film 22, as described in Patent Document 1 below, an electrolytic stripping solution containing a cyanide compound has been used. Patent Document 1: Japanese Patent J P 5 9-0 3 1 9 0 0 A (pages 2 to 3). As shown in Patent Document 1, the lead frame 10 (on which the silver-plated film 22 is formed only on the top 20 of the inner lead 12) is immersed in a cyanide-containing compound 6 312XP / Invention Specification (Supplement Pieces) / 94-02 / 93132149 200521270 and the electrolytic stripping of copper (using this lead frame 10 as the anode and stainless steel plate as the cathode), electrolytic peeling exuded silver 2 4 and copper plated film 16 and It is possible that the silver-plated film 22 is not substantially peeled. However, if an electrolytic stripping solution containing a cyanide compound is continuously used, the peeling speed of the copper-plated film 16 and the exuded silver 24 is in a relatively short period during the electrolytic peeling of the exuded silver 2 4 and the copper-plated thin film 16. Within reduced. For this reason, it is necessary to frequently replace the electrolytic stripping solution. Furthermore, if you want to recover silver (as a precious metal) from a cyanide-containing electrolytic stripping solution that you want to exchange and process, you need another special recovery step. [Summary of the Invention] Therefore, an object of the present invention is to provide an electrolytic stripping method using an electrolytic stripping solution, which is an electrolytic stripping solution that does not contain a cyanide compound and has a lifespan relative to an electrolytic stripping solution that contains a cyanide compound. Can be greatly extended. Other objects and effects of the present invention will be apparent from the following description. To achieve the above object, the present inventors have conducted extensive research. As a result, the lead frame 10 (as shown in FIG. 2B, in which the silver-plated thin film 22 was formed only at the top 20 of the inner lead 12) was used as the anode, and an electrolytic stripping solution containing no cyanide compound (which Triammonium phosphate, which contains silver and ammonium complex ions that can be more easily dissociated than silver and cyanide complex ions, is electrolytically stripped. At the same time, platinum cathodes are used as leadframes 10 (as anodes). As a result, it was found that when the silver 24 and the copper-plated thin film 16 were exfoliated electrolytically, silver and copper were deposited on the cathode without substantially peeling the silver-plated thin film 2 2. Furthermore, it was found that by this way Electrode 7 312XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270 is used to deposit silver and copper at the cathode for de-stripping. Compared with electrolytic stripping solution containing cyanide compounds, its life can be prolonged, which leads to the realization of the present invention. Specifically, the present invention relates to an electrolytic peeling method, which includes electrolytic peeling: a copper-plated film is exposed by a silver-plated film that partially covers a copper-plated film formed on the entire surface of a component ; And Exuded silver, using the mineral copper film as an anode, formed on the exposed portion of the bell copper film and having a smaller thickness than the silver-plated film, wherein the electrolytic stripping is performed using an electrolytic copper stripping solution without cyanide, And the electrolytic stripping solution contains a compound that can form complex ions with silver more easily than the complex ions of silver and cyanide; and wherein silver and copper are deposited on the cathode, and the cathode is used as the counter electrode of the anode And it is made of a metal that is chemically stable to the electrolytic stripping solution. In the present invention, the compound that can form complex ions that are more easily dissociated with silver than the complex ions of silver and cyanide is a compound that is compatible with Silver forms a complex ion with a lower complex stability constant than the complex ion of silver and cyanide. For this compound, at least one selected from the group consisting of ammonia, salt, tartrate, phosphoric acid, and citric acid can be used. A compound composed of a salt. In addition, since the electrolytic stripping solution to be used in the present invention is an electrolytic stripping solution for electrolytic stripping of a copper-plated film, it is preferred that the electrolytic stripping solution contains copper Or an aromatic nitro compound as a copper oxidant, and is adjusted to have a pH of 9 to 12. Here, the copper compound is preferably a derivative 8 312XP / Invention Specification (Supplementary) added to the electrolytic stripping solution Pieces) / 94-02 / 93132] 49 200521270 The ammonium and copper sources that can form copper complexes. Furthermore, by surrounding the cathode with a cathode bag, the silver and copper particles (including separately deposited on the cathode) are collected by the cathode bag. Silver and copper) are possible; and it is possible to recover silver and copper (containing silver and copper deposited on the cathode) by taking out the cathode bag through the electrolytic stripping solution. Incidentally, a lead frame made of an iron-based alloy may be It is suitably used as a component. The reason why the life of the electrolytic stripping liquid containing a cyanide compound used so far is short can be considered as follows. Since the cyanide ion in the electrolytic stripping solution and the silver ion in the electrolytic stripping solution form a stable complex ion, the silver concentration in the electrolytic stripping solution increases as the amount of electrolytic stripping treatment of exuded silver increases. When the silver concentration in the electrolytic stripping solution is increased, the peeling speed of the exuded silver and the copper-plated film decreases. On the other hand, in the present invention, the electrolytic stripping is performed using an electrolytic copper stripping solution containing no cyanide (a compound containing a complex ion capable of dissociating with silver more easily than the complex ion of silver and cyanide). ), Simultaneously depositing silver and copper on the cathode used as a copper-plated film and the counter electrode of exuded silver (as the anode). Therefore, according to the electrolytic stripping method of the present invention, it is possible to prevent the peeling speed of the copper-plated film and exuded silver from being lowered due to the accumulation of silver in the electrolytic stripping solution; It is possible to extend its life. [Embodiment] The electrolytic stripping solution used in the present invention is an electrolytic stripping solution that does not contain a cyanide compound. 9 312XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270 Release liquid. As the electrolytic stripping solution, an electrolytic stripping solution containing a copper compound or an aromatic nitro compound as a copper oxidant can be suitably used. As the copper compound as a copper oxidant, a copper ammonium complex is suitable. This copper ammonium complex can be formed by adding ammonia water or ammonium salt as an ammonium source and copper sulfate, copper carbonate, copper oxalate, or copper hydroxide as a copper source to the electrolytic stripping solution. A copper ammonium complex formed in an electrolytic stripping solution having an ammonium source and a copper source added includes [Cu (NH3) 2] 2+, [Cu (NH3) 4] 2+, and [Cu (NH3) 6] At least one of 2+. As the aromatic nitro compound, chloronitrobenzoic acid, 2-gas-4-nitrobenzoic acid, o-nitrobenzoic acid, m-nitrobenzoic acid, p-nitro Benzoic acid, ethyl p-nitrobenzoate and sodium p-nitrobenzoate. An electrolytic stripping solution containing an aromatic nitro compound as a copper oxidant but added with a cyanide compound cannot be expected to have a prolonged life. The content of the copper oxidizing agent used in the electrolytic stripping solution of the present invention is usually 1 to 100 g / liter, preferably 5 to 40 g / liter. Moreover, it is preferable to adjust the electrolytic stripping solution so that the pH is 9 to 12. The p Η adjustment can be achieved by using ammonia as the ammonium source to be added to form a copper ammonium complex, or by using a p Η modifier (such as sodium hydroxide). Here, in the case where the pH of the electrolytic stripping solution is less than 9, or in the case where the p Η of the electrolytic stripping solution exceeds 12, the peeling speed of the copper-plated film tends to decrease. A compound capable of forming a complex ion with silver that is more easily dissociated than the complex ion of silver and cyanide is added to the electrolytic copper stripping solution used in the present invention 10

312ΧΡ/發明說明書(補件)/94-02/93132149 200521270 中。此化合物之實例包含一種可與銀形成具有比銀和氰之 絡合物離子更低絡合物安定性常數之絡合物離子之化合 物。特別地，可使用一或多種選自由氨水、銨鹽、酒石酸 鹽、磷酸及檸檬酸鹽組成之群之化合物。 順便一提，氨水或銨鹽（係為可與銀形成絡合物離子之 化合物）亦可用作供形成銅銨絡合物之銨源。 可與銀形成比銀和氰之絡合物離子更容易解離的絡合 物離子之化合物於電解剝離液中之含量通常為0. 1毫克至 1 00克/升。 「絡合物安定性常數」一詞於此中係為表示絡合物離子 解離程度之常數。其較低數值代表所形成的絡合物離子較 不安定且較易解離。 舉例來說，銀和氰之絡合物離子係以下式1所示之銀離 子和氰離子之間的平衡反應為基礎，並且銀和銨之絡合物 離子係以下式2所示之銀離子和氨之間的平衡反應為基 礎。 式1312XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270. Examples of this compound include a compound which can form a complex ion with silver having a complex stability constant lower than that of a complex ion of silver and cyanide. In particular, one or more compounds selected from the group consisting of ammonia, ammonium, tartrate, phosphoric acid, and citrate can be used. Incidentally, ammonia or ammonium salt (a compound capable of forming a complex ion with silver) can also be used as an ammonium source for forming a copper ammonium complex. The content of the compound capable of forming complex ion with silver more easily dissociated than the complex ion of silver and cyanide in the electrolytic stripping solution is generally from 0.1 mg to 100 g / L. The term "complex stability constant" here is a constant indicating the degree of dissociation of the complex ion. Its lower value indicates that the complex ion formed is less stable and easier to dissociate. For example, the complex ion of silver and cyanide is based on the equilibrium reaction between the silver ion and cyanide ion shown in the following formula 1, and the complex ion of silver and ammonium is the silver ion shown in the following formula 2. Based on the equilibrium reaction with ammonia. Formula 1

Ag+ + 2CN' Ag(CN)2' 式2Ag + + 2CN 'Ag (CN) 2' Formula 2

Ag+ + 2NHs ^ Ag(NH3)2 + 於此等平衡反應中，可以以下方程式1表示代表銀和氰 之絡合物離子的解離困難度之指標之安定性常數（K c N )，且 其數值（KCN)為ΙχΙΟ21。 方程式1 11 312XP/發明說明書(補件)/94-02/93132149 200521270Ag + + 2NHs ^ Ag (NH3) 2+ In these equilibrium reactions, the stability constant (K c N), which is an indicator of the difficulty of dissociation of the complex ion of silver and cyanide, can be expressed by Equation 1 below, and its value (KCN) is χΙΟ21. Equation 1 11 312XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270

Kcn ^ [ Ag(CN)2-]/{ [ Ag+] [CN·]2} 另一方面，可以以下方程式2表示作為代表銀和銨之絡 合物離子的解離困難度之指標之安定性常數（K〇3)，且其 數值（Κ Ν Η 3 )為 1 · 5 X 1 0 7。 方程式 2 Κν 丨丨 3 = [Ag(NH3)2+]/{[Ag+][NH3]2} 依此方式，K C N大於Κ Ν Π 3，相較於銀和氰之絡合物離子， 銀和銨之絡合物離子容易解離為銀離子和氨。 藉去除電解剝離液中之銀離子，銀和氰之絡合物離子更 容易解離為銀離子和氨。 於進行如圖2 B所示有關鍍銅薄膜1 6及滲出銀2 4之電 解剝離時，藉沉積銀於陰極（其為用作陽極之導線架1 0之 反電極）上，可容易地去除電解剝離液中之銀離子。較佳的 是，一種由對電解剝離液具化學安定性之金屬（例如鉑或不 銹鋼）所製成之電極係用作陰極。 可使用圖3所示之裝置進行使用此一電解液之電解剝 離。於圖3所示之裝置中，如圖1所示由鐵-鎳合金（42合 金）所製成之導線架1 0係浸潰於貯存於電解剝離容器 32(具有攪拌器34)中之電解剝離液30中，而成為一構件。 於導線架10上，鍍銅薄膜16係透過電鍍電解銅而形成於 其整個表面上，並且供連接用之結合區1 2 a係形成於每一 内引線1 2的頂部。鍍銀薄膜2 2係形成於結合區1 2 a上， 並且渗出銀2 4亦存在。 導線架1 0係連接於直流電源3 6的陽極，並且欲連接於 12 312XP/發明說明書(補件)/94-02/93132149 200521270 直流電源3 6的陰極之鉑製陰極3 8係以導線架1 0 (陽極）的 反電極而浸潰於電解剝離液3 0中。此一陰極3 8被陰極袋 4 0包圍。陰極袋4 0收集銀和銅顆粒（包含分別沉積於陰極 上之銀和銅）及類似物，並且係由對於電解剝離液3 0具有 而寸久性之纖維（例如P T F E (聚四氟乙婦）或P P (聚丙稀））製 成，且成型為袋子形狀。 貯存於電解剝離容器3 2中之電解剝離液3 0係透過循環 泵4 2循環，並且於循環管線4 4之路徑中具有一濾器4 6 (用 以分離浮在電解剝離液3 0中之顆粒）等等。 藉著自直流電源3 6通過直流電於作為陽極及陰極 3 8 (每一者係浸潰於如圖3所示貯存於電解剝離容器3 2中 之電解剝離液3 0中）之導線架1 0之間，於導線架1 0上露 出之鍍銅薄膜1 6及滲出銀2 4被剝離。藉剝離而於電解剝 離液3 0中產生之銀離子或滲出銀2 4之類似物不會形成安 定的絡合物離子（例如銀和氰之絡合物）。基於此理由，電 解剝離液3 0中之銀離子和銅離子變為銀和銅顆粒（包含分 別沉積於陰極3 8上之銀和銅）及類似物，並且由陰極袋4 0 收集。經由設在循環管線4 4中之濾器4 6收集已通過陰極 袋40之細銀顆粒或類似物。 依此方式，藉分離電解剝離液3 0中之銀離子為含有銀 或類似物之銀顆粒，降低電解剝離液中之銀濃度是可能 的。基於此理由，本發明之方法未於電解剝離液中形成安 定的氰和銀之絡合物（此可見於使用含氰化合物電解剝離 液之習用的電解剝離）。再者，根據本發明之方法，避免鍍 13 3 ] 2XP/發明說明書(補件)/94-02/93132149 200521270 銅薄膜和滲出銀的剝離速度因電解剝離液中之銀累 低是可能的；相較於含有氰化合物之習知的電解剝 大大地延長電解剝離液的壽命是可能的。 於圖3中，雖然使用導線架1 0作為陽極，但於4 脂基材的例子中，藉使用鍍銅薄膜（經非電鍍於樹脂 整個表面而形成）進行電解剝離鍍銅薄膜或類似物J 的。 (實施例） 本發明將參照以下實施例而更詳細地說明，但本 受限於此。 (實施例1 ) . 於經由電鍍電解銅而形成鍍銅薄膜於由鐵-鎳合1 合金）製成之導線架的整個表面上之後，經由電鍍電 將鍍銀薄膜形成於鍍銅薄膜上。 接著，使用如圖3所示之裝置及使用如以下表1 電解剝離液，於如以下表2之條件下，經形成於作 之導線架1 0上之鍍銅薄膜及鍍銀薄膜則連續地電库 於陽極與陰極3 8之間。於銀處理量達1，0 0 0 p p m時 貯存於電解剝離容器3 2中之電解剝離液3 0的濃度 的結果亦顯示於表2中。 312XP/發明說明書(補件)/94-02/93 ] 32149 積而降 離液， t用樹 基材的 :可能 發明不 “42 解銀， 所示之 為陽極 -剝離 ，測量 。所得 14 200521270 表1 電解剝離液1 磷酸三銨：1 0 0克/升 氫氧化銅（II): 10克/升 2 5 %氨水（供p Η調整用） pH ： 10.0 電解剝離液2 酒石酸銨：2 0 0克/升 對-硝基苯曱酸：1 0克/升 pH ： 9. 5 電解剝離液3 檸檬酸三銨：1 5 0克/升 氫氧化銅（II): 5克/升 2 5 %氨水（供p Η調整用） pH ： 9.8 表2 電解剝離條件 電解剝離液中 之銀濃度 (ppm) 電解剝離液 電流密度 (A/dm2) 浴溫 (°C ) 電解剝離液1 1 30 8 電解剝離液2 0. 5 50 7 電解剝離液3 3 30 3 於使用表2所示之任一種電解剝離液進行電解剝離時， 呈顆粒形式之銀或類似物係透過陰極3 8、陰極袋4 0及濾 器4 6收集，並且電解剝離液3 0中之銀濃度是低的。 當使用電解剝離液1進行電解剝離時，測量被黏附於陰 極3 8之顆粒或類似物中之銀濃度、透過陰極袋4 0收集之 顆粒或類似物中之銀濃度以及透過濾器4 6收集之顆粒或 類似物中之銀濃度。所得到的結果係顯示於表3中。此銀 濃度係透過溶解被黏附於陰極3 8或透過陰極袋4 0或濾器 4 6收集於5 0 %硝酸中之顆粒或類似物而測得。 表 被黏附於陰 極38 透過陰極袋 40收集 透過濾器4 6 收集 電解剝離液1 200 ppm 9, 700 ppm 70 ppm (實施例2 ) 15 312XP/發明說明書(補件)/94-02/93132149 200521270 於與實施例1之電解剝離液1的例子相同的電流密度及 浴溫下，除移走陰極袋4 0外，依與實施例1相同方式，使 用電解剝離液1，連續地電解剝離形成於導線架1 0上鍍銅 薄膜及鍍銀薄膜。當銀的處理量達1，0 0 0 p p m時，測量貯 存於電解剝離容器3 2中之電解剝離液3 0的濃度、被黏附 於陰極3 8之顆粒或類似物中之銀濃度以及透過濾器4 6收 集之顆粒或類似物中之銀濃度。所得的結果係顯示於表4 中。依與實施例1相同方式進行銀濃度之測量。 表4 電解剝離液 中之銀濃度 被黏附於陰 極3 8 透過濾器4 6 收集 電解剝離液1 13 ppm 210 ppm 9, 500 ppm 自表4當可明白，電解剝離液3 0中之銀濃度是低的， 並且銀係透過陰極3 8及濾器 4 6收集。 (比較例1 ) 於與實施例1之電解剝離液1的例子相同的電流密度及 浴溫下，除使用氰基底電解剝離液（氰化鉀：8 0克/升、對 -硝基苯曱酸：1 0克/升，pH : 1 1 )作為電解剝離物外，與 實施例2相同方式，連續地電解剝離形成於導線架1 0上鍍 銅薄膜及鍍銀薄膜。當銀的處理量達1，0 0 0 p p m時，測量 貯存於電解剝離容器3 2中之電解剝離液3 0的濃度、被黏 附於陰極3 8之顆粒或類似物中之銀濃度以及透過濾器4 6 收集之顆粒或類似物中之銀濃度。所得的結果係顯示於表 5中。依與實施例1相同方式進行銀濃度之測量。 表5 16 312XP/發明說明書(補件)/94-02/93132149 200521270 電解剝離液 中之銀濃度 被黏附於陰 極3 8 透過濾器4 6 收集 氰基底電解 剝離液 6,100 ppm 550 ppm 0 ppm 自表5當可明白，於氰基底電解剝離液中，雖然銀稍微 地沉積於陰極3 8上，但銀未沉積達到形成可透過濾器4 6 收 集 的 顆 粒 或 類 似 物 之 程 度 0 基 於 此 理 由 1 電 解 剝 離 液 30 中 之 銀 濃 度 是 南 的 〇 雖 然 本 發 明 已 參 昭 "%、 特 殊 具 體 例 詳 細 敘 述 5 惟 熟 習 本 技 藝 者 在 不 離 開 本 發 明 之 精 神 及 範 圍 内 5 當 可 進 行 許 多 變 化 及 修 改 〇 本 中 請 案 係 以 2 0 0 3 年 12 月 26 日1 令請之 曰- 專： 利 申1 凊 案 第 2003-433701 號 為 基礎 ，其户 3容 合併 於· 案以供參考 〇 [ 圖 式 簡 單 說 明 ] 圖 1 係 為 說 明 一 種 作 為 欲 受 到 電 解 剝 離 之 構 件 之 導 線 架 的 部 分 平 面 圖 〇 圖 2A至 2C 係 為 說 明 欲 形 成 於 如 圖 1 所 示 之 導 線 架 上 之 部 分 鍍 銀 薄 膜 及 滲 出 銀 的 部 分 斷 面 圖 〇 圖 3 係 為 解 釋 電 解 剝 離 裝 置 之 一 具 體 例 的 示 意 圖 〇 [ 主 要 元 件 符 號 說 明 ] 10 導 線 架 12 内 引 線 12 a 結 合 區 14 晶 粒 座 16 鍵 銅 薄 膜 312XP/發明說明書(補件)/94-02/93132149 17 200521270Kcn ^ [Ag (CN) 2-] / {[Ag +] [CN ·] 2} On the other hand, the stability constant as an indicator of the difficulty of dissociation of the complex ion of silver and ammonium can be expressed by Equation 2 below. (K〇3), and its value (K Ν Η 3) is 1 · 5 X 1 0 7. Equation 2 Κν 丨 丨 3 = [Ag (NH3) 2 +] / {[Ag +] [NH3] 2} In this way, KCN is larger than Κ Ν Π 3, compared to the complex ion of silver and cyanide. Ammonium complex ions are easily dissociated into silver ions and ammonia. By removing silver ions from the electrolytic stripping solution, silver and cyanide complex ions are more easily dissociated into silver ions and ammonia. When the electrolytic stripping of the copper-plated thin film 16 and the exuded silver 24 is performed as shown in FIG. 2B, it can be easily removed by depositing silver on the cathode (which is the counter electrode of the lead frame 10 used as the anode). Silver ions in electrolytic stripping solution. Preferably, an electrode system made of a metal (such as platinum or stainless steel) that is chemically stable to the electrolytic stripping solution is used as the cathode. The electrolytic stripping using this electrolyte can be performed using the apparatus shown in FIG. In the device shown in FIG. 3, a lead frame 10 made of iron-nickel alloy (42 alloy) as shown in FIG. 1 is immersed in an electrolytic solution stored in an electrolytic peeling container 32 (having a stirrer 34). The peeling liquid 30 becomes a member. On the lead frame 10, a copper-plated film 16 is formed on the entire surface thereof by electroplating electrolytic copper, and a bonding area 12a for connection is formed on the top of each inner lead 12. The silver-plated film 2 2 is formed on the bonding region 12 a, and the exuded silver 24 is also present. The lead frame 10 is connected to the anode of the DC power supply 36, and is to be connected to 12 312XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270 The cathode of the DC power supply 3 6 is a platinum cathode 3 8 is connected to the lead frame The counter electrode of 10 (anode) was immersed in the electrolytic stripping solution 30. This cathode 38 is surrounded by a cathode bag 40. Cathode bag 40 collects silver and copper particles (including silver and copper deposited on the cathode respectively) and the like, and is made of long-lasting fibers (such as PTFE (polytetrafluoroethylene)) for electrolytic stripping solution 30 or PP (Polypropylene)) and molded into a bag shape. The electrolytic stripping solution 3 0 stored in the electrolytic stripping container 32 is circulated through the circulation pump 4 2 and has a filter 4 6 (for separating the particles floating in the electrolytic stripping solution 30) in the path of the circulation line 44. )and many more. By direct current from the direct current power source 3 6 to the anode and cathode 3 8 (each of which is immersed in the electrolytic stripping solution 30 stored in the electrolytic stripping container 3 2 as shown in FIG. 3), the lead frame 1 0 In between, the copper-plated film 16 and the exuded silver 24 exposed on the lead frame 10 were peeled off. The silver ions generated in electrolytic stripping solution 30 or the like exuding silver 2 4 by peeling will not form stable complex ions (such as the complex of silver and cyanide). For this reason, the silver ions and copper ions in the electrolytic stripping solution 30 become silver and copper particles (including silver and copper deposited on the cathode 38 respectively) and the like, and are collected by the cathode bag 40. Fine silver particles or the like that have passed through the cathode bag 40 are collected through a filter 4 6 provided in the circulation line 44. In this way, by separating the silver ions in the electrolytic stripping solution 30 from silver particles containing silver or the like, it is possible to reduce the silver concentration in the electrolytic stripping solution. For this reason, the method of the present invention does not form a stable complex of cyanide and silver in the electrolytic stripping solution (this can be seen in the conventional electrolytic stripping using a cyanide-containing electrolytic stripping solution). Furthermore, according to the method of the present invention, it is possible to avoid the plating speed of 13 3] 2XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270 The peeling speed of the copper film and exuded silver is low due to the accumulation of silver in the electrolytic stripping solution; It is possible to greatly extend the life of the electrolytic stripping liquid compared to the conventional electrolytic stripping containing a cyanide compound. In FIG. 3, although the lead frame 10 is used as the anode, in the example of a greased substrate, a copper-plated film (formed by non-plating on the entire surface of the resin) is used to electrolytically peel the copper-plated film or the like. of. (Examples) The present invention will be described in more detail with reference to the following examples, but the present invention is not limited thereto. (Example 1) After a copper plating film was formed on the entire surface of a lead frame made of iron-nickel alloy 1 by electrolytic copper plating, a silver plating film was formed on the copper plating film by electroplating. Next, using the device shown in FIG. 3 and the electrolytic stripping solution as shown in Table 1 below, under the conditions shown in Table 2 below, the copper-plated film and silver-plated film formed on the lead frame 10 were continuously formed. The battery is between the anode and the cathode 38. Table 2 shows the results of the concentration of the electrolytic stripping solution 30 stored in the electrolytic stripping container 32 at a silver processing amount of 1,000 p pm. 312XP / Invention Specification (Supplements) / 94-02 / 93] 32149 The product is used to remove the liquid from the substrate: it is possible to invent the "42 solution of silver, which is shown as anode-peel, measured. Result 14 200521270 Table 1 Electrolytic stripping solution 1 Triammonium phosphate: 100 g / L copper (II) hydroxide: 10 g / L 25% ammonia water (for adjustment of p Η) pH: 10.0 Electrolytic stripping liquid 2 Ammonium tartrate: 2 0 0 g / L p-nitrophenylarsinic acid: 10 g / L pH: 9. 5 electrolytic stripping solution 3 triammonium citrate: 150 g / L copper (II) hydroxide: 5 g / L 2 5 % Ammonia water (for adjustment of p p) pH: 9.8 Table 2 Electrolytic stripping conditions Silver concentration in the electrolytic stripping solution (ppm) Current density of the electrolytic stripping solution (A / dm2) Bath temperature (° C) Electrolytic stripping solution 1 1 30 8 Electrolytic stripping liquid 2 0. 5 50 7 Electrolytic stripping liquid 3 3 30 3 When electrolytic stripping is performed using any of the electrolytic stripping liquids shown in Table 2, silver or the like in the form of particles penetrates the cathode 3 8, the cathode bag 4 0 and filter 46 were collected, and the silver concentration in electrolytic stripping solution 30 was low. When electrolytic stripping was performed using electrolytic stripping solution 1, the adhesion to the cathode 3 8 was measured. The silver concentration in the particles or the like, the silver concentration in the particles or the like collected through the cathode bag 40, and the silver concentration in the particles or the like collected through the filter 46. The results obtained are shown in Table 3. This silver concentration is measured by dissolving particles or the like collected by dissolving and being adhered to the cathode 38 or through the cathode bag 40 or filter 46 in 50% nitric acid. The surface is adhered to the cathode 38 through the cathode bag 40 Collected through the filter 4 6 Collected electrolytic stripping solution 1 200 ppm 9, 700 ppm 70 ppm (Example 2) 15 312XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270 The same as the electrolytic stripping solution 1 of Example 1 Example At the same current density and bath temperature, except that the cathode bag 40 is removed, in the same manner as in Example 1, the electrolytic stripping solution 1 is used to continuously electrolytically strip the copper-plated film and silver plating formed on the lead frame 10 Thin film. When the processing amount of silver reaches 1,000 ppm, measure the concentration of electrolytic stripping solution 30 stored in electrolytic stripping container 32, the concentration of silver in particles or the like adhered to cathode 38, and Particles or the like collected through the filter 4 6 The silver concentration in the solution is shown in Table 4. The measurement of the silver concentration was performed in the same manner as in Example 1. Table 4 The silver concentration in the electrolytic stripping solution was adhered to the cathode 3 8 through the filter 4 6 to collect the electrolytic peeling Liquid 1 13 ppm 210 ppm 9, 500 ppm As can be understood from Table 4, the silver concentration in the electrolytic stripping solution 30 is low, and the silver is collected through the cathode 38 and the filter 46. (Comparative Example 1) A cyanide-based electrolytic stripping solution (potassium cyanide: 80 g / L, p-nitrophenylhydrazone) was removed at the same current density and bath temperature as in the example of the electrolytic stripping solution 1 of Example 1. Acid: 10 g / L, pH: 1 1) A copper-plated film and a silver-plated film formed on the lead frame 10 were continuously electrolytically peeled in the same manner as in Example 2 except for the electrolytic peeling. When the processing amount of silver reaches 1,000 ppm, measure the concentration of the electrolytic stripping solution 30 stored in the electrolytic stripping container 32, the silver concentration of the particles or the like adhered to the cathode 38, and the filter 4 6 Silver concentration in collected particles or similar. The results obtained are shown in Table 5. The measurement of the silver concentration was performed in the same manner as in Example 1. Table 5 16 312XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270 The silver concentration in the electrolytic stripping solution was stuck to the cathode 3 8 Permeable filter 4 6 Collected cyanide-based electrolytic stripping solution 6,100 ppm 550 ppm 0 ppm from Table 5 When it can be understood that although the silver is slightly deposited on the cathode 38 in the cyan-based electrolytic stripping solution, the silver is not deposited to the extent that particles or the like collected by the permeable filter 4 6 are collected. 0 For this reason 1 electrolytic stripping solution The silver concentration in 30 is south. Although the present invention has been shown "%, special specific examples are described in detail 5 but those skilled in the art will not depart from the spirit and scope of the present invention. 5 Many changes and modifications can be made. The case is based on the Decree No. 1 of December 26, 2003-Special: Lishen 1 凊 Case No. 2003-433701, whose households are incorporated in the case for reference. [Schematic Simple explanation] Figure 1 is an illustration of a Partial plan view of the lead frame of the debonded member. Figures 2A to 2C are partial cross-sectional views illustrating a portion of the silver-plated film and exuded silver to be formed on the lead frame shown in Figure 1. Figure 3 is an explanation of electrolysis. Schematic diagram of a specific example of the peeling device. [Description of main component symbols] 10 Lead frame 12 Inner leads 12 a Bonding area 14 Die holder 16-key copper film 312XP / Invention specification (Supplement) / 94-02 / 93132149 17 200521270

18a、 18b 遮罩 -板 20 頂 部 22 鍍 銀 薄 膜 24 滲 出 銀 30 電 解 剝 離液 32 電 解 剝 離容器 34 攪 拌 器 36 直 流 電 源 38 陰 極 40 陰 極 袋 42 循 環 泵 44 循 環 管 線 46 濾· 器 312XP/發明說明書(補件)/94-02/93132149 1818a, 18b Mask-plate 20 Top 22 Silver-plated film 24 Exuded silver 30 Electrolytic stripping liquid 32 Electrolytic stripping container 34 Agitator 36 DC power source 38 Cathode 40 Cathode bag 42 Circulation pump 44 Circulation line 46 Filter 312XP / Invention Specification ( (Supplement) / 94-02 / 93132149 18

Claims (1)

200521270 十、申請專利範圍： 1. 一種電解剝離方法，其包含電解剝離： 一鍍銅薄膜，其係由一鍍銀薄膜露出，該鍍銀薄膜係部 分地覆蓋形成於構件之整個表面上之鐘銅薄膜；及 滲出銀，使用該鍍銅薄膜作為陽極，而形成於該鍍銅薄 膜的露出部分上且具有比該鍍銀薄膜更小厚度， 其中該電解剝離係使用不含氰化物之電解銅剝離液進 行，並且該電解剝離液包含一種可與銀形成比銀和氰之絡 合物離子更容易解離的絡合物離子之化合物；且 其中銀和銅係沉積於陰極上，該陰極係用作陽極之反電 極且由對該電解剝離液具化學安定性之金屬製成。 2 .如申請專利範圍第1項之電解剝離方法，其中可與銀 形成比銀和氰之絡合物離子更容易解離的絡合物離子之該 化合物係為一種可與銀形成具有比銀和氰之絡合物離子更 低絡合物安定性常數之絡合物離子。 3 .如申請專利範圍第1項之電解剝離方法，其中可與銀 形成比銀和氰之絡合物離子更容易解離的絡合物離子之該 化合物包含至少一種選自由氨水、銨鹽、酒石酸鹽、磷酸 及檸檬酸鹽組成之群之化合物。 4.如申請專利範圍第1項之電解剝離方法，其中該電解 剝離液進一步包含作為銅氧化劑之銅化合物或芳族硝基化 合物，並且具pH為9至12。 5 .如申請專利範圍第4項之電解剝離方法，其中該銅化 合物係為衍生自銨源與銅源之銅銨絡合物。 19 312XP/發明說明書(補件)/94-02/93132149 200521270 ，其中該陰極 顆粒。 ，其中該構件 ，進一步包含 器之循環管 6 .如申請專利範圍第1項之電解剝離方法 係以一陰極袋圍繞，俾收集含有沉積銀之銀 7 .如申請專利範圍第1項之電解剝離方法 係為由鐵基底合金製成之導線架。 8 .如申請專利範圍第1項之電解剝離方法 使該陰極附近之電解剝離液通過具有一濾 線循環，藉以收集含有沉積銀之銀顆粒。 20 312XP/發明說明書(補件)/94-02/93132149200521270 10. Scope of patent application: 1. An electrolytic peeling method, which includes electrolytic peeling: a copper-plated film, which is exposed by a silver-plated film, which partially covers a bell formed on the entire surface of a component A copper thin film; and exuding silver, using the copper-plated thin film as an anode, formed on the exposed portion of the copper-plated thin film and having a smaller thickness than the silver-plated thin film, wherein the electrolytic stripping uses electrolytic copper without cyanide The stripping solution is performed, and the electrolytic stripping solution includes a compound that can form complex ions with silver that is more easily dissociated than the complex ions of silver and cyanide; and wherein silver and copper are deposited on the cathode, and the cathode is used as The counter electrode of the anode is made of a metal that is chemically stable to the electrolytic stripping solution. 2. The electrolytic stripping method according to item 1 of the scope of patent application, wherein the compound capable of forming complex ions with silver that is more easily dissociated than the complex ions of silver and cyanide is a compound that can form silver with specific silver and Cyanide complex ions Complex ions with lower complex stability constants. 3. The electrolytic stripping method according to item 1 of the scope of patent application, wherein the compound can form a complex ion with silver that is more easily dissociated than the complex ion of silver and cyanide. The compound contains at least one selected from the group consisting of ammonia, ammonium salt, and tartaric acid. A group of compounds consisting of salts, phosphoric acid and citrate. 4. The electrolytic stripping method according to item 1 of the patent application range, wherein the electrolytic stripping solution further comprises a copper compound or an aromatic nitro compound as a copper oxidant, and has a pH of 9 to 12. 5. The electrolytic stripping method according to item 4 of the application, wherein the copper compound is a copper ammonium complex derived from an ammonium source and a copper source. 19 312XP / Invention Specification (Supplement) / 94-02 / 93132149 200521270, where the cathode particles. Among them, the component further includes the circulation tube 6. The electrolytic stripping method of item 1 in the scope of patent application is surrounded by a cathode bag, and the silver containing deposited silver is collected 7. The electrolytic stripping of item 1 in scope of patent application The method is a lead frame made of an iron-based alloy. 8. The electrolytic stripping method according to item 1 of the scope of the patent application, the electrolytic stripping solution near the cathode is circulated through a filter line to collect silver particles containing deposited silver. 20 312XP / Invention Manual (Supplement) / 94-02 / 93132149
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