TW593756B - Method of forming chromium coated copper for printed circuit boards - Google Patents

Method of forming chromium coated copper for printed circuit boards Download PDF

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Publication number
TW593756B
TW593756B TW089120719A TW89120719A TW593756B TW 593756 B TW593756 B TW 593756B TW 089120719 A TW089120719 A TW 089120719A TW 89120719 A TW89120719 A TW 89120719A TW 593756 B TW593756 B TW 593756B
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TW
Taiwan
Prior art keywords
copper
layer
item
chromium
patent application
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TW089120719A
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English (en)
Inventor
Jiang-Tao Wang
John Callahan
Dan Lillie
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Gould Electronics Inc
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Publication of TW593756B publication Critical patent/TW593756B/zh

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    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/06—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of metallic material
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K1/00—Printed circuits
    • H05K1/16—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor
    • H05K1/167—Printed circuits incorporating printed electric components, e.g. printed resistor, capacitor, inductor incorporating printed resistors
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
    • C23C14/025—Metallic sublayers
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/321—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer with at least one metal alloy layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
    • C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
    • C23C28/3225—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only with at least one zinc-based layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
    • C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
    • C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
    • C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
    • C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/388—Improvement of the adhesion between the insulating substrate and the metal by the use of a metallic or inorganic thin film adhesion layer
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/01—Dielectrics
    • H05K2201/0137—Materials
    • H05K2201/0179—Thin film deposited insulating layer, e.g. inorganic layer for printed capacitor
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0302—Properties and characteristics in general
    • H05K2201/0317—Thin film conductor layer; Thin film passive component
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
    • H05K2201/03—Conductive materials
    • H05K2201/0332—Structure of the conductor
    • H05K2201/0335—Layered conductors or foils
    • H05K2201/0355—Metal foils
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K2203/00—Indexing scheme relating to apparatus or processes for manufacturing printed circuits covered by H05K3/00
    • H05K2203/03—Metal processing
    • H05K2203/0361—Stripping a part of an upper metal layer to expose a lower metal layer, e.g. by etching or using a laser
    • H—ELECTRICITY
    • H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
    • H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
    • H05K3/00—Apparatus or processes for manufacturing printed circuits
    • H05K3/38—Improvement of the adhesion between the insulating substrate and the metal
    • H05K3/382—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal
    • H05K3/384—Improvement of the adhesion between the insulating substrate and the metal by special treatment of the metal by plating
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/12—All metal or with adjacent metals
    • Y10T428/12431—Foil or filament smaller than 6 mils
    • Y10T428/12438—Composite

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Manufacturing & Machinery (AREA)
  • Ceramic Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Laminated Bodies (AREA)
  • Manufacturing Of Printed Wiring (AREA)
  • Other Surface Treatments For Metallic Materials (AREA)
  • Electroplating Methods And Accessories (AREA)
  • Chemical Treatment Of Metals (AREA)
  • Physical Vapour Deposition (AREA)

Description

五 、發明說明（】） 本發明係闕於一種處理 至銅箔之至少一側之方法。 法，更特別關於塗佈金屬 銅箱用於製造印刷電路^^ 需々要將銅箱附著至介電基材、，=印刷電路板時，一般 之洛片。雖然銅箔為極佳電j提供具尺寸和結構穩定性 題。例如，豸易被氧化和腐餘，體，但其使用存在固有問 軋，均對此類基材附著不良。，且銅自身無論製板或滾 或催化；|電基材分解。因此，且我們已知銅能狗加速 夕個保護層。 叙對銅箔表面施加一個或 我們知道，使鉻層沈積至銅 用。將薄鉻層沈積到銅表面冷對印刷電路板有多種應 法，另一種為真空沈積法。兩種方法，一種為電沈積 電沈積法有多種缺點。首，上 昂處理及廢除之環境有宝材’該方法使用難以及代價高 且低效。 ° ;斗。其次，該方法不精確，而 對於真空沈積法，為保證 之附著性。需要在直空沈：加鉻和銅之間有令人滿意 為克服此等以：，去氧化鋼。 ' 形成經金屬塗佈銅：：：，本發明藉由真空沈積提供-種 程。 万法’而無需徹底嚴格之預處理製
第5頁 593/30 五、發明說明（2) 本發明之較佳且 法，其包括以 /、體貝施例提供一種塗佈金屬至銅層之方 表面穩定I f驟··對銅層表面塗佈穩定層，以使銅層 合物，且具^ ^疋層包括氧化鋅、氧化鉻、氧化鎳或其混 銅層之穩埃和約7〇埃間之厚度；然使金屬沈積至 鐵、銦、鋅、上，該沈積金屬選自由鋁、鎳、鉻、銅、 群。-種本文二^、銳、鵪、鍅、铜及其合金組成之 本發明另3 =明讀合金為鎳—鉻合金。 定層組成之片材 七:種由銅層和位於該銅表面上之穩 穩定層^提供氣相沈積金屬 埃間之厚度。然後在該 之ΪΪ明—個目的為提供用於製造印刷電路板之經鉻塗佈 本电明另—個目的兔担μ 鉻塗佈之銅層之方法為^ 一種由真空沈積法形成上述短 行徹底、嚴格洗该方法在沈積鉻前無需對銅表面； 本發明又一個目的為提供一 之方法。 、種使金屬真空沈積至鋼表面 本發明進—舟&说 _ ，自以下較佳具體實施例二：圖=續方：。 等及其它目的將更加明顯。 、加申請專利範圍，此 本發明對某些部分和各=置 布置以及較佳具體實施例 593756 五、發明說明（3) 採取實際形式，並由專利說明書詳述及形成部分之 明，其中·· 寸圖說 圖1為根據本發明將金屬塗佈至銅箔表面一 圖； 乃凌之示意 圖2為圖1流線2 - 2之擴展截面圖，以顯示銅箔 圖3為圖1流線3-3之擴展截面圖，以顯示圖2 ’ 定層之銅箔片；及 〃上具穩 圖4為圖1流線4-4之擴展截面圖，以顯示其 相沈積金屬之銅片。 /、“、、’侧具氣 圭具體實施例 本發明係關於將金屬塗佈至銅表面之方法。 ’’金屬’’指能夠由本文揭示方法真空沈積之金在本文中， 發明特別用於將鉻塗至銅箔上，並著重對其#及合金。本 但 應瞭解，所揭示方法亦可將其它金屬塗至^ ^出描述， 金 鎳、銅、鐵、銦、鋅、鈕、錫、飢、 Γ名上，如銘 螞、锆、鈕 可用兩種技術之一製造本發明使用之 製方法機械減小銅或鋼合金條或錠掣，。可用（ 而製造電沈積箱片係首先將銅離子；；：製或 h f “、…· ..... ，尤積到旋轉陴0 積鋼_ t A極鼓 ^ ^ 有利用 該銅箔一般具有自約0 · 0 0 0 2英寸至约 。銅箔厚度有時用重量表示，本私明> 02英寸之幹 0 21 ΛΑ 1 , ^ ^ h 明之绽 P ^ % 厚 銦及其合 上，然後將經沈積猪自陰極剝離。^ ^ =到旋轉陰 發明。 沈積鋼箔右^ 用於本 度 1/8至、力14盎司/平方英尺（〇z/ft2) 片〜報
〜蕙夏或厚泠 "有約 逻。椏士 位有用 W756
之鋼落具有1/3、1/2或2盎司/平方英尺之重量。 電沈積銅箔具有光滑或光亮侧（鼓）和粗糙或 積生長前）侧。由本發明塗佈之稃定M / “、、/ (銅沈 =但有時用於雙側。#一個具體實施例中之 去塗佈之層係塗至該箔片之光亮侧。 ^月方 由本發明方法塗佈層覆蓋箱片之單側或 剖面分布表面"、"低剖面分布表面"或"才虽低剖面^表丰 面所用具體實施例包括使用具低剖面分布表面和極面 表面之猪片。在本文中’"標準剖面分布表面"指猪 H具大於10.2微米之Rtm(IPC_MF_i5〇F)。"低剖面分布表 =扎箱表面具小於10. 2微米之K ipc_mf_15〇f)。"極低 纠面分布表面”指剖面具有小於5· }微米之R^(Ipc—mf — = 0F)。Rtm(I PC-MF-15OF)之含義為自5個連續樣品測量之 =大峰-谷垂直尺寸，可用英格蘭、列斯特、朗克—泰勒— 赫森公司（Rank Tayl〇r H〇bs〇n，Ltd·，Leicester，
EngUnd)銷售之SURTR〇NIC(商標）3型剖面分布儀測量。 热於此藝者應瞭解，本發明不僅用於其表面上具穩定層 之銅猪，而且用於經沈積或附著其它基材之銅層，以及沈 積後或經附著至另一種基材之前或之後其表面塗佈穩定層 之銅層。此類基材包括但不限於聚醯亞胺（見美國專利第 5，685，970號及第5，681，443號，二者明確以參考之方式併 於本文）’其它聚合性基材、有機基材、鋁（參閱以參考方 式併於本文之美國專利第5,丨53, 〇5〇號），金屬基材（參閱 以參考方式併於本文之美國專利第5, 674, 596號）或銅和
第8頁 593756 五、發明說明（5) UVAR之層合物。 具$ ^ ^考附圖’其中顯示内容僅用於說明本發明之較佳 ^ -實施例’而未用以限制其範圍。圖1為用於將金屬塗 之=表面之一般連續製造方法丨〇示意圖，其顯示本發明 供二^具肢實施例。在所示之較佳具體實施例中，輥11提 圖、。5箱1 2 ^ 一般連續條帶。圖2為銅箔1 2之放大截面視 二5亥銅箔1 2具有光亮側1 4和烏澤側1 6。（為便於在圖中 σ兄明’銅箔1 2之烏澤側1 6顯得誇張。） 銅治、1 2較佳能夠經受第一清潔製程（在繪圖中指定為 &，以+自其表面除去氧化物。在所示之具體實施例中， 二=—2藉助導輥26輸入槽22，且繞於導輕24上。槽22内包 ‘=匕膜自銅，表面上移除之清潔溶液。較佳是用酸 ^ 2將氧化膜自銅㈣表面上移除。冑潔銅箔12之典型 中“ 包括10—80克/升之H2S04。在一個具體實施例 中，用50克/升ISCM將氧化銅自銅箔12除去。 f :潔製程20後，鉑猪經歷清清洗製程3 12上：：下方布置噴洗元件32,並用水喷洗銅羯 面；Ϊ洗元件32下方布置之槽3“其收集喷洗水。 在>月潔製謂和清洗製程3〇後 40。鉑箔12導入槽42，且園婊^道, 、工疋衣私 導輕46與導親44定位。該槽42含有1周圍°銅兔12經由 個較佳具體實施例i該ί =溶液。在本發明一 用於電解溶液之鋅離子原；含辞離子和鉻離子。
ZnS〇4、ZnC〇3、ZnCr〇4等、。用於带解'?，其實例包括 ^^解溶液之鉻離子源可為 五、發明說明（6) 任:六，絡鹽或化合物，其實例包括Μ，、Cr〇3等。 佳：η解:谷液中鋅離子之濃度-般為約〇· 1至約2克/升，較 , 至約0 · 6克/升，更佳約0 · 4至約〇 · 5克/升。電解溶 L 子之濃度一般為約〇.3至約5克/升，較佳約0 5至 、，、勺3克/升’更佳約0.5至约1〇克/升。 · 積在2 :個具體實施例中，亦可使氧化鎳或鎳金屬自身沈 編鋅或氧化鉻或二者-起沈積形成穩定：。 用於电解洛液之鎳離子源可為任何一種以下物暂★甘 人 物：Ni2S04、NiC〇3等 為7種以下物1或其混合 升电解/谷液中錄離子之濃度一般為約〇· 2克/升至约U克/ 專一二具實：例中’可使用其它穩定劑層，如美國 考之f式二本 如約1至約50克/升 更佳約1 2至約1 8克 1較佳約4至約5， 、、曲：電解溶液可包含其它習知添加劑 /辰又之Na2S〇4，較佳約10至約20克/升 /升。該電解溶液之？11 一般為約3至約6 更佳約4 · 8至5 . 〇。 該電解溶液之溫度一般為 。。至爾，更佳約心=。:至約10°c，較佳約25 1二乂所示’陽極48與鋼落1 2各側相鄰布置，以认+扪 >白12電流密度。導輕46為陰極親，^布置—以給予銅 對陽極48施加能量時，由氧化 1、 由电源（未顯示） 沈積於銅箔12之铖A f/ u和乳化鉻組成之穩定層49 白12之經暴路先党側14和烏澤側16。圖3為光亮 593756 發明說明（7) 側1 4和烏澤側1 6具穩定層4 9之銅箔1 2截面圖。 該電流密度一般為約！至約丨〇〇安培/英尺;^ " 較佳約25至約50安培/英尺2，更佳約3〇安培 用多個陽極時，電流密度可在各陽極間變化。、 ‘心 更：=時ΓΓ為約1至約30秒，較佳約5至約2。秒， 處理時間‘ "3至固二體實施例t，於光亮或光滑側之總 1約5；^。自約3至約1〇秒，於烏澤側之總處理時間為約！ 在一個具體實施例中，電解溶中 耳比為約0.2至約1〇…μ $于對鋅離子之莫 車乂佺約1至約5，更佳約1. 4。 χ明中，塗佈鋼箔1 2之穩定層4 9厚度俜介於 至約70埃之間，軔4认〇λ 予沒你"於約5埃 二/ 间 1乂佳約20埃至50埃之間。 天 f =述較佳具體實施例中，該 鋅組成。在本發明另_ 和氧化 士、、么从产 方面中，该穩疋層4 9只由惫儿 '。二：氧化鉻穩定層之浴化學和方法條件如下組 Η0克/升以〇3溶液， · 較佳5克/升CrOq pH-2 >谷液溫度：2 5 ίο-:。安培/英尺2進行5]。秒鐘 或次〉貝處理·· 1 0秒鐘 穩定製程40後，μ …Λ Λ 程，在圖中指定為50 ;穩定銅羯12經過清洗製 側，並將水噴至鋼;。噴洗元件52布置於㈣12之上下 ' >自12(具穩定層49)清洗’以自其去除任
第11頁 593756 五、發明說明（9) 及利範圍中，除非另外指明，所有份數和百分數均 以重1計，所有溫度均為攝氏度，所有壓力均為大氣壓。 將未電沈積處理之1/3去gi/# 益司/夬尺2銅箔雙側用穩定層如 下預處理。 穩定處理： 0.53 克 / 升鋅（如2ns〇) , 〇 R + 7 … 、謂4; ϋ· 6克/升鉻（如Cr03)，1 1克/升 硫酸鈉 3 浴液p Η : 5. 〇
浴液溫度：42 °C 電流密度 電鍍時間 烏澤側8 - 1 5安培/英尺2 光亮側2 - 2 · 5安培/英尺2 光亮側：6 - 8秒 烏澤侧：3 - 4秒 然後如下將鉻塗佈至穩定層·· 鉻濺射： 測射機 功率：5-8千瓦 馨 線性速度Μ.4至2.2英尺/分鐘 鉻層厚度：烏澤側，1, 2 0 0埃 光澤側，1，3 0 0埃 一 實例2 »用銅鑛覆聚酿亞胺之雙側[丨8微米銅/ 5 〇微米聚醯亞胺薄 膜/5微米銅；該產品為一種由古德電子公司（G〇uld
第13頁 593756 五、發明說明（ίο)
Electronics Inc.)製造之Gould(商標）撓曲產物]’如下 進行處理： 穩定處理： 0.53克/升鋅（如ZnS04)，〇·6克/升鉻（如Cr03，11克/升 硫酸鋅
浴液p Η : 5. 0 浴液溫度：4 2 °C 電流密度：2 5安培/英尺2，雙側 電鍍時間：單側或雙側：3-8秒 然後如下將鉻塗佈至穩定層： 鉻濺射： 1 4"測射機 功率：5-8千瓦 線性速度：1 · 8至2 · 8英尺/分鐘 鉻層厚度：1 8微米銅側’ 1，0 0 0埃 5微米銅侧’未塗佈鉻層 實例3 用銅鍍覆聚醯亞胺薄膜之雙側（1 8微米銅/5〇微米聚驢亞 胺薄膜/ 5微米銅··該產物為古德電子公司製造之Gou 1 d (商 標）撓曲產物），如下進行處理： 穩定處理： 5克/升鉻（如Cr03)
浴液pH : 2· 0 浴液溫度：25 °C
第14頁 593756 五、發明說明（11) 浸漬處理 然後如下將鉻塗佈至穩定層·· 鉻濺射： 14’’測射機 功率·· 5-8千瓦 線性速度：1 · 8至2. 8英尺/分鐘 鉻層厚度·· 1 8微米銅侧，1，〇 〇 〇埃 實例4
如下用穩定層預處理經電鍍於丨N VAr上之雙側8微米銅層 穩定處理： 〇·53克/升鋅（如ZnS04)，0.6克/升絡（如Cr03)，11克/升 硫酸鋼 浴液pH : 5. 〇 浴液溫度：4 2 °C 電流密度：2 5安培/英尺2 電錢時間· 3 - 4秒 然後如下將鉻塗佈至穩定層： 鉻濺射：
14π測射機 功率：5-8千瓦 線性速度· 1 · 8至2 · 8英尺/分鐘 鉻層厚度：8微米鋼側，丨，〇 〇 〇埃 以前所述為本發明之具體實施例。應瞭解，該具體實施 例僅作為說明描述，熟諳此藝者可在不離開本發明之主旨
第15頁 593756 五、發明說明（12) 和範圍内實施多種變動和修改。例如，如果製程1 0為電成 形製程之擴展，使其中生成純銅並引入製程流線1 0，那麼 可不需要清潔製程2 0。另外，雖然前述方法與銅有關進行 描述，但本發明亦可將金屬（如鉻）塗佈至經塗於聚合物之 銅上。所有此類修改和變動均應處於本發明申請專利範圍 及其等價範圍内。
第16頁

Claims (1)

  1. 593756 • ， .· '、： ·, ..::厂 ΐ.Γ'·, -μ--'· , ，. 卜.‘ r i ' 93. 5. -7 /?.; Γ〆 Β案號 89120719 年 5> 月 曰__ 丨、.…'...-.....-.. 六、申請專利範® 1 . 一種塗佈金屬至銅層之方法，其包括以下步驟： 由塗佈穩定層使銅層表面穩定，該穩定層包括氧化鋅、 氧化鉻、鎳、氧化錄或其混合物，且具有約5埃和約7 0埃 間之厚度；及 將一金屬沈積至該銅層之穩定化表面上，該金屬選自由 ‘ 鋁、鎳、鉻、銅、銦、鋅、鈕、錫、釩、鎢、锆、鉬及其 合金組成之群。 2 · 根據申請專利範圍第1項之方法，其中該銅層係選自 ’ 由銅箔，位於聚醯亞胺上之銅層及位於INVAR上之銅層組 -成之群。 3. 根據申請專利範圍第2項之方法，其中該金屬為鉻。讀. 4. 根據申請專利範圍第3項之方法，其中該穩定層係由 氧化鋅和氧化鉻之混合物組成。 5 . 根據申請專利範圍第4項之方法，其中該銅箔具有閃 光側和烏澤側，且該鉻係塗佈至該烏澤側或該閃光側。 6 . 根據申請專利範圍第3項之方法，其中該穩定層係由~ 氧化鉻組成。 . 7. 根據申請專利範圍第6項之方法，其中該銅箔具有閃 光側和烏澤側，且該鉻係塗佈至該烏澤側或該閃光侧。 8. 根據申請專利範圍第1項之方法，其中該銅層為一般 連續條帶，且該穩定層和氣相沈積金屬係以一般連續方法¢1 塗佈。 9. 一種片材，該片材包括： 一銅層；
    O:\66\66668-930507.ptc 第19頁 593756 _案號 89120719 年芗月 日_魅_ 六、申請專利範圍 一位於該銅表面之穩定層，該穩定層包括氧化鋅、氧化 鉻或其混合物，且具有5埃和7 0埃間之厚度；及 一位於該穩定層上之氣相沈積金屬。 10. 根據申請專利範圍第9項之片材，其中該金屬係選 自由鋁、鎳、鉻、銅、鐵、銦、鋅、钽、錫、釩、鎢、 锆、鉬及其合金組成之群。 11. 根據申請專利範圍第1 0項之片材，其中該金屬為 鉻。 12. 根據申請專利範圍第1 1項之片材，其中該穩定層係 由氧化鋅和氧化鉻組成。 13. 根據申請專利範圍第1 1項之片材，其中該穩定層係❻ 由氧化鉻組成。 14. 根據申請專利範圍第1 0項之片材，其中該鉻具有5 0 埃至5，0 0 0埃間之厚度。 15. 根據申請專利範圍第1 0項之片材，其中該氣相沈積 金屬係濺射於該穩定層上。 — 16. 根據申請專利範圍第1 5項之片材，其中該穩定層係 以電沈積法塗佈。 17. 根據申請專利範圍第1 5項之片材，其中該穩定層係 以機械浸潰方法塗佈。 18. 根據申請專利範圍第1 0項之片材，其中該銅箔係經 電沈積。
    O:\66\66668-930507.ptc 第20頁
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KR100352280B1 (ko) 2002-09-12
CN1315591A (zh) 2001-10-03
EP1123988B1 (en) 2008-07-09
EP1123988A1 (en) 2001-08-16
JP3311338B2 (ja) 2002-08-05
DE60039407D1 (de) 2008-08-21
US6489034B1 (en) 2002-12-03
CA2322363C (en) 2004-09-14
JP2001220689A (ja) 2001-08-14
CN1280448C (zh) 2006-10-18
KR20010077901A (ko) 2001-08-20

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