201037104 四、指定代表圖： (一） 本案指定代表圖為：第圖。 (二） 本代表圖之元件符號簡單說明： ◎:極良好（最佳）； 〇·良好； △:實用上無障礙； X :有障礙。 徵的化學式 五、本案若有化學式時，請揭示最能顯示發明特 〇 六、發明說明： 【發明所屬之技術領域】 本發明係關於金屬荡及其製造方法。特別係本㈣ 關於為在絕緣基板利用薄膜導體層形成配線 箔及其製造方法。 、用金肩 鑄模用金屬箔特別係適用於製造供搭载諸如半導體— 件、積體電路、電子零件等之用的配線基板。 凡 再者’本發明係關於使用金屬箱形成粗化處理面的絕 緣基板’以及在該絕緣基板的粗 土极97才且化羼理面上，形成既定配 線圖案的配線基板。 —201037104 IV. Designated representative map: (1) The representative representative of the case is: Figure. (2) A brief description of the symbol of the representative figure: ◎: very good (best); 〇·good; △: practically barrier-free; X: obstacle. Chemical formula of the levy 5. If there is a chemical formula in this case, please reveal the best indication of the invention. 6. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a metal sway and a method of manufacturing the same. In particular, (4) a wiring foil formed by using a thin film conductor layer on an insulating substrate and a method for producing the same. Metal shoulders for metal molds are particularly suitable for the production of wiring boards for mounting semiconductors, integrated circuits, electronic parts, and the like. In addition, the present invention relates to an insulating substrate in which a roughened surface is formed using a metal case, and a wiring board in which a predetermined wiring pattern is formed on the roughened surface of the insulating substrate. -
先前技術J 近年隨電子技術的進展，供搭載諸如半導體元件、積 201037104 體電路、電子零件等之用的配線基板，除輕薄短小化之外， 亦朝高積體化、高輸出化及高速化急速進展。所以，例如 當在半導體基板上形成諸如銅等金屬配線之際，一般併用 賤鍍成膜與電解電鍍。特別係半導體裝置隨高機能、高速 化，亦朝銅配線細微化的製程開發急速進展。隨如上述的 配線基板高積體化，在輕薄短小化時便會導致配線寬度減 少與配線長度增加，例如配線材料的電阻將會造成信號延 Ο ❹ 遲，更甚者會阻礙及傳輸高速化。因而，配線材料便使用 電阻較小的極薄金屬材料。 習知配線基板的極薄金屬膜之形成技術，係採用錢 /、CVD(化學蒸鍍）法。其中，就從成膜的量產性與安定 =點’-般係採用有利的濺鍍法 '然而，依濺鍍法所形 線’會有因電致遷移、或配線的伸縮而產生的應力 :二而容易發生斷線意外的困難處，導致配線基板 低問題發生。更且必需使用特殊處理設備， '、阿就成本效益面仍有待改善的課題。 上轉頗適用於配線基板製造時，在絕緣基板 金屬薄層之所：：形狀，再於所轉印的表面上形成 之所明鑄模法使用的金屬箔。 在此首先針對將金屬箔使用為鑄模用Μ #用古 模法)進行說明。另外η 埼杈用的使用方法(鑄 單侧表面_簡單’針對在配線基板 表面上形成金屬箱鑄模的步驟進行說明。 供搭載諸如半導體元件、 配線基板，係右I. 積體電路、電子零件等用的 •將環氧系接著性樹脂或半硬化樹脂塗 3 201037104 佈，f面上的醯亞胺系樹脂、或諸如液晶聚合物等樹脂薄 膜等等絕緣基板。此外，該配線基板係使諸如料族聚酿 胺樹脂或玻璃等絕緣性纖維中含潤環氡樹脂，更依例如厚 度5〜20㈣左右的環氧層半硬化狀態（即B平台）形成的玻 璃環氧基板等絕緣基板。 在該、'，邑緣基板上積層金屬箱。金屬落係採用例如具有 粗化處理面的銅@。金屬猪係將該粗化處理面側依真空教 壓積層於絕緣基板表面上。 /二… 接著，將所積層的金屬 表面上，將真空熱壓的金屬 屬箔粗化處理面之金屬，例 用配線基板製造時一般所使 施行钱刻除去。 箔施行蝕刻除去。在絕緣基板 箔、及咬入於絕緣基板中的金 如金屬箔係銅箔的情況，便利 用的氯化鐵或氣化銅等蝕刻液 錯由將金屬箔施行蝕刻除 „ ,^ 仃蝕到除去，而從絕緣基板表面將才 化處理面的金屬除去。 金屬V自粗化處理面的凹π开 狀便轉印於絕緣基板上，在絕 的凹凸开 ^ ^ ，土板表面上便形成由凹ΰ (鱗褀j所造成的粗化虛 處面°相凸（鑄模）係若金屬笛的 粗化處理面呈粒狀，在 屬泊的 « A ^ ^ 、’土板表面上所轉印的凹凸形狀 便成為夕數粒狀形狀的凹 .. ° °亥凹4不僅依照表面積大 小，亦依照凹部表面的 檟In the recent years, with the advancement of the electronic technology, the wiring board for semiconductor devices, the 201037104 body circuit, electronic components, etc., has been reduced in size, reduced in size, high in output, and high in speed. Rapid progress. Therefore, for example, when a metal wiring such as copper is formed on a semiconductor substrate, ruthenium plating and electrolytic plating are generally used in combination. In particular, semiconductor devices are rapidly evolving in the process of miniaturization of copper wiring with high performance and high speed. As described above, the wiring board is highly integrated, and the wiring width is reduced and the wiring length is increased when the thickness is reduced. For example, the resistance of the wiring material causes signal delay, and even higher, the transmission speed is increased. . Therefore, the wiring material uses an extremely thin metal material having a small electric resistance. The technique for forming an extremely thin metal film of a conventional wiring substrate is a money/, CVD (chemical vapor deposition) method. Among them, from the mass production of film formation and stability = point '-like use of favorable sputtering method ' However, according to the sputtering method, the line 'has the stress caused by electromigration, or the expansion and contraction of the wiring. : Second, it is prone to the difficulty of disconnection accidents, resulting in low wiring substrate problems. It is also necessary to use special processing equipment, 'A, the cost-effective aspect still needs to be improved. The upturn is quite suitable for the metal foil used in the molding method of the insulating substrate, in the shape of the thin layer of the insulating substrate, and on the surface to be transferred. Here, first, the description will be made on the use of a metal foil as a mold for Μ # using the ancient mold method. In addition, the use method of η ( (casting one side surface _ simple ' is described for the step of forming a metal box mold on the surface of the wiring board. For mounting such as semiconductor elements, wiring boards, and right I. integrated circuits, electronic parts An epoxy-based adhesive resin or a semi-cured resin is coated with an insulating substrate such as a bismuth imino resin or a resin film such as a liquid crystal polymer on the surface of the surface of the 201037104 fabric. An insulating substrate such as a glass epoxy substrate formed of a semi-cured epoxy layer (that is, a B-platform) having a thickness of about 5 to 20 (four), for example, is contained in an insulating fiber such as a melamine resin or glass. In this case, a metal case is laminated on the edge substrate. For example, the metal drop is made of copper having a roughened surface. The metal pig system laminates the roughened surface on the surface of the insulating substrate by a vacuum. Next, on the surface of the metal layer to be laminated, the metal which is vacuum-hot pressed by the metal foil is roughened, and the metal is generally removed by the wiring substrate. In the case of an insulating substrate foil and a gold such as a metal foil-based copper foil which is bitten in an insulating substrate, an etchant solution such as ferric chloride or vaporized copper which is convenient for use is etched by removing the metal foil, ^, 仃After the etch is removed, the metal of the surface is removed from the surface of the insulating substrate. The metal V is transferred from the roughened surface of the roughened surface to the insulating substrate, and is formed on the surface of the earth plate. It is formed by the concave ΰ (the coarse imaginary surface caused by the scale 褀 j. The phase convex (molding) is if the roughened surface of the metal flute is grainy, on the surface of the berthed « A ^ ^ , ' soil plate The transferred concavo-convex shape becomes a concave shape of the granule shape. The ° ° recess 4 is not only according to the surface area, but also according to the surface of the concave portion.
的開口部截面積較大邻八卢— 肝依凹4内J #或和乂乂 Ρ刀存在的形狀形成。所以，凹部將 成為知釘效應的最佳形狀。 丨， 其 鈀之後 次，在絕緣基板表 ，再利用無電解電 面上附著將成為無電解 鍍施行電阻率較小金屬 電鑛核的 例如厚 201037104 • 度0.1〜5/zm左右銅的薄層電鍍。 接著，在薄層電鑛的電鍍層表面上除所需配線圖案以 外的區域設置電鑛遮罩。電鍵遮罩係例如在電鑛層表面上 設置感光性樹脂之後，便利用供所需圖案形成用的光遮罩 施行曝光’經顯影而形成。 然後，藉由從上述所形成的無電解電鑛層施行供電， 便在未被覆感光性樹脂的所需配線圖案區域中，施行良導 ❹電性金屬（例如銅）的電氣電鍍而形成配線。 接著，將感光性樹脂除去後，利用諸如硫酸過氧化氣 系、過硫酸鹽類、或氨錯鹽類系等姓刻液施行姓刻，而將 纟由電氣電鍍層所覆蓋部分的無電解電鍍層除去。因為無 電解電鍍層在相較於電氣電鍍金屬層的配線之下屬㈣ 薄，因而钱刻速度較快速。而，所需圖案的電氣電錄層配 線則幾乎未被钱刻。所以，依電氣電錢層所形成所需圖案 下方的無電解電鍍層’因為電氣電鍍層的配線將成為遮罩 〇並保護，因而未被姓刻。最後，浸潰於過猛酸卸與氯氧化 鈉的混合液中。藉此，將附著於絕緣基板露出的表面上， 且無法由上述㈣液施行餘刻的㈣去。（該方法係有如專 利文獻1所揭示。） [先行技術文獻] [專利文獻] [專利文獻1]日本專利特開2006-196813號公報 【發明内容】 5 201037104 (發明所欲解决之課題） 專利文獻1有記t㈣ 上，將電氣電鍍的電产^ 处里面係在銅V白表面 用異常電鍍現象(焦電:)常的數倍而施行電鑛’即利 子。本文獻中，雖有記載：而Μ成長出粒狀銅的細微粒 .該粒子的大小、粗糖度及& # 等綜合性粗化形狀，將忐A Α 又汉粒狀 冑成為與絕、緣基板間之密接強度的重 要!素銅Μ造商進行最純，且取得亦容易，但相 關詳細内谷卻無揭示。 本發明針對適用於供搭載諸如半導體元件、積體電 路、電子零件等用的配線基板製造的合適鑄模用金屬箱進 行深入鑽研’成功地提供形成頗適用於鑄模用途金屬箱之 較佳形狀粗化㈣金屬帛，且亦提供具有絕緣基板與配線 圖案間之密接性優盈，日总Μ 士 Λ 聽馒/、1蝕刻直線性與厚度均勻性亦均優 異之配線圖案的配線基板。 習知市售電解銅羯，一般係為提高與基板間之密接性 的粗化處理形狀’呈現銅粒的瘤&，且該銅粒瘤間亦依根 部緻密地緊密在一起。 本發明主要的鑄模用途表面處理金屬落，較大特徵在 於：在粗化處理面側形成具有0.丨# m以上、丨.〇 # m以下 間隙之細微柱狀形狀凹凸。 (解決課題之手段） 本發明金屬猪的特徵在於：具有電鍍粗化表面的金屬 ’ δ亥電鍍粗化表面係對未處理金屬箔至少其中一面利用 焦電鍍施行粗化鍍瘤，並對該粗化鍍瘤上施行膠囊電铲 201037104 (capsule plate)，該表面粗糙度係依JIS B 〇6〇1規定的 RZ值（以下同）為1. 0 " m至2· 5 # m，且依上述粗化艘瘤所 形成的粗化瘤，係相鄰粗化瘤間具有0.1# m以上1. 以下間隙的柱狀形狀。 本發明的金屬箔係對上述電鍍粗化表面施行防銹處理 的金屬箔。 本發明的金屬箔係上述未處理金屬箔為軋延銅箔或電 ◎解銅落；上述未處理銅箱至少電鍍粗化表面形成側的表面 粗經度，依Rz值計係以”至2 2"m的金屬箱。 本發明金屬箔的主要用途係鑄模用途。 -本發明絕緣基板係經轉印上述金屬箔的電鍍粗化表面 之凹凸形狀’而形成粗化處理面的絕緣基板。 本發明的配線基板係在上述絕緣基板的粗化處理面 上’形成既定配線圖案的配線基板。 本發明金屬箔之製造方法，其特徵在於：對表面粗糙 ❹度依Rz值計為1.0以m至2.2"m的未處理金屬箔，利用在 硫酸-硫酸銅鍍液、焦磷酸銅鍍液或碳酸銅鍍液中加入添加 金屬的鍍浴，施行焦電鍍而形成粗化鍍瘤表面，並對該粗 化鍍瘤表面施行膠囊電鍍’形成表面粗糙度依RZ值計為 1. ID至2. 5/z m，相鄰粗化瘤間具有〇. J # m以上h 〇以爪 以下間隙的柱狀形狀電鍍粗化表面。 本發明金屬箔之製造方法中，上述鍍液中所添加的添 加金屬係鐵、鉻、鉬、鎢、以及釩與銻二者或任一者。 本發明金屬箔之製造方法中，對上述電鍍粗化面施行 7 201037104 防銹處理。 本發明金屬箔之製造方法中，上述未處理金屬箔係軋 延銅箔或電解銅箔。 依照本發明金屬箔之製造方法施行粗化處理的金屬 4 ’主要用途係鑄模用途。 (發明效果） 本發明金屬箔主要係因為在鑄模用途中的投錨效果 (利用鑄㈣騎效應）優異，因而僅降低後❹驟施行無 电解電鑛時的電鍍量成本。此外，本發明的金屬ϋ因為絕 緣基板與配線圖案間之密接性優異，目而在電路製作時的 細線電路_步驟中，㈣直線性優異。所以，本發 製造供搭载諸如半導體元件、積體電路、電子零件等用 配線基板時，具有優異效果。 ， L貫袍方式】 本發明的金屬箔係不銹鋼箔、鋁 只要屬於相用途㈣且可㈣的金制便;4特… 以下，針對本發明’就金屬箱係以預 解銅箔為例進杆线“ β aa σ 較夕的1 J進仃4細说明。另外，相關軋延銅 同樣的結果，因而省政4 έ…、 白亦可獲相 囚而肩略砰細說明。 本發明所使用電鍍粗化表 β 1上 衣曲形成刖的電解鋼笮γ 稱「未處理鋼箔、，伤留去广 則治（以*7 h白」），係早重厚度60^至 於公稱厚度9〜18" 一 e声由 0g/ni (相Ί ΜαπΟ’且厚度方向的結晶構 微結晶）。「單會厘许 r DO 至、、、田礅粒（知 早重厚度」係「單重（每單位面 201037104 銅比重（8. 9)」的理論厚度（即，「單重厚度」= /「銅比重（8·9)」）。而，「公稱厚度」係指實測厚度。」 將未處理銅箔的單重厚九 j平里与度δ又為60g/m至153 2 内的理由係將未處琿笮始；L 祀固 处理泊施仃粗化處理、或將粗化 層於絕緣基板上之蚌的步要α ^ 之時的處置性，且利用蝕刻將羯除去時的 #刻處理容易性等特性均優異之緣故所致。 對該未處理銅猪施行焦電鍍。在施行焦電鍍的鍍浴 Ο 中’於硫酸-硫酸銅鑛液、焦磷酸銅鑛液或碳酸銅鍍液任一 基本鍍液組成中，添加金屬添加劑。金屬添加％係^ 以（鐵）、Μο(翻）、Cr(鉻）、w(鶴）、以及ν(飢）或处（録） 任一者或二者。 肖由對未處理銅箔表面，於上述鍍浴的極限電流密度 附近施行焦電鍍’而形成細微結晶的瘤狀柱狀形狀。因： 在焦鍍浴中將Fe(鐵）、Mo(鉬）、Cr(鉻）、w(鎢）依如下述 添加既定量，因而細微複數柱狀形狀便形成有設計間隙狀 〇 態。此外’藉由V(鈒）或Sb(錄），當形成單面處理箱時， 便可提升耐藥性。相關電鍍方法的詳細内容，容後述。 接著，依照利用焦電鍍施行粗化鍍瘤而形成的粗化鍍 瘤表面，為使瘤狀細微柱狀形狀的銅粒不會輕易地脫落， 便施行平滑電鍍（所謂膠囊電鍍），而形成表面粗化銅箱、 或鑄模用途銅箱（以下簡稱「鑄模用鋼落」）。相關膠囊電 鍵方法，容後述。 上述膠囊電鍍係施行所完成電鍍粗化表面的粗化處理 形狀’依JIS-B-0601所規定Rz值（以下同）為1〇#m以 9 201037104 上、2. 5 # m以下， 微柱狀形狀（柱狀） 以下的柱狀間隙。 即便銅粒施行膠囊電 ，§亥柱狀間具有〇 1 鍍後，仍可保持細 # m 以上、1. 0 # m 依如上述所製得鑄模用銅箔， 如别述，首先將以鑄模 用銅箔為積層對象的絕緣基板，積 、 層於例如環氧基材或聚 酿亞fe树脂或有機薄膜上。然後 俛將該鑄模用銅箔利用蝕 刻而完全溶解除去，便在絕緣基板 风衣甸形成具有柱狀間隙 的細微柱狀鑄模。即，轉印鑄模用鋼箔（金屬…的電鍍粗 化表面之凹凸形狀，而在絕緣基板上形成粗化處理面。然 後’在該絕緣基板的粗化處理面上，利用電鍍處理形成金 屬膜後’再針對該金屬膜實施濕式_處理而施行圖案加 工，藉由形成既定配線圖案，便形成配線基板。 習知鑄模用途就頻度較高的市售單面粗化處理銅猪， 一般係表面凹部呈研缽狀，且銅粒瘤間依根部緻密地緊密 在一起。因而，投錨效果（利用鑄模的錨釘效應）差，無電 解電链時的電鍍量會變多，導致成本提升。且，爾後的電 路製作時，會造成細線電路蝕刻步驟中的蝕刻直線性亦差 之結果。 主要用途為鑄模用的本發明銅箔，係形成粗化處理面 側具有0. 1 # m以上、1. 0 "m以下間隙的細微柱狀形狀。 因而’藉由使用該銅箔’便可在絕緣基板表面上，依均勻 且凹程度健全的間隔與形狀’輕易地形成投錨效果（利用鑄 換的錯釘效應）優異之凹凸（鑄模）。所以，可將後續步驟的 無電解電鑛時之電鍍量節省至最小極限，在後續的電路製 10 201037104 作時’於細線電路蝕刻步驟中的蝕刻直線性優異。所以， 可提供頗適用於製造供搭載半導體元件、積體電路、電子 零件等用的配線基板製造之鑄模用銅箔，具有粗化面的表 面處理銅羯。 對銅箱表面施行的細微柱狀形狀（粗化處理形狀），係 使表面粗糙度依！^值計為1〇#m以上、下的狀 態形成。 ❹ 藉由依此規範，便可在不致殘留不需要蝕刻殘渣的情 況下，依細微柱狀在絕緣基板表面上形成具有柱狀間隙的 鑄模。 在此’當Rz(相當於鑄模深度）小於1.〇 Am的情況， 就耐熱可靠度的觀點’會有發生不良情況的顧慮。而，當 Rz超過2.5# m的情況，在絕緣基板表面上所形成凹部的 大小會變A ’當t路形&日寺會有構成障礙的彳能性。因而， ❹ 鑄模用銅fl的粗化處理形狀，特佳係依Rz值計為1〇㈣ 以上、2. 5 // m以下。 本發明中，在鑄模用銅箱的粗化處理面侧，形成具有 0.1 A m以上、l.〇em以下間隙的細微柱狀形狀。 電鍍粗化處理前的β α J的銅泪係具有細微粒結晶構造。「具 有細微粒結晶構造的銅箔 、 J冶」，係才曰施仃粗化處理前的表面 粗度，依Rz值計為1· 〇 υ以m μ上、2. 2 # m以下之光澤形狀 銅箔。藉由對具有細微抑紝a 犮拉…日日構造的銅-冶施行粗化瘤處 理，便可設計具有上述„旭、& , , 《間隙的粗化形狀。即，藉由具有柱 狀結晶的一般電解銅箔其矻 白基底施订粗化瘤處理，係較難形成 11 201037104 本發明的鑄模形狀。 本發明中，將未處理銅箔的表面粗度依Rz值叶規— 以上的理由，係Rz值小於丨·。…未處二 /白在氣泊步驟中的生產性極低，並不適用為工業用材料 且，當Rz值超過2. 2 // m時’在焦電鍍步驟中，初期電: 的銅粒子將集中並附著（電鍍）於粗度較高的前端，結果成 為樹枝狀極脆的粗化，為能形成健全狀態，便必需過产施 :下-步驟的平滑電鍍。結果，無法獲得當作鑄模用：適 虽凹凸間隔，或當施行㈣日夺，樹枝狀前端會成為基板内 的殘逢，導致引發遷移不良情況的顧慮頗高。因而，將未 處理銅荡的表面粗度依Rz值計，規定在22“以下。 將本發明施行粗化鍍瘤，Rz(相當於鑄模深度）為 1. Mm以上、2. 5^以下’且粗化瘤間的間隙為。 以上、1·。…乂下之鑄模用銅箱，貼合於絕緣基板上。缺 後’在下—步驟中，制施行為將㈣除去的祕酸處理 等處理，而施行潔淨化處理，便在不致損及該鑄模形狀的 情況下，對絕緣基板面施行拋光。_，在該絕緣基板面 上利用無電解電錢形成超極薄銅膜，再對該超極薄銅膜表 面施行電解鑛銅處理。依此’便可輕易地形成密接性優異， 且蚀刻直線性、厚度均勾性均優異的極薄銅落層。 本發明的鑄模用銅箱係使用表面粗度依Rz值計為 1· Op以上、2·2㈣以下光澤形狀的㈣，並對該表面施 行粗化瘤處理。 對上述銅羯施行粗化瘤處 理的焦鍍浴組成’係如下述 12 201037104 .硫酸濃度：80〜12〇g/l •源自硫酸銅的銅濃度：20〜30g-Cu/l、較佳23〜25g-Cu/l •源自鉬化合物的鉬濃度：150〜350mg-Mo/l •源自鐵化合物的鐵濃度：150〜300mg-Fe/1 '較佳250士 50mg-Fe/1 •源自鉻化合物的三價鉻濃度：150〜300mg-Cr/；l、較佳250 ±50mg-Cr/1 •源自鎢化合物的鎢濃度：〇. 1〜2〇mg-Cr/l、較佳1〇 土 2.5mg-W/l •源自鈒化合物或銻化合物的釩濃度或銻濃度： 50〜200mg-V/l 或 50~200mg-Sb/l、較佳 i5〇±3〇mg_v/i 或 150±30mg-Sb/l •源自氯化合物的氣濃度：〇.卜2· 〇mg_n/1、較佳 〇·1〜0·5mg-Cl/l m Wl Ο •浴溫：20〜30°C、較佳 23. 5〜25. ， •電流密度：直流整流，25〜35A/dm2、較佳28±ι.5α/^2 土施行焦電鑛的銅箱表面，係只要電解電鍛製箱不管係 #從陰極滚筒表面上拉剝之一側的面（出1 , 甸1先澤面），或靠液面 m 側之-面(粗糙面)任一者，表面粗度依Rz值計為u从 以上2. 2 // m以下的面便可，其餘並無限制。 、‘ 一般利用柱狀結晶構造進行 仃I》自的電解銅箔時，早 好使用光澤面侧。但是，當利用細檄沾 攻、％晶進行製箔的錐 係平滑銅箔（例如古河電氣工業股 胥限公司所製造電解 13 201037104 銅猪的WSH)時，相較於光澤面之下，粗糙面較富平滑性。 因而，當使用該WS箔時，對平滑的粗糙面側施行焦電鍍， 接著施灯膠囊電鍍處理，而施行健全的粗化瘤處理，便可 製成依Rz值計2· 5 // m以下，且粗化瘤的瘤間隙在〇. i # m 以上1 · 0 # m以下形狀的粗化面。 其-人’對依上述焦電鍍所形成粗化瘤處理形狀的表 面，在下述條件下施行平滑膠囊電鍍： •硫酸;辰度· 80〜120g/l •源自硫酸銅的銅濃度：4〇〜60g-Cu/l、較佳50±2· 5g-Cu/l •浴溫：45〜60°C、較佳55±2.5。匚 •電流密度：直流整流，18〜25A/dm2、較佳2〇±2. 5A/dm2 依此藉由對粗化瘤處理面施行平滑膠囊電鍍處理，便 可達成不會粉落的牢固且健全柱狀形狀。 然後’對該銅箔施行防銹處理的有機防銹處理、鉻酸 處理、鎳處理或鋅處理，便可形成鑄模用粗化處理銅箔。 有機防錢劑較佳係苯并三。坐（1，2，3-Bnzotr iazo 1 e[通 稱· BTA ])，亦可為市售衍生物。處理量係只要施行在 JIS-Z-2371所規定的鹽水噴霧試驗（鹽水濃度：5%_NaC1、 溫度35°C )條件下，於24小時内，表面均不會發生氧化銅 變色程度的浸潰處理便可。 錄處理防銹的情況，附著N i金屬施行定量分析的量係 只要0· 06〜0. 12mg-Ni/dm2(每10cm的分析值）便可。當粗化 處理面側超過〇· 12mg/dm2的情況’發生遷移不良情況的顧 慮會提高，因而最好避免。且，小於0. 〇6mg-Ni/dm2時， 14 201037104 便無法獲得充分地防銹效果。 當辞處理防錢的情況，附著Ζη金屬施行定量分析的量 係只要0. i 5〜0. 35mg-Zn/dmM ! 〇cm的分析值）便可。即便 粗化處理面側超過0.35mg/dm2,僅會因擴散效果導致表面 黃銅化，雖不會有特別的障礙，但適當的上限量最好 〇.35mg-Zn/dm、反之’若小於〇.___，則經驗性 會發生變色不良的情況，因而最好避免。 Ο Ο 另外，可任意選擇對銅羯單面施行粗化處理、或雙面 均施行粗化處理。 當將所獲得鑄模用銅H(例如公稱厚度的粗化處 理用銅箱），使用為例如BGA(Bal卜㈤士㈣）（鑄模）用 途構件的情況，便將粗化處理面側與對象基材相貼合。然 後，於積層後便將該銅羯全部效率佳地㈣除去，並利用 過猛酸處理液施行清洗。另外，過猛酸處理液係具有將舞 電鑛時，被取入之除銅以外的金屬殘渣予以溶解的效果。 所以，過猛酸處理液係屬於能消除遷移顧慮的手段、與使 健王達成後續無電解鍍銅步驟的前處理劑之最佳藥劑。 田BGA用途構件需要3 0 厚度極薄銅箔的情況，只要 在該基材的缚模面上根據無電解鑛銅藥劑的製程，施行無 電解鑛銅便可。且’依情況，對無電解鑛銅上利用電解電 鍍附加厚度，亦可降低成本。 另外，當組合無電解電鍍與電解電鍍，對une/space 、 4 L/S」以下的細微配線電路施 行#刻加工時’在無電解電鐘的結晶與電解電鐘的結晶間 15 201037104 之界面，偶而會有發生因蝕刻液滲入導致電路不良情况， 因而在細線加工時必需留意。 以上未處理金屬箔係以電解銅箔為例進行說明。佝 :’未處理金屬箔係除電解銅箔之外，相關軋延銅箔、鋁 冶、不銹鋼箔等亦均同樣的可應用。 [實施例] 其次，針對本發明實施形態，根據以下的實施例進行 說明。 [實施例1] '在皁重厚度l〇7g/m2(相當於公稱厚度12//m)且具有細 概結晶粒的未處理電解銅箔之液面側，對表面粗度依Rz值 叶1. 5 # m的面上’依以下條件施行形成粗化瘤的焦電鍍。 依下述浴組成與電鍍條件施行電解處理（焦電鍍）： •硫酸濃度：l〇〇g/1 •源自硫酸鋼的鋼濃度：23.5g-Cu/l .源自鉬化合物的鉬濃度：25 0mg-Mo/1 •源自鐵化合物的鐵濃度：200mg-Fe/M •源自鉻化合物的三價鉻濃度· 2〇〇mg Cr/i •源自鎢化合物的鎢濃度：8.5mg-W/1 •源自釩化合物的釩濃度：150mg-V/lThe cross-sectional area of the opening is larger than that of the eight lobes - the shape of the liver in the concave 4 J or the Ρ Ρ 存在. Therefore, the recess will be the best shape for the nailing effect.丨, after the palladium, on the surface of the insulating substrate, and then attached to the electroless metal surface, it will become a thin layer of copper with a small resistivity and a small metal oxide core, such as a thickness of 201037104 • 0.1 to 5/zm. plating. Next, an electric ore mask is disposed on the surface of the plating layer of the thin layer of electric ore except for the area of the desired wiring pattern. The key mask is formed, for example, by providing a photosensitive resin on the surface of the electric ore layer, and then performing exposure by developing a photomask for forming a desired pattern. Then, by supplying electric power from the electroless ore layer formed as described above, electric wiring is formed by conducting electrical plating of a conductive metal (for example, copper) in a desired wiring pattern region where the photosensitive resin is not coated. Next, after the photosensitive resin is removed, electroless plating is performed by using a surname engraving such as a sulfuric acid peroxidation gas system, a persulfate type, or an ammonia-missing salt type, and the portion covered with the electroplated layer is electrolessly plated. The layer is removed. Since the electroless plating layer is thinner than the wiring of the electroplated metal layer, the speed is faster. However, the electrical lithography wiring of the desired pattern is hardly engraved. Therefore, the electroless plating layer under the desired pattern formed by the electric electricity money layer will be unmasked because the wiring of the electroplated layer will become a mask and be protected. Finally, it is immersed in a mixture of excessive acid and sodium oxychloride. Thereby, it adheres to the surface exposed by the insulating substrate, and it is not possible to carry out the remaining (four) from the above (4) liquid. (This method is disclosed in Patent Document 1.) [Prior Art Document] [Patent Document] [Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-196813 [Summary of Invention] 5 201037104 (Problem to be solved by the invention) Patent In the literature 1, there is a t (four), the electric plating of the electroplating is placed on the copper V white surface with an abnormal plating phenomenon (pyroelectric:) often several times to implement the electric mine's profit. In this document, it is described that fine particles of granular copper are grown in the crucible. The size of the particles, the coarseness of the sugar, and the comprehensive roughening shape such as &#, and the 忐A Α and the granules are The bonding strength between the edge substrates is important! The copper bismuth manufacturer is the purest and easy to obtain, but the related details are not revealed. The present invention is directed to a metal case suitable for mounting a wiring board for mounting a wiring board such as a semiconductor element, an integrated circuit, an electronic component, etc., and successfully provides a preferable shape roughening which is suitable for a metal case for molding use. (4) Metal enamel, and also provides a wiring board having a wiring pattern excellent in the adhesion between the insulating substrate and the wiring pattern, and the wiring pattern which is excellent in both linearity and thickness uniformity. Commercially available electrolytic copper ruthenium is generally a roughened shape for improving the adhesion to a substrate, and a copper granule is present, and the copper granules are densely close together at the root. The main mold application of the present invention is to surface-treat the metal drop, and is characterized in that a fine columnar shape unevenness having a gap of 0. 丨 # m or more and 丨. 〇 # m is formed on the roughened surface side. (Means for Solving the Problem) The metal pig of the present invention is characterized in that the metal having a plated roughened surface is subjected to roughening plating on at least one side of the untreated metal foil by coke electroplating, and the coarse metal The capsule shovel 201037104 (capsule plate) is applied to the plaque, and the surface roughness is 1. 0 " m to 2· 5 # m, and according to the RZ value (the same below) specified in JIS B 〇6〇1 The roughening tumor formed by the roughening of the tumor is a columnar shape having a gap of 0.1# m or more and 1. The metal foil of the present invention is a metal foil which is subjected to rustproof treatment on the above-mentioned electroplated roughened surface. In the metal foil of the present invention, the untreated metal foil is a rolled copper foil or a copper strip; the untreated copper tank is at least plated with a rough surface on the surface side of the roughened surface, and the Rz value is "to 2 2 " The metal foil of the present invention is mainly used for molding. The insulating substrate of the present invention is an insulating substrate which is formed into a roughened surface by transferring the uneven shape of the plated roughened surface of the metal foil. The wiring board is a wiring board that forms a predetermined wiring pattern on the roughened surface of the insulating substrate. The method for producing a metal foil according to the present invention is characterized in that the roughness of the surface is 1.0 to m in terms of Rz. "m untreated metal foil, using a plating bath containing a metal added to a sulfuric acid-copper sulfate plating solution, a copper pyrophosphate plating solution or a copper carbonate plating solution, and performing coke plating to form a roughened plating surface, and The surface of the roughened tumor surface is subjected to capsule plating to form a surface roughness of 1. ID to 2. 5/zm, and the adjacent roughening tumor has a 〇. J # m or more 〇 a columnar shape with a gap below the claw The shape is plated to roughen the surface. In the method for producing a metal foil according to the invention, the metal to be added to the plating solution is iron, chromium, molybdenum, tungsten, and vanadium or niobium. In the method for producing a metal foil according to the present invention, the plating is coarse. In the method for producing a metal foil according to the present invention, the untreated metal foil is a rolled copper foil or an electrolytic copper foil. The metal 4' is mainly subjected to roughening treatment according to the method for producing a metal foil of the present invention. The use is a mold application. (Effect of the Invention) The metal foil of the present invention is mainly excellent in the anchoring effect (using the casting (four) riding effect) in the mold application, and thus only reduces the plating cost when the electroless ore is applied in the subsequent step. The metal crucible of the present invention is excellent in adhesion between the insulating substrate and the wiring pattern, and is excellent in linearity in the thin-line circuit step in the production of the circuit. Therefore, the present invention is manufactured to mount, for example, a semiconductor element or an integrated circuit. In the case of a wiring board for electronic parts and the like, it has an excellent effect. The L-shaped gown method] The metal foil-based stainless steel foil and aluminum of the present invention are as long as they belong to each other. (Iv) (iv) the way and may then gold; Patent 4 ... Hereinafter, the present invention is' based on pre-metal box into strongyloidiasis copper foil Example "1 J Ding 4 into fine described more β aa σ Xi. In addition, the relevant results of the rolling of copper, so the provincial government 4 έ ..., white can also be obtained from the prisoner. The electrolytic steel 笮γ of the electroplating roughening table β 1 is used to form 刖 「 「 「 「 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 未 广 广 广Thickness 9~18" An acoustic sound consists of 0g/ni (phase ΜαπΟ' and crystallographic microcrystals in the thickness direction). "The single thickness of r DO to,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, "Copper specific gravity (8·9)"). The "nominal thickness" refers to the measured thickness. The reason for the untreated copper foil is that the single-thickness and the thickness δ are 60g/m to 153 2 The treatment is not performed; the treatment of the roughening of the L tamping treatment, or the step of roughening the layer on the insulating substrate, and the removal of the crucible by etching The characteristics of the handling are excellent. The untreated copper pig is subjected to coke electroplating. In the plating bath of the coke plating, the sulfuric acid-copper sulfate ore, copper pyrophosphate or copper carbonate bath is used. Add any metal additive to any of the basic plating compositions. The metal addition % is ^ (iron), Μο (turn), Cr (chromium), w (he), and ν (hunger) or at (record) Or both. On the surface of the untreated copper foil, the pyroelectric plating is performed near the limiting current density of the above plating bath to form a fine crystalline tumor. Shape: Because: In the coke plating bath, Fe (iron), Mo (molybdenum), Cr (chromium), and w (tungsten) are added as follows, so that a fine columnar shape is formed with a design gap. In addition, 'V(鈒) or Sb(recording) can improve the resistance when forming a single-sided processing box. The details of the related plating method will be described later. Next, the roughening is performed according to the use of coke plating. The surface of the roughened tumor formed by the tumor is formed so that the copper particles of the fine columnar shape of the tumor do not easily fall off, and smooth plating (so-called capsule plating) is performed to form a surface roughened copper box or a copper for mold use. Box (hereinafter referred to as "steel for casting mold"). The method of the capsule key is described later. The above-mentioned capsule plating system is used to perform the roughening treatment of the roughened surface of the plating. The Rz value according to JIS-B-0601 (the same below) ) is 1〇#m to 9 201037104, 2. 5 # m or less, a columnar gap below the micro-columnar shape (columnar). Even if the copper particles are subjected to capsule electricity, §H column has 〇1 plating, It can still be kept fine # m or more, 1. 0 # m according to the above In the case of a copper foil for a mold, as described above, an insulating substrate made of a copper foil for a mold is laminated on, for example, an epoxy substrate or a poly-resin resin or an organic film. When the foil is completely dissolved and removed by etching, a fine columnar mold having a columnar gap is formed on the insulating substrate, and the steel foil for transferring the mold (the metal plated roughened surface has a concave-convex shape on the insulating substrate). Then, a roughened surface is formed, and then a metal film is formed on the roughened surface of the insulating substrate by a plating process, and then the wet processing is performed on the metal film to perform pattern processing, thereby forming a predetermined wiring pattern. A wiring board is formed. Conventional single-sided roughening copper pigs with high frequency of use are generally in the form of a mortar, and the copper granules are closely packed together according to the roots. Therefore, the anchoring effect (using the anchoring effect of the mold) is poor, and the amount of plating in the absence of the electrolysis chain is increased, resulting in an increase in cost. Moreover, when the circuit is subsequently fabricated, the etching linearity in the etching process of the thin line circuit is also poor. The main purpose is a copper foil of the present invention for molding, and a fine columnar shape having a gap of 0.1 m or more and 1.0 k " m or less is formed on the side of the roughened surface. Therefore, by using the copper foil, it is possible to easily form the unevenness (molding) excellent in the anchoring effect (the stud effect by the casting) on the surface of the insulating substrate in a uniform and concavely sound interval and shape. Therefore, the amount of electroless plating in the subsequent step can be saved to the minimum limit, and the etching linearity in the thin line circuit etching step is excellent in the subsequent circuit system 10 201037104. Therefore, it is possible to provide a copper foil for a mold which is suitable for the production of a wiring board for mounting a semiconductor element, an integrated circuit, an electronic component, or the like, and a surface-treated copper crucible having a roughened surface. The fine columnar shape (roughening shape) applied to the surface of the copper box is based on the surface roughness! The value of ^ is calculated as 1 〇 #m above and below.依 By following this specification, a mold having a columnar gap can be formed on the surface of the insulating substrate in a fine column shape without leaving unnecessary etching residue. Here, when Rz (corresponding to the mold depth) is less than 1. 〇 Am, there is a concern that there is a problem in terms of heat resistance reliability. On the other hand, when Rz exceeds 2.5 # m, the size of the concave portion formed on the surface of the insulating substrate becomes A'. When the T-shaped & Therefore, the shape of the roughening treatment of the copper mold fl is preferably 1 〇 (four) or more and 2. 5 // m or less in terms of Rz value. In the present invention, a fine columnar shape having a gap of 0.1 A m or more and 1.0 μm or less is formed on the roughened surface side of the copper box for a mold. The copper tear system of β α J before the electroplating roughening treatment has a fine particle crystal structure. "Copper foil with a fine-grained crystal structure, J-smelting" is the surface roughness before the roughening treatment, and is based on the Rz value of 1· 〇υ in m μ, 2. 2 # m or less. Shape copper foil. By performing a roughening treatment on a copper-smelting method having a fine structure, a day-to-day structure, it is possible to design a roughened shape having the above-mentioned "Xu, &," gaps, that is, by having a columnar shape The crystallized general electrolytic copper foil is subjected to roughening treatment on the white base, and it is difficult to form the mold shape of the present invention. In the present invention, the surface roughness of the untreated copper foil is determined by the Rz value leaf gauge - The reason is that the Rz value is less than 丨·....the second/white is not very productive in the air-porting step, and is not suitable for industrial materials, and when the Rz value exceeds 2. 2 // m, the in-focus plating In the step, the initial electricity: the copper particles are concentrated and adhered (electroplated) to the front end having a high degree of coarseness, and as a result, the dendritic shape is extremely brittle and rough, and in order to form a sound state, it is necessary to pass the production: the next step Smooth plating. As a result, it can not be used as a mold: if the unevenness is used, or when the (four) day is taken, the dendritic front end will become a residue in the substrate, which causes a high risk of causing migration failure. Therefore, it will be untreated. The surface roughness of the copper is calculated according to the Rz value, which is specified in 22 the following. The present invention is subjected to roughening and plating, and Rz (corresponding to the mold depth) is 1. Mm or more and 2. 5 or less and the gap between the roughened tumors is. Above, 1·. ...The copper mold for the mold under the arm is attached to the insulating substrate. In the next step, in the next step, the manufacturing process treats the (4) removed acid treatment, and performs the cleaning treatment to polish the insulating substrate surface without damaging the shape of the mold. _, an ultra-thin copper film is formed on the surface of the insulating substrate by electroless electricity, and the surface of the ultra-thin copper film is subjected to electrolytic copper treatment. According to this, it is possible to easily form an extremely thin copper falling layer which is excellent in adhesion and excellent in etching linearity and thickness. In the copper box for a mold of the present invention, (4) having a surface roughness of 1· Op or more and 2·2 (four) or less of a gloss shape in terms of Rz value is used, and the surface is subjected to roughening treatment. The composition of the coke plating bath for the above-mentioned copper ruthenium treatment is as follows: 12 201037104. Sulfuric acid concentration: 80 to 12 〇g / l • Copper concentration derived from copper sulfate: 20 to 30 g-Cu / l, preferably 23~25g-Cu/l • Molybdenum concentration derived from molybdenum compound: 150~350mg-Mo/l • Iron concentration derived from iron compound: 150~300mg-Fe/1 'better 250±50mg-Fe/1 • Trivalent chromium concentration derived from chromium compound: 150~300mg-Cr/; 1, preferably 250 ± 50mg-Cr/1 • Tungsten concentration derived from tungsten compound: 〇. 1~2〇mg-Cr/l, Jia 1 bauxite 2.5mg-W / l • Vanadium concentration or bismuth concentration derived from bismuth compound or bismuth compound: 50~200mg-V/l or 50~200mg-Sb/l, preferably i5〇±3〇mg_v/ i or 150±30mg-Sb/l • Gas concentration derived from chlorine compound: 〇. Bu 2· 〇mg_n/1, preferably 〇·1~0·5mg-Cl/lm Wl Ο • Bath temperature: 20~30 °C, preferably 23. 5~25. , • Current density: DC rectification, 25~35A/dm2, preferably 28±ι.5α/^2 The surface of the copper box for the implementation of coke ore, as long as electrolytic forging The box is pulled from the surface of the cathode roller by one side (out of 1 , Dian 1 Xianze surface), or by liquid level m For the side-surface (rough surface), the surface roughness may be u from the above 2. 2 // m or less, and the rest is not limited. In the case of the electrolytic copper foil which is generally used in the columnar crystal structure, the gloss side is used as early as possible. However, when a cone-shaped smooth copper foil (for example, WSH manufactured by Furukawa Electric Co., Ltd., manufactured by Furukawa Electric Co., Ltd.) is used, it is rougher than the gloss surface. The surface is more smooth. Therefore, when the WS foil is used, the smooth rough surface side is subjected to coke electroplating, and then the lamp capsule plating treatment is performed, and a sound roughening treatment is performed to obtain a Rz value of 2.5·m or less. And the interstitial space of the roughened tumor is in the roughened surface of the shape below 〇. i # m above 1 · 0 # m. The skin-forming surface of the roughened tumor-treated shape formed by the above-mentioned coke plating is subjected to smooth capsule plating under the following conditions: • sulfuric acid; elongation · 80 to 120 g/l • copper concentration derived from copper sulfate: 4 〇 ~60g-Cu/l, preferably 50±2·5g-Cu/l • Bath temperature: 45~60°C, preferably 55±2.5.匚•Current density: DC rectification, 18~25A/dm2, preferably 2〇±2. 5A/dm2 According to this, by performing smooth capsule plating on the roughened surface, it can achieve firmness without powder. Sound columnar shape. Then, the copper foil is subjected to an antirust treatment, an organic antirust treatment, a chromic acid treatment, a nickel treatment or a zinc treatment to form a roughened copper foil for a mold. The organic anti-money agent is preferably a benzotriene. Sit (1,2,3-Bnzotr iazo 1 e [general · BTA ]), or a commercially available derivative. The treatment amount is as long as the salt spray test (salt water concentration: 5%_NaC1, temperature 35 °C) specified in JIS-Z-2371 is applied, and the surface is not immersed in the discoloration of copper oxide within 24 hours. Processing can be. In the case of recording rust prevention, the amount of quantitative analysis of the metal attached to the Ni metal is 0. 06~0. 12 mg-Ni/dm2 (analytical value per 10 cm). When the roughening treatment side exceeds 〇·12 mg/dm2, the risk of occurrence of migration failure is improved, so it is preferable to avoid it. Moreover, when it is less than 0. 〇6mg-Ni/dm2, 14 201037104 cannot obtain sufficient rust prevention effect. In the case of dealing with anti-money, the amount of quantitative analysis of the attached Ζ metal is as long as 0. i 5~0. 35mg-Zn/dmM ! 分析cm analysis value). Even if the roughened surface side exceeds 0.35 mg/dm2, the surface is only brassized due to the diffusion effect. Although there is no particular obstacle, the appropriate upper limit is preferably 3535mg-Zn/dm, and vice versa. 〇.___, the experience will be poorly discolored, so it is best to avoid. Ο Ο In addition, the copper enamel can be arbitrarily roughened on one side or roughened on both sides. When the obtained copper H for a mold (for example, a copper box for roughening treatment of a nominal thickness) is used as a member for use of, for example, BGA (Bal), the roughened surface side and the object base are used. The materials are attached. Then, after the lamination, the copper crucible is completely removed (4), and the cleaning is carried out using a persulfate treatment solution. Further, the pulverized acid treatment liquid has an effect of dissolving the metal residue other than copper which is taken in the dance. Therefore, the super acid treatment liquid is a suitable means for eliminating the migration concern and a pretreatment agent for the subsequent electroless copper plating step. In the case where the field BGA use member requires an extremely thin copper foil of 30%, it is only necessary to apply electroless copper ore according to the process of the electroless copper mineral agent on the binding surface of the substrate. And depending on the case, the thickness can be increased by electroless plating on the electroless copper ore, and the cost can also be reduced. In addition, when electroless plating and electrolytic plating are combined, the interface between the crystallization of the electroless clock and the crystal of the electrolysis clock 15 201037104 is applied to the fine wiring circuit of une/space or 4 L/S" or less. Occasionally, there is a circuit failure caused by the penetration of the etching solution, so it is necessary to pay attention to the processing of the thin wire. The above untreated metal foil is described by taking an electrolytic copper foil as an example.佝 : 'Untreated metal foil is used in addition to electrolytic copper foil, and the relevant rolled copper foil, aluminum smelting, stainless steel foil, etc. are equally applicable. [Embodiment] Next, an embodiment of the present invention will be described based on the following embodiments. [Example 1] 'The liquid surface side of the untreated electrolytic copper foil having a thickness of l〇7 g/m2 (corresponding to a nominal thickness of 12/m) and having fine crystal grains, the surface roughness was determined by the Rz value leaf 1. On the surface of 5 #m, coke plating for forming a roughening tumor is performed under the following conditions. Electrolytic treatment (coke plating) according to the following bath composition and plating conditions: • Sulfuric acid concentration: l〇〇g/1 • Steel concentration derived from sulfuric acid steel: 23.5 g-Cu/l. Molybdenum concentration derived from molybdenum compound: 25 0 mg-Mo/1 • Iron concentration derived from iron compound: 200 mg-Fe/M • Trivalent chromium concentration derived from chromium compound · 2 〇〇 mg Cr/i • Tungsten concentration derived from tungsten compound: 8.5 mg- W/1 • Vanadium concentration derived from vanadium compound: 150 mg-V/l
•源自氣化合物的氯濃度：0. 5mg-Cl/l •浴温：24. 5°C .電流密度：直流整流、28A/dm2 其人為能藉由對上述焦電鍍粗化面施行平滑電鍍， 16 201037104 而形成不會粉落的牢固且健全粗化瘤處理形狀，便依下述 洛組成與電鑛條件施行膠囊電鑛： •硫酸濃度：100g/l• Chlorine concentration derived from gas compound: 0. 5mg-Cl/l • Bath temperature: 24. 5°C. Current density: DC rectification, 28A/dm2. It can be artificially smoothed by the above coke electroplated roughened surface. , 16 201037104 And form a firm and sound rough tumor treatment shape that does not fall into powder, and then perform capsule electric ore according to the following composition and electro-mineral conditions: • Sulfuric acid concentration: 100g/l
•源自硫酸銅的銅濃度：5〇g~Cu/l •浴溫：55°C •電流在、度.直流整流、22A/dni2 然後，將該銅箔雙面利用公知鉻酸處理液（依Cr〇3濃 0 度計，相當於3. Og/ΐ)施行防銹處理。 將依實施例1所製得銅箔，依22(rc、3〇kgf/cm2、i〇〇min 條件，積層於市售高周波對應絕緣基板（三菱瓦斯化學股份 有限公司製）上。然後，將在該表面上積層的所有銅箔利用 • 氯化銅蝕刻（比重：丨.265;浴溫：45t)完全溶解除去，並 充分施行水洗洗淨。接著，使用日本MacDermid股份有限 a司製去膠渣製程步驟液（MacuDizer 92〇4、m76、 9279)，對鑄模部施行所謂的過錳酸蝕刻，並充分施行水洗 〇洗淨。然後，對該表面根據公知增厚用無電解鍍銅製程(日 立製作所AP2製程），形成厚度約3.〇#m的銅膜。 其次，在該具有無電解銅膜的基板之鋼膜表面上，形 成L/S = 50 # m/50 # m的蝕刻測試用細線電路，並利用光學 顯微鏡觀察經蝕刻後的電路直線性（參照第1(A)圖）。然 後，利用ΕΡΜΑ實施構成遷移原因的金屬殘渣（特別係銅） 的粗糙觀察（參照第1(Β)圖）。結果如表i所示。 再者，測定銅膜與絕緣基板間之密接強度，結果合併 、、表1中。密接強度（kN/m)的測定係對具有無電解銅膜 17 201037104 的基板之銅膜表面，估、， 用么知硫酸-硫酸銅洛，鍵厚出3 ^m 厚度’並在經鍍厚的类品L ^ 緞与的表面上，利用經ϋν照射而硬化的uy 油墨與網版施行_安h H丨^ 1 仃圖木印刷形成〇_ lm/m寬度的圖案，並根據 J IS C 6481測定依照蝕刻所獲得的該圖案。 更針對處理表面的粗化瘤間隔、與有無，就利用實 體顯微鏡的倍率所拍攝截面照片（參照第i(c)圖）之粗化瘤 最外側輪廓的間隔，使用爪規格合格的市售微測游標卡 尺進行實測’並依據倍率進行換算而求取間隔。此處，如 第1(c)圖所不’藉由在處理表面上分散銅粒子並附著，而 電鍍成長出樹枝狀，便依相隔間隔形成複數柱狀形狀。複 數柱狀形狀係形成隨遠離處理表面而寬度逐漸變狹窄狀 [、因❿依如上料行該柱狀形狀的底部間隔的實測。 該測定結果合併記於表1。 表1所示姓刻後的電路直線性判定，係依光學顯微鏡 的觀察結果實施。生丨$ I准& , 衣耳施#疋基準係如第1(A)圖所示，將顯微鏡 照片中’餘刻面大致呈亩綠參 呈直線者砰為◎」，將略難具直線 性但實用上不會構成問題者評為「△」，將實用上會有問 題者評為「X」。 因銅殘渣所造成粗縫的觀察，係如第1(B)圖所示，將 依ΕΡΜΑ觀察完全無法確認到銅殘渣者評為「◎」，將略可 確認到者評為「〇」，將略有殘㈣在但實用上不會構成 問題者評為「△」。 相關處理表面的粗化瘤間隔、與有無，如第i(c)圖所 示’就利用實體顯微鏡的倍率所拍攝截面照片之粗化瘤最 18 201037104 外側輪廓的 進行實測， [實施例2] 間隔’使用JIS規格合格的市售微測游標卡尺 並依據倍率進行換算而求取間隔間的距離。 實施例1所使用具有細微結晶粒的未處理銅箱之單重 厚度係63g/m2(相當於公稱厚冑7#m)。除此點之外，其餘 就焦電鍍條件、膠囊電鍍條件及防銹處理條件，均完全如• Copper concentration derived from copper sulfate: 5〇g~Cu/l • Bath temperature: 55°C • Current in, degree, DC rectification, 22A/dni2 Then, the copper foil is coated on both sides with a known chromic acid treatment solution ( According to Cr〇3 concentration 0 degree, equivalent to 3. Og / ΐ) to carry out anti-rust treatment. The copper foil obtained in the first embodiment was laminated on a commercially available high-frequency corresponding insulating substrate (manufactured by Mitsubishi Gas Chemical Co., Ltd.) under the conditions of 22 (rc, 3 〇 kgf/cm 2 , i 〇〇 min). All the copper foil laminated on the surface was completely dissolved and removed by etching with copper chloride (specific gravity: 丨.265; bath temperature: 45t), and fully washed with water. Then, using Japan MacDermid Co., Ltd. The slag process step liquid (MacuDizer 92〇4, m76, 9279) is subjected to a so-called permanganic acid etching on the mold portion, and is sufficiently washed with water, and then the surface is subjected to an electroless copper plating process according to a known thickening method ( Hitachi, Ltd. AP2 process), forming a copper film having a thickness of about 3. 〇 #m. Next, an etching test of L/S = 50 # m/50 #m is formed on the surface of the steel film of the substrate having the electroless copper film. Using a thin-line circuit, the linearity of the etched circuit is observed by an optical microscope (see Fig. 1(A)). Then, the rough observation of the metal residue (especially copper) constituting the cause of migration is performed by ΕΡΜΑ (refer to the first ( Β) Figure). The results are shown in Table i In addition, the adhesion strength between the copper film and the insulating substrate was measured, and the results were summarized in Table 1. The measurement of the adhesion strength (kN/m) was performed on the surface of the copper film of the substrate having the electroless copper film 17 201037104. , using the so-called sulfuric acid-copper sulfate, the thickness of the bond is 3 ^m thick' and on the surface of the plated thick L ^ satin and the uy ink hardened by ϋν irradiation and the screen version h H丨^ 1 仃 木 印刷 印刷 印刷 lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm lm The interval between the outermost contours of the roughened tumors of the magnification of the microscope (see the i-th (c)) is measured by using a commercially available micro-measured vernier caliper with a good claw specification, and the interval is calculated based on the magnification. Where, as shown in Fig. 1(c), by dispersing copper particles on the treated surface and attaching them, and electroplating grows into a dendritic shape, a plurality of columnar shapes are formed at intervals, and the plurality of columnar shapes are formed in a distance-dependent manner. Surface and width gradually narrow [The actual measurement of the bottom spacing of the columnar shape as described above. The results of the measurement are summarized in Table 1. The linearity determination of the circuit after the last name is shown in Fig. 1 based on the observation results of the optical microscope.丨$I准&, 衣耳施#疋The reference system is shown in Figure 1(A), and the microscope image shows that the 'the remaining facets are roughly the same as the acre of green ginseng. ◎" Those who do not pose a problem in terms of practicality will be rated as "△", and those who have problems in practical use will be rated as "X". The observation of the coarse seam caused by copper residue is as shown in Figure 1(B). According to the observation, those who could not confirm the copper residue were rated as "◎", and those who were slightly confirmed were rated as "〇", and those who were slightly disabled (4) were rated as "△" in those who did not pose a problem in practical use. The roughening of the surface of the relevant treatment surface, with or without, as shown in Figure i(c), was measured on the outer contour of the roughened tumor of the cross-sectional photograph taken by the magnification of the stereomicroscope. [Example 2] Interval 'Using a commercially available micro-measuring vernier caliper that is qualified by JIS and calculating the distance between the intervals based on the magnification. The untreated copper tank having fine crystal grains used in Example 1 had a single thickness of 63 g/m2 (corresponding to a nominal thickness of #7#m). In addition to this, the rest of the coke plating conditions, capsule plating conditions and anti-rust treatment conditions are exactly the same.
同實施例1般的實施各處理’評估測定結果合併記於表卜 [實施例3] 實施例1所使用具有細微結晶粒的未處理銅荡之單重 厚度係153g/m2(相當於公稱厚度18# m)。除此點之外其 餘就焦電鍍條件、膠囊電鍍條件及防銹處理條件，均完全 如同實施例1般的實施各處理，評估測定結果合併記於表 [實施例4] 對厚度為單重厚度l〇7g/m2(相當於公稱厚度12 )， 且具有細微結晶粒的未處理電解銅箔靠液面側之表面粗度 依Rz值計1. 5 " m之一面，依照以下的浴組成與電鍍條件 施行形成粗化瘤的焦電鍍。 在此’對下述基本浴，依成為下述濃度方式使各化合 物溶解後，再利用工業用濃硫酸將pH調整為1. 2，而形成 焦磷酸銅電解鍍浴。 •基本浴：依來自焦磷酸銅的銅濃度為23. 5g-Cu/l進行溶 解的溶液中，添加焦磷酸鉀（焦磷氧化合物）3〇〇g/i 源自銷化合物的翻濃度：25Omg-Mo / 1 19 201037104 •源自鐵化合物的鐵濃度：200mg-Fe/l •源自鉻化合物的三價鉻濃度：200mg-Cr/1 •源自鶴化合物的鎢濃度·· 8.5mg-W/l •源自鈒化合物的鈒濃度：150mg-V/l •源自氯化合物的氯濃度：0. 5mg-Cl/l 然後，使用上述組成的焦磷酸電解鍍浴，依下述條件 實施電解處理（焦電鍍The results of the evaluation of the evaluations in the same manner as in the first embodiment are shown in the table. [Example 3] The untreated copper having fine crystal grains used in Example 1 has a single thickness of 153 g/m 2 (corresponding to the nominal thickness). 18# m). Except for this point, the coke plating conditions, the capsule plating conditions, and the rust-preventing treatment conditions were all carried out exactly as in the case of Example 1, and the evaluation results were combined and summarized in the table [Example 4] The thickness was a single thickness. L〇7g/m2 (corresponding to the nominal thickness of 12), and the surface roughness of the surface of the untreated electrolytic copper foil having fine crystal grains on the liquid surface side is 1. 5 " m one side, according to the following bath composition Coking plating to form a roughened tumor is performed with plating conditions. Here, in the following basic bath, the respective compounds were dissolved in the following concentration mode, and then the pH was adjusted to 1.2 by using concentrated sulfuric acid for industrial use to form a copper pyrophosphate electroplating bath. • Basic bath: Add potassium pyrophosphate (Coke Phosphate) 3 〇〇g/i from a solution in which the copper concentration of copper pyrophosphate is 23. 5g-Cu/l. 25Omg-Mo / 1 19 201037104 • Iron concentration derived from iron compound: 200 mg-Fe/l • Trivalent chromium concentration derived from chromium compound: 200 mg-Cr/1 • Tungsten concentration derived from crane compound · 8.5 mg- W/l • Hydrazine concentration derived from hydrazine compound: 150 mg-V/l • Chlorine concentration derived from chlorine compound: 0.5 mg-Cl/l Then, using a pyrophosphate electroplating bath of the above composition, the following conditions were carried out Electrolytic treatment
•液溫：28. 5°G •電流密度：直流整流、32A/dm2 焦電鍍以後的膠囊電鍍亦是可為焦磷酸銅浴，但本實 &例則依完全如同實施们相同的膠囊電鍍條件、防錢處 理條件施行處理。評估測定結果合併記於表卜 [實施例5] 在厚度為單重厚度1〇7g/m2(相當於公稱厚度心約， 且具有細微結晶粒的未處理電解銅猪靠液面側，表面粗度 依 Rz 值計 A t 上’依以下的條件施行形成粗化 瘤的焦電鍍。 在此，對下述基本浴，依成為下述濃度的方式添加各 化合物，而形成碳酸鋼電解鍍浴。 •基本浴：依來自碳酸鋼的銅濃度為23.5g-cu/1方式溶 解，利用工業用濃硫酸將PH調整為1>2 •源自鉬化合物的鉬濃度：25〇mg-Mo/l •源自鐵化合物的鐵濃度：2〇〇mg Fe/i •源自鉻化合物的三價鉻濃度：2〇〇mg —以八 201037104 •源自鶴化合物的鎢濃度：8. 5mg-W/l •源自鈒化合物的釩濃度：150mg-F/i •源自氯化合物的氯濃度·· 0. 5mg-Cl/l 施行電解 然後’使用該碳酸鋼電解鍍浴，依下述條件 電鍍處理（焦電鍍）。• Liquid temperature: 28. 5°G • Current density: DC rectification, 32A/dm2 After the electroplating, the capsule plating can also be a copper pyrophosphate bath, but the actual & Conditions and anti-money treatment conditions are applied. The evaluation results are combined and shown in the table [Example 5] The thickness is a single thickness of 1 〇 7 g / m 2 (corresponding to the nominal thickness of the core, and the untreated electrolytic copper pig with fine crystal grains on the liquid side, the surface is thick In the following basic conditions, the above-described basic bath was added with the respective concentrations to form a carbon steel electroplating bath. • Basic bath: dissolved in a copper concentration of 23.5 g-cu/1 from carbonate steel, adjusted to 1 by industrial concentrated sulfuric acid; 2 • Molybdenum concentration derived from molybdenum compound: 25 〇 mg-Mo/l • Iron concentration from iron compound: 2 〇〇 mg Fe/i • Trivalent chromium concentration derived from chromium compound: 2 〇〇 mg - to eight 201037104 • Tungsten concentration from crane compound: 8.5 mg-W/l • Vanadium concentration derived from cerium compound: 150 mg-F/i • Chlorine concentration derived from chlorine compound ··································· Coke plating).
•浴溫：28. 5°C •電流密度：直流整流、32A/dm2 Ο• Bath temperature: 28. 5 ° C • Current density: DC rectification, 32 A / dm2 Ο
焦電鍍以後的膠囊電鍍條件、防銹處理條件，完全如 同實施例1般的施行各處理，評估測定結果合併記於表1。 [實施例6] ' _取代未處理金屬箱’改為使用工業用通用軋延鋁落， 且單重量：68g/m2(相當於公稱厚度25/zm)。又，在焦電鑛 前’對其表面利用25g/1氫氧化納液（浴溫度·阶）施行 表面脫脂洗淨。_，如同施行健全焦電鍍，利用在醋酸 酸性浴中溶解50g/1氧化鋅的溶液’ S已施行過焦電鍍處 理之-面施行0.35mHn/dm2辞電鑛前處理。除該等事項 之外，就焦電鍍處理條件、膠囊電鍍條件 件均完全如同實施例1般的施行各處理， 併記於表1。 、及防銹處理條 評估測定結果合 [比較例1 ] 當施行實施例1形成粗化瘤的焦電錢處理時，在該浴 中並未使用添加金屬、*添加物的銦、鐵、絡'鶴、飢、 氣。除該等事項之外，垃 '、餘均如同實施例1的膠囊電鍍與 防銹處理，並施行同樣的評估、、丨— 幻十估/則疋，結果合併記於表1。 201037104 [比較例2 ] 取代實施例1所使用具有細微結晶粒的未處理銅箱， 改為使用公稱12厚度，且具有一般柱狀結晶的市售單 面粗化處理電解銅箱（古河電氣工業股份有限公司製 GTS-MP-12” II)。除該等事項之外，就焦電鍍處理條件、 膠囊電鍍條件、及防銹處理條件均如同實施例j般的施行 各處理，評估測定結果合併記於表i。 [比較例3] 對高周波對應核心基板的單面，依照通用濺鍍工法形 ΓΙ 成大約0.5/ΖΙΠ厚度的超薄厚銅膜之材料，對超薄銅臈表面 使用公知硫酸-硫酸銅浴，依電解鍍厚出總計5· 〇 #⑺與 35 m厚度的膜。然後，施行如同實施例相同的評估與測 ' 定，結果合併記於表1。 - [表1] 單重量 (g/m2) 35//m鍍厚後 的密接強度 (kN/m) 蝕刻後的電路直線性 (參照第1(A)圖） (光學顯微鏡觀察） 利用ΕΡΜΑ施行 的殘渣銅粗糙 (參照第1(B) 圖） (目視觀察） 粗化瘤間隙、有無 (參照第1(C)圖） (0.卜1· 0卵） 貝％例1 107 1.15 ◎ ◎ 有 貫施例2 63 1.12 ◎ @~〇 有 貝％例3 153 1.21 ◎ ◎ 有 貫知例4 ΓΪ07 1.13 ◎ ◎ 有 κ苑例5 107 1.14 ◎ @ 有 貝死例6 68 1.18 ◎ ◎~〇 有 t匕較例1 107 0. 95 ◎ Δ-Ο 無 比牧例2 比較0 107 —--- 1.45 Δ~χ Δ 無 一 0.15 ◎ 〇 — 從民好（最佳） -----—-——— 〇：良好 △•實用 1- US· rfei X :有障礙 22 201037104 由上述表1所示結果得知，根據本發明 v々/5* ，相齡 '比較例之下，可形成電路蝕刻直線性優昱 、$必& 6上 文，、亦無電路 κ的顧慮，密接強度亦具備有所使用構件的必要充分 強度，較習知工法所獲得極薄銅膜更加提升品 刀 線膜。 、』|屬配 再者’利用無電解鍍銅可形成銅結晶呈緻密且厚产均 勻性優異的良好銅薄膜。因而，可提升積體電路等的製造 〇 製程良率，俾可提升品質，不論濺鍍法或半蝕刻法均可廉 價地製造提供能消除細微配線因遷移所造成不良情況的極 薄銅箔。 【圖式簡單說明】 第1圖：（Α)係表示判斷蝕刻後電路直線性基準（水準） 的照片； (Β)係利用EPMAU射線電子微探分析儀；Electron O PFQbe Micro-Analysis)施行殘渣銅粗糙判斷基準（水準） 的照片； (C)係粗化瘤間隙的說明照片。 【主要元件符號說明】 ◎:極良好（最佳）； 〇··良好； △:實用上無障礙； x :有障礙。 23The capsule plating conditions and the rust-preventing treatment conditions after the coke plating were completely carried out as in the same manner as in Example 1, and the evaluation results were collectively shown in Table 1. [Example 6] The '_substituted untreated metal box' was changed to use a general-purpose rolled aluminum alloy for industrial use, and the single weight was 68 g/m2 (corresponding to a nominal thickness of 25/zm). Further, in the front of the pyroelectric ore, the surface was degreased and washed with 25 g/1 sodium hydroxide solution (bath temperature step). _, as in the case of a perfect coke electroplating, a solution of 50 g/1 zinc oxide dissolved in an acid bath of acetic acid has been subjected to a coke electroplating treatment to perform a pretreatment of 0.35 mHn/dm2. Except for these matters, the conditions for the electroplating treatment and the conditions for the capsule plating were completely the same as those of the first embodiment, and are shown in Table 1. And the rust-proof treatment strip evaluation measurement result [Comparative Example 1] When the coke money treatment of the formation of the roughening tumor of Example 1 was carried out, indium, iron, and the addition of metal, *additives were not used in the bath. 'He, hungry, angry. Except for these matters, the same as in the capsule plating and rust-preventing treatment of Example 1, and the same evaluation, 丨-幻十估//, and the results are summarized in Table 1. 201037104 [Comparative Example 2] Instead of the untreated copper tank with fine crystal grains used in Example 1, a commercially available single-sided roughening electrolytic copper box with a nominal columnar crystal size and a general columnar crystal was used (Furukawa Electric Industry Co., Ltd.) GTS-MP-12, manufactured by the company, II). In addition to these matters, the conditions of coke plating treatment, capsule plating conditions, and rust-preventing treatment conditions are the same as in the case of Example j, and the evaluation results are combined. [Table 3] [Comparative Example 3] For a single surface of a high-frequency-corresponding core substrate, a material of an ultra-thin thick copper film having a thickness of about 0.5 / ΖΙΠ was formed in accordance with a general sputtering method, and a known sulfuric acid was used for the surface of the ultra-thin copper ruthenium. - Copper sulphate bath, a total of 5 · 〇 # (7) and 35 m thick film were thickened by electrolytic plating. Then, the same evaluation and measurement as in the examples were carried out, and the results were combined and summarized in Table 1. - [Table 1] Weight (g/m2) 35//m adhesion strength after plating (kN/m) Straightness of the circuit after etching (see Fig. 1(A)) (observation by optical microscope) Residual copper roughness by ΕΡΜΑ (Refer to 1(B) Fig.) (visual observation) Gap, presence or absence (refer to Figure 1 (C)) (0. Bu 1 · 0 eggs) Shell % Example 1 107 1.15 ◎ ◎ There are examples 2 63 1.12 ◎ @~〇有贝% Example 3 153 1.21 ◎ ◎ Yes知知例4 ΓΪ07 1.13 ◎ ◎ 有κ苑例5 107 1.14 ◎ @有贝死例6 68 1.18 ◎ ◎~〇有匕1 Example 1 107 0. 95 ◎ Δ-Ο Incomparable case 2 Comparison 0 107 — --- 1.45 Δ~χ Δ None 0.15 ◎ 〇 —— From Minhao (Best) --------—— 〇: Good △• Practical 1- US· rfei X : Obstacle 22 201037104 From the above The results shown in Table 1 show that, according to the present invention v々/5*, the age of the 'comparative example, the circuit can be etched linearly superior, $ must & 6 above, and there is no circuit κ concern, The adhesion strength also has the necessary sufficient strength to use the components, and the ultra-thin copper film obtained by the conventional method is used to enhance the product of the stencil film. 』||Assembled by the use of electroless copper plating, the copper crystal is dense and A good copper film with excellent uniformity in thickness, thus improving the manufacturing process yield of integrated circuits and the like, and improving the quality regardless of sputtering or half. The engraving method can be inexpensively manufactured to provide an ultra-thin copper foil capable of eliminating the trouble caused by migration of the fine wiring. [Simplified Schematic] Fig. 1: (Α) indicates the determination of the linearity standard (level) of the circuit after etching. Photograph; (Β) is a photograph of the residue copper roughness judgment standard (level) using EPMAU ray electronic micro-analyzer; Electron O PFQbe Micro-Analysis; (C) Photograph of the roughening tumor gap. [Description of main component symbols] ◎: Very good (best); 〇··Good; △: Practically barrier-free; x: Obstacle. twenty three