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TWI668330B - Electroless plating process - Google Patents

Electroless plating process Download PDF

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Publication number
TWI668330B
TWI668330B TW107122017A TW107122017A TWI668330B TW I668330 B TWI668330 B TW I668330B TW 107122017 A TW107122017 A TW 107122017A TW 107122017 A TW107122017 A TW 107122017A TW I668330 B TWI668330 B TW I668330B
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TW
Taiwan
Prior art keywords
nickel
electroless
film
plated film
plating
Prior art date
Application number
TW107122017A
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English (en)
Other versions
TW201905239A (zh
Inventor
加藤友人
渡邊秀人
Original Assignee
日商小島化學藥品股份有限公司
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Publication of TW201905239A publication Critical patent/TW201905239A/zh
Application granted granted Critical
Publication of TWI668330B publication Critical patent/TWI668330B/zh

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    • 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
    • H01L24/47—Structure, shape, material or disposition of the wire connectors after the connecting process
    • H01L24/48—Structure, shape, material or disposition of the wire connectors after the connecting process of an individual wire connector
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1635—Composition of the substrate
    • C23C18/1637—Composition of the substrate metallic substrate
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1689—After-treatment
    • C23C18/1692—Heat-treatment
    • C23C18/1694—Sequential heat treatment
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    • 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
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    • C23C18/18—Pretreatment of the material to be coated
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    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
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    • 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
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    • C23C18/31—Coating with metals
    • C23C18/32—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron
    • C23C18/34—Coating with nickel, cobalt or mixtures thereof with phosphorus or boron using reducing agents
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    • 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
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    • C23C18/42—Coating with noble metals
    • C23C18/44—Coating with noble metals using reducing agents
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/52—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating using reducing agents for coating with metallic material not provided for in a single one of groups C23C18/32 - C23C18/50
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    • H01L21/76841—Barrier, adhesion or liner layers
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    • 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
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Abstract

本發明之目的，係提供一種依照順序成膜形成鍍鎳皮膜及鍍金皮膜在銅材表面時，能夠將鍍鎳皮膜的膜厚薄化且能夠得到包括優異的封裝特性的皮膜之無電解電鍍製程。為了解決上述課題，係提供一種使用無電解電鍍法而將依照順序成膜形成鍍鎳皮膜及鍍金皮膜在銅材表面之無電解電鍍製程，其特徵在於包括：使用無電解觸擊電鍍法而成膜形成鍍鎳皮膜在銅材表面之步驟；及使用還原型無電解電鍍法而成膜形成鍍金皮膜之步驟。

Description

無電解電鍍製程
本發明係有關於一種使用無電解電鍍法而成膜形成鍍金皮膜在銅材表面之無電解電鍍製程。
近年來，要求電子機器的高功能化和多功能化，另一方面被使用在該等電子機器之樹脂基板、陶瓷基板、晶圓基板等的電子電路基板，係被要求進一步輕薄短小化。因為必須高密度封裝用以因應該輕薄短小化，所以被要求能夠實現高密度封裝之表面處理技術。而且，在電子電路基板的技術領域，係確立使用焊料和引線接合作為將封裝零件接合的技術之封裝技術。
為了確保封裝時的連接可靠性之目的，係在電子電路基板上的電路圖案之封裝部分亦即配線墊片，施行電鍍處理作為表面處理。例如在使用低電阻的銅等金屬所形成的電路圖案上，藉由電鍍處理而依照順序成膜形成鍍鎳皮膜及鍍金皮膜。以下，將依照順序成膜形成鍍鎳皮膜及鍍金皮膜而成之皮膜記載為「Ni/Au皮膜」。為了防止銅往鍍金皮膜擴散而成膜形成鍍鎳皮膜，而為了得到良好的封裝特性而成膜形成鍍金皮膜。
而且，亦已知在鍍鎳皮膜與鍍金皮膜之間成膜形成鈀皮膜之技術。以下，將依照順序成膜形成鍍鎳皮膜、鍍鈀皮膜及鍍金皮膜而成的皮膜記載為「Ni/Pd/Au皮膜」。為了在電鍍基板的熱處理時防止鎳往鍍金皮膜擴散而成膜形成鈀皮膜。在鍍鎳皮膜上成膜形成鈀皮膜時，鍍鎳皮膜能夠薄膜化。
作為上述電鍍處理，係電解電鍍製程為主流，針對無法採用電解電鍍製程因應之物係能夠應用無電解電鍍製程。
先前，作為在銅表面成膜形成Ni/Pd/Au皮膜之無電解電鍍製程，例如專利文獻1，係如第10圖所顯示，揭示對銅材進行脫脂步驟(步驟(以下記載為「S」)11)及蝕刻(S12)而對銅材表面賦予鈀觸媒(S14)後，進行無電解鍍鎳(Ni)(S15)、無電解鍍鈀(Pd)(S16)及無電解鍍金(Au)(S17)。專利文獻1雖未記載，通常係在蝕刻(S12)與鈀觸媒賦予處理(S14)之間進行去沾污(desmut)(S13)。為了在無電解鍍鎳(S15)時使鎳析出，鈀觸媒賦予處理(S14)通常被視為必要。
在專利文獻1所揭示的無電解鍍鎳(S15)，係使用含有硫酸鎳‧六水合物22.5g/L(鎳換算為5g/L)，作為還原劑的次磷酸鈉、作為錯合劑的蘋果酸及琥珀酸，同時含有作為安定劑之錯鹽、鉍鹽、硫化合物等且調整成為pH為4.6、浴溫為60~90℃之無電解鎳電鍍液。亦能夠使用二甲胺硼烷代替次磷酸鈉作為還原劑。然後，藉由無電解鍍鎳(S15)而成膜形成膜厚0.1~15μm的鍍鎳皮膜，藉由無電解鍍鈀(S16)而成膜形成膜厚0.001~2μm的鍍鈀皮膜，藉由無電解鍍金(S17)而成膜形成膜厚0.001~1μm的鍍金皮膜。
在Ni/Au皮膜或Ni/Pd/Au皮膜，為了實現進一步高密度封裝，被期望鍍鎳皮膜的進一步薄膜化。 先前技術文獻 專利文獻
[專利文獻1] 日本特開2008-174774號公報
發明欲解決之課題
但是，藉由上述無電解鍍鎳(S15)，成膜形成膜厚為例如0.01μm以下之非常薄的鍍鎳皮膜時，有被覆變為不充分而在鍍鎳皮膜表面形成微小的凹部(孔穴)之情形。而且，在進行後續的無電解鍍金(S17)時，係有該凹部腐蝕而產生貫穿鍍鎳皮膜的貫穿孔之情形。將該現象稱為「鎳局部腐蝕現象」。此時，在Ni/Au皮膜或Ni/Pd/Au皮膜有無法得到優異的封裝特性之不良。
本發明的課題，係提供一種無電解電鍍製程，其在銅材表面依照順序成膜形成鍍鎳皮膜及鍍金皮膜時，能夠將鍍鎳皮膜的膜厚薄化且能夠得到包括優異的封裝特性之皮膜。 用以解決課題之手段
本發明之無電解電鍍製程，係使用無電解電鍍法而將依照順序成膜形成鍍鎳皮膜及鍍金皮膜在銅材表面之無電解電鍍製程，其特徵在於包括：使用無電解觸擊電鍍法而成膜形成鍍鎳皮膜在銅材表面之步驟；及使用還原型無電解電鍍法而成膜形成鍍金皮膜之步驟。
在本發明之無電解電鍍製程，前述無電解觸擊電鍍法係使用含有鎳換算為0.002~1g/L的水溶性鎳鹽、羧酸或其鹽、及選自二甲胺硼烷、三甲胺硼烷、肼、肼衍生物的群組之1種以上的還原劑且調整成為pH為6~10、浴溫為20~55℃之無電解觸擊鍍鎳液，藉由將前述銅材浸漬在該無電解觸擊鍍鎳液而進行為佳。
而且，前述無電解觸擊鍍鎳液，藉由將前述水溶性鎳鹽、前述羧酸或其鹽及水混合且攪拌而調製含有鎳錯合物之水溶液之後，將前述還原劑混合在該水溶液且攪拌來調製為佳。
在本發明之無電解電鍍製程，成膜形成前述鍍鎳皮膜之步驟，成膜形成膜厚為0.005~0.3μm之鍍鎳皮膜為佳。
而且，本發明之無電解電鍍製程，係在銅材表面依照順序成膜形成鍍鎳皮膜、鍍鈀皮膜及鍍金皮膜，在成膜形成前述鍍鎳皮膜之步驟與成膜形成前述鍍金皮膜之步驟之間，包括使用還原型無電解電鍍法而成膜形成鍍鈀皮膜之步驟為佳。 發明效果
在本發明之無電解電鍍製程，藉由採用無電解觸擊電鍍法，即便不進行在先前的無電解電鍍製程所進行鈀觸媒賦予處理(S14)亦能夠在銅材表面直接成膜形成鍍鎳皮膜。又，即便膜厚較薄，亦能夠確實地將銅材表面被覆且能夠成膜形成對銅材具有優異的密著性之鍍鎳皮膜。因此，依照本發明之無電解電鍍製程，能夠實現鍍鎳皮膜的薄膜化。而且，在本發明之無電解電鍍製程，藉由採用還原型無電解電鍍法，不會使其之前成膜形成的皮膜之金屬溶出而能夠成膜形成鍍金皮膜或鍍鈀皮膜。而且，依照本發明之無電解電鍍製程，能夠得到具有優異的封裝特性之Ni/Au皮膜或Ni/Pd/Au皮膜。
其次，說明本發明的無電解電鍍製程的實施形態。本實施形態的無電解電鍍製程係例如在樹脂基板、陶瓷基板、晶圓基板等絕緣基材表面所設置的電極和配線等的銅材表面，使用無電解電鍍法依照順序成膜形成鍍鎳皮膜及鍍金皮膜之無電解電鍍製程。具體而言，係包括下列步驟之無電解電鍍製程：使用無電解觸擊電鍍法而成膜形成鍍鎳皮膜在銅材表面之步驟；及使用還原型無電解電鍍法而成膜形成鍍金皮膜之步驟。以下，藉由在銅材表面依照順序成膜形成鍍鎳皮膜、鍍鈀皮膜及鍍金皮膜，來說明在銅材表面，形成Ni/Pd/Au皮膜之無電解電鍍製程。
在本實施形態的無電解電鍍製程，係如第1圖顯示，首先，進行脫脂步驟(S1)、蝕刻步驟(S2)及去沾污步驟(S3)作為成膜形成鍍鎳皮膜之前的前處理。隨後，藉由無電解鎳(Ni觸擊電鍍步驟(S4)而在銅材表面成膜形成鍍鎳皮膜。接著，藉由無電解鍍鈀(Pd)步驟(S5)而成膜形成鍍鈀皮膜且藉由無電解鍍金(Au)步驟(S6)而成膜形成鍍金皮膜。在各步驟之後，係進行水洗處理。水洗處理係以進行3次為佳。
1.脫脂步驟(S1) 在脫脂步驟(S1)，係藉由將銅材浸漬在酸性溶液而將附著在銅材表面之油脂成分除去。
2.蝕刻步驟(S2) 在蝕刻步驟(S2)，係藉由將經施行脫脂步驟(S1)之銅材浸漬在過硫酸系、過氧化氫系、硫醇系等的蝕刻液而將形成在銅材表面之銅氧化膜除去。
3.去沾污步驟(S3) 在去沾污步驟(S3)，係藉由將經施行蝕刻步驟(S2)之銅材，例如浸漬在10%硫酸而將附著在銅材表面之沾污除去。
4.無電解觸擊鍍鎳步驟(S4) 在無電解觸擊鍍鎳步驟(S4)，係使用無電解觸擊電鍍法而在經前處理的銅材表面成膜形成鍍鎳皮膜。無電解觸擊電鍍法係將經施行去沾污步驟(S3)之銅材浸漬在無電解觸擊鍍鎳液來進行。
無電解觸擊鍍鎳液： 無電解觸擊鍍鎳液係含有水溶性鎳鹽、羧酸或其鹽、選自二甲胺硼烷、三甲胺硼烷、肼、肼衍生物的群組之1種以上的還原劑。在本說明書，所謂「1種以上」，係表示可只有1種亦可為2種以上的複數種。
作為水溶性鎳鹽： 在無電解觸擊鍍鎳液所使用的水溶性鎳鹽，例如能夠舉出硫酸鎳、氯化鎳、碳酸鎳、乙酸鎳、次磷酸鎳、胺基磺酸鎳、檸檬酸鎳等的有機酸鎳。該等可單獨使用，亦可組合2種以上而使用。在本發明，作為水溶性鎳鹽，係以使用硫酸鎳六水合物為最佳。
無電解觸擊鍍鎳液之水溶性鎳鹽的鎳換算含量，係以0.002~1g/L的範圍為佳。這是在先前技術的無電解電鍍製程的無電解鍍鎳(S15)所使用的無電解鎳電鍍液之鎳濃度5g/L的Ⅰ/5以下且為相當低的濃度。藉由無電解觸擊鍍鎳液之水溶性鎳鹽的鎳換算含量為上述範圍，能夠實現無電解觸擊電鍍法且在未被賦予鈀觸媒的銅材表面直接成膜形成鍍鎳皮膜。
水溶性鎳鹽的鎳換算含量小於0.002g/L時因為析出速度變為太慢，所以必須增長浸漬時間用以得到所需要的膜厚之鍍鎳皮膜且無法滿足工業生產性，乃是不佳。另一方面，水溶性鎳鹽的鎳換算含量大於1g/L時，析出速度變為太快且無法得到表面均勻的鍍鎳皮膜，乃是不佳。水溶性鎳鹽的鎳換算含量係以0.01~0.5g/L的範圍為較佳，以0.03~0.1g/L的範圍為最佳。
羧酸或其鹽： 無電解觸擊鍍鎳液係含有羧酸或其鹽。該等係作為錯合劑和pH調整劑的作用。作為羧酸，例如能夠使用選自單羧酸(甲酸、乙酸、丙酸、酪酸等)、二羧酸(草酸、丙二酸、琥珀酸、葡糖酸、己二酸、反丁烯二酸、順丁烯二酸、琥珀酸等)、三羧酸(烏頭酸等)、羥基羧酸(檸檬酸、乳酸、蘋果酸)、芳香族羧酸(苯甲酸、鄰苯二甲酸、柳酸等)、含氧酸(oxoacid)(丙酮酸等)、及、胺基酸(精胺酸(arginine)、天冬醯胺(asparagine)、天冬胺酸(aspartic acid)、半胱胺酸、麩胺酸(glutamic acid)、甘胺酸等)之1種以上。
羧酸或其鹽係其合計以在0.5~5g/L的範圍使用為佳，以0.8~2g/L的範圍為較佳。相較於在先前技術的無電解電鍍製程的無電解鍍鎳(S15)所使用的無電解鎳電鍍液，因為本實施形態的無電解觸擊鍍鎳液之鎳含量較低，所以將羧酸或其鹽的含量設定為較低。羧酸或其鹽亦取決於其種類，含量小於0.5g/L時，因為無電解觸擊鍍鎳夜中的鎳離子之錯合物形成變為不充分且產生沈澱，乃是不佳。另一方面，羧酸或其鹽的含量即便大於5g/L，不僅是無法得到特別的效果而且成為資源的浪費使用，乃是不佳。
還原劑： 無電解觸擊鍍鎳液，係含有選自二甲胺硼烷、三甲胺硼烷、肼、肼衍生物的群組之1種以上的還原劑。藉由無電解觸擊鍍鎳液係使用該等物質作為還原劑，能夠在未被賦予鈀觸媒的銅材表面實現鎳析出。從對人體的安全性之觀點而言，以二甲胺硼烷、三甲胺硼烷為較佳。
還原劑係以在2~10g/L的範圍使用為佳，以在4~8g/L的範圍為較佳。上述還原劑的含量小於2g/L時，無法得到充分的還原作用且無法在銅表面進行鎳析出，乃是不佳。上述還原劑的含量大於10g/L時，鎳在銅以外的表面(絕緣基材表面)異常析出、或無電解觸擊鍍鎳液產生浴分解，乃是不佳。
無電解觸擊鍍鎳液，係藉由使上述成分在水中混合且攪拌而溶解來調製。該無電解觸擊鍍鎳液，藉由將前述水溶性鎳鹽、前述羧酸或其鹽及水混合且攪拌來調製含有鎳錯合物的水溶液之後，藉由將前述還原劑混合在該水溶液且攪拌來調製為佳。如此進行而調製的無電解觸擊鍍鎳液，鎳錯合物能夠長期間穩定地存在且能夠得到優異的浴安定性。
無電解觸擊鍍鎳液，係上述成分以外，亦可含有硫酸鹽、硼酸、氯化物鹽等的成分。
pH： 無電解觸擊鍍鎳液之pH，係以調整成為6~10之中性區域為佳。pH小於6時，鎳析出速度低落且鍍鎳皮膜的成膜性低落，而且在鍍鎳皮膜表面產生孔部和凹部(孔穴)，乃是不佳。另一方面、pH大於10時，鎳析出速度為過度地變快且鍍鎳皮膜的膜厚控制變為困難、或無法使析出的鎳之結晶狀態緻密化，乃是不佳。
浴溫： 無電解觸擊鍍鎳液之浴溫，係以調整成為20~55℃為佳。這是比先前技術的無電解鍍鎳(S15)所使用的無電解鎳電鍍液之浴溫60~90℃更低的值。浴溫小於20℃時，鎳析出速度低落且鍍鎳皮膜的成膜性低落，而且在鍍鎳皮膜表面產生孔部和凹部(孔穴)、或是有產生鎳未析出之情形，乃是不佳。另一方面、浴溫大於55℃時，無電解觸擊鍍鎳液的浴安定性低落而有無法實現無電解觸擊電鍍法之情形，乃是不佳。
膜厚： 鍍鎳皮膜的膜厚，係能夠藉由在無電解觸擊鍍鎳液的浸漬時間而調整。鍍鎳皮膜的膜厚係在能夠防止銅擴散之範圍，以盡可能較薄為佳，以0.005~0.3μm為佳。鍍鎳皮膜的膜厚小於0.005μm時，銅材表面的被覆變成不充分且在鍍鎳皮膜表面產生微小的凹部，其結果，在進行後續的無電解鍍金步驟(S6)時，有產生鎳局部腐蝕現象、或是銅和鎳擴散至鍍金皮膜表面之情形，乃是不佳。另一方面，雖然亦能夠成膜形成膜厚大於0.3μm之鍍鎳皮膜，但是因為鍍鎳皮膜的柔軟性低落，而且成為為資源的浪費使用，乃是不佳。
藉由本實施形態的無電解觸擊鍍鎳步驟(S4)，能夠實現在先前的無電解鍍鎳(S15)為困難之鍍鎳皮膜的薄膜化且能夠得到膜厚為0.005~0.3μm的鍍鎳皮膜。而且，為了邊確保良好的封裝特性邊實現薄膜化，藉由無電解觸擊鍍鎳步驟(S4)而成膜形成的鍍鎳皮膜之膜厚，係以0.007~0.1μm為較佳。
在本實施形態無電解觸擊鍍鎳步驟(S4)，在無電解觸擊鍍鎳液所含有之選自二甲胺硼烷、三甲胺硼烷、肼、肼衍生物的群組之1種以上的物質係作為還原劑的作用，能夠在未被賦予鈀觸媒的銅材表面使鎳析出。而且，無電解觸擊鍍鎳液的鎳含量較低，並且能夠調整成為pH為6~10、浴溫為20~55℃。藉此，能夠使鎳析出速度減慢而實現無電解觸擊電鍍法且能夠在銅材表面直接成膜形成鍍鎳皮膜。此時，因為鎳的析出速度較慢，所以能夠使鎳在銅材表面均勻地析出，其結果，膜厚均勻即便膜厚較薄亦能夠成膜形成確實將銅材表面被覆之鍍鎳皮膜。相較於在先前的無電解電鍍製程所得到的鍍鎳皮膜，所得到的鍍鎳皮膜係對銅材具有優異的密著性，同時具有優異的防止銅擴散之阻障特性。
相對於此，在先前技術的無電解電鍍製程所進行的無電解鍍鎳(S15)，藉由鈀觸媒賦予處理(S14)而對銅材表面所賦予的鈀係作為觸媒的作用而進行鎳析出。因此，在銅材表面之已被賦予鈀觸媒的區域與未被賦予的區域，所形成的鍍鎳皮膜之膜厚產生偏差且難以得到均勻膜厚的鍍鎳皮膜。而且，在無電解鍍鎳(S15)所使用的無電解鎳電鍍液，由於鎳含量和浴溫較高，鎳的析出速度較快之緣故，所以難以得到對銅材具有優異的密著性之鍍鎳皮膜。
藉由本實施形態的無電解觸擊鍍鎳步驟(S4)，使用二甲胺硼烷、三甲胺硼烷作還原劑時，能夠得到由鎳與硼的合金(鎳-硼合金)所構成之鍍鎳皮膜。該鍍鎳皮膜之硼含量為非常少(例如0.1%以下)且實質上由純鎳所構成之鍍鎳皮膜。又，使用肼、肼衍生物作為還原劑時，能夠得到由純鎳所構成之鍍鎳皮膜。
又，在無電解觸擊鍍鎳步驟(S4)，在上述無電解觸擊鍍鎳液之水溶性鎳鹽的含量為較低之0.002~1g/L。因此，即便不使用在先前技術的無電解電鍍製程的無電解鍍鎳(S15)所使用之錯鹽、鉍鹽等的安定劑，亦能夠防止產生浴分解。又，因為上述無電解觸擊鍍鎳液係不含有錯鹽、鉍鹽等的安定劑，所以能夠得到不含有鉛、鉍等的重金屬之鍍鎳皮膜。
5.無電解鍍鈀步驟(S5) 在無電解鍍鈀步驟(S5)，係使用還原型無電解電鍍法而在上述鍍鎳皮膜表面成膜形成鍍鈀皮膜。因為使用取代型無電解電鍍法而成膜形成鈀皮膜時，有產生鎳局部腐蝕現象，亦即鎳溶出且產生貫穿鍍鎳皮膜的貫穿孔之情形，所以採用還原型無電解電鍍法。
作為在無電解鍍鈀步驟(S5)所使用的還原型無電解鈀電鍍液，係能夠得到習知物。例如，能夠使用含有鈀化合物0.001~0.1mol/L、胺化合物0.05~5mol/L、無機硫化合物0.01~0.1mol/L、及次磷酸或次磷酸化合物0.05~1.0mol/L之還原型無電解鈀電鍍液。或使用甲酸或甲酸化合物0.001~0.1mol/L代替上述次磷酸或次磷酸化合物之還原型無電解鈀電鍍液。
在無電解鍍鈀步驟(S5)，係藉由採用還原型無電解電鍍法，在成膜形成鍍鈀皮膜時能夠防止鎳從鍍鎳皮膜溶出。而且，在本實施形態的無電解電鍍製程，藉由無電解觸擊鍍鎳步驟(S4)而成膜形成的鍍鎳皮膜係膜厚均勻且具有優異的平滑性，所以藉由無電解鍍鈀步驟(S5)能夠成膜形成具有均勻的膜厚之鍍鈀皮膜。
6.無電解鍍金步驟(S6) 在無電解鍍金步驟(S6)，使用還原型無電解電鍍法而在上述鍍鈀皮膜表面成膜形成鍍金皮膜。使用取代型無電解電鍍法而成膜形成鍍金皮膜時，因為鈀溶出且產生貫穿鍍鈀皮膜的貫穿孔之情形，所以採用還原型無電解電鍍法。
作為在無電解鍍金步驟(S6)所使用的還原型無電解金電鍍液，能夠使用習知物。例如能夠使用含有水溶性金化合物、檸檬酸或其鹽、乙二胺四乙酸或其鹽、作為還原劑的六亞甲基四胺、及含有碳數3以上的烷基及3個以上的胺基之鏈狀多元胺之還原型無電解金電鍍液。
在無電解鍍金步驟(S6)，藉由採用、還原型無電解電鍍法，在成膜形成鍍金皮膜時，能夠防止鈀從鍍鈀皮膜溶出。而且，在本實施形態的無電解電鍍製程，因為藉由無電解鍍鈀步驟(S4)而成膜形成的鍍鈀具有均勻的膜厚，所以藉由無電解鍍金步驟(S6)，能夠成膜形成具有均勻的膜厚之鍍金皮膜。
無電解鍍金步驟結束後，進行水洗處理且使其乾燥。如上述，藉由進行第1圖顯示之無電解電鍍製程，能夠在銅材表面成膜形成Ni/P/Au皮膜。
在本實施形態的無電解電鍍製程，藉由無電解觸擊鍍鎳步驟(S4)而能夠在未被賦予鈀觸媒之銅材表面直接成膜形成鍍鎳皮膜。而且，即便膜厚較薄亦能夠將銅材表面確實地被覆且能夠成膜形成對銅材具有優異的密著性及阻障特性之鍍鎳皮膜。因而，能夠實現鍍鎳皮膜的薄膜化。
而且，因為能夠使鍍鎳皮膜的膜厚較薄，所以能夠得到全體膜厚較薄的Ni/Pd/Au皮膜。又，藉由無電解觸擊鍍鎳步驟(S4)，因為膜厚為均勻且能夠得到具有優異的平滑性之鍍鎳皮膜，所以在其上成膜形成的鍍鈀皮膜及鍍金皮膜亦能夠成膜形成均勻的膜厚且能夠成膜形成膜厚的偏差較小的Ni/Pd/Au皮膜。而且，使用無電解觸擊電鍍法成膜形成的鍍鎳皮膜係與銅材具有優異的密著性，並且因為具有優異的防止銅擴散之阻障特性，所以能夠成膜形成包括優異的封裝特性之Ni/Pd/Au皮膜。
又，上述鍍鎳皮膜之膜厚較薄，而且與藉由先前技術的無電解鍍鎳(S15)而成膜形成的鍍鎳皮膜不同且不含有磷。從此種情形，因為上述鍍鎳皮膜能夠得到優異柔軟性，所以Ni/Pd/Au皮膜能夠得到優異的柔軟性。
而且，在本實施形態的無電解電鍍製程，與先前技術的無電解電鍍製程不同，因為在無電解觸擊鍍鎳步驟(S4)之前不必進行鈀觸媒賦予處理(S14)，所以能夠減少步驟的數目。
上述本實施形態的無電解電鍍製程，係在無電解觸擊鍍鎳步驟(S4)之後，進行無電解鍍鈀步驟(S5)及無電解鍍金步驟(S6)之製程。本實施形態的無電解電鍍製程，亦可為在無電解觸擊鍍鎳步驟(S4)之後，不進行無電解鍍鈀步驟(S5)而藉由進行無電解鍍金步驟(S6)，而在銅材表面成膜形成Ni/Au皮膜之製程。
以下，基於實施例等而具體地說明本發明。 [實施例1]
在本實施例的無電解電鍍製程，藉由依照順序進行第1圖顯示之各步驟S1~S6(全部為6步驟)，在銅材表面成膜形成Ni/Pd/Au皮膜。依照順序進行上述脫脂步驟(S1)、蝕刻步驟(S2)及去沾污步驟(S3)之後，進行無電解觸擊鍍鎳步驟(S4)。在無電解觸擊鍍鎳步驟(S4)，係將銅材浸漬在以下組成的無電解觸擊鍍鎳液而在銅材表面成膜形成鍍鎳皮膜。無電解觸擊鍍鎳液係藉由將硫酸鎳六水合物、DL-蘋果酸及水混合且攪拌來調製含有鎳錯合物的水溶液之後，藉由添加二甲胺硼烷且攪拌來調製。在將銅材浸漬在無電解觸擊鍍鎳液之期間，係將該無電解觸擊鍍鎳液藉由通氣(aeration)而攪拌。 (無電解觸擊鍍鎳液)
接著進行無電解鍍鈀步驟(S5)。將成膜形成有鍍鎳皮膜之銅材浸漬在以下組成的還原型無電解鈀電鍍液，而在鍍鎳皮膜的表面成膜形成鍍鈀皮膜。 (還原型無電解鈀電鍍液)
隨後，進行無電解鍍金步驟(S6)。成膜形成有鍍鈀皮膜之銅材浸漬在以下組成的還原型無電解金電鍍液，而在鍍鈀皮膜表面成膜形成鍍金皮膜。藉由上述，而在銅材表面成膜形成Ni/Pd/Au皮膜。 (還原型無電解金電鍍液) [比較例]
[比較例1] 本比較例的無電解電鍍製程，係除了在先前技術的無電解電鍍製程進行鈀觸媒賦予處理(S14)及無電解鍍鎳(S15)代替無電解觸擊鍍鎳步驟(S4)以外，係藉由與實施例1的無電解電鍍製程完全同樣地進行而在銅材表面成膜形成Ni/Pd/Au皮膜。本比較例的無電解電鍍製程的步驟係全部為7步驟。
在鈀觸媒賦予處理(S14)，係將經去沾污的銅材浸漬在含有鈀換算為30mg/L的鈀化合物及硫酸離子之鈀觸媒溶液，而對銅材表面賦予鈀觸媒。
在無電解鍍鎳(S15)，係將經賦予鈀觸媒的銅材浸漬在以下組成的無電解鎳電鍍液。 (無電解鎳電鍍液)
[比較例2] 本比較例的無電解電鍍製程，係除了在無電解鍍鎳(S15)使用以下組成的無電解鎳電鍍液以外，係與比較例1完全同樣地進行。本比較例的無電解電鍍製程的步驟係全部為7步驟。 (無電解鎳電鍍液)
[參考例1] 本參考例的無電解電鍍製程，係除了在進行無電解鍍鎳(S15)之前進行鈀觸媒賦予處理(S14)以外，係與比較例1完全同樣地進行。本參考例的無電解電鍍製程的步驟係全部為6步驟。
[參考例2] 本參考例的無電解電鍍製程，係除了在進行無電解鍍鎳(S15)之前不進行鈀觸媒賦予處理(S14)以外，係與比較例2完全同樣地進行。
＜評價＞ 1.對鍍鎳皮膜之評價 首先，藉由進行至實施例1的無電解電鍍製程的無電解觸擊鍍鎳步驟(S4)為止、或進行至比較例1及比較例2的無電解電鍍製程的無電解鍍鎳(S15)為止之步驟，而在銅材表面成膜形成膜厚0.01μm的鍍鎳皮膜。針對所得到的鍍鎳皮膜進行以下的評價。
1-1.鎳析出性 在此，係使用將30個直徑0.45mm的銅墊片以30μm間隔在絕緣基材上配置成為格子狀而成之測試板(test board)。然後，藉由進行至實施例1的無電解電鍍製程的無電解觸擊鍍鎳步驟(S4)為止、或進行至比較例1及比較例2的無電解電鍍製程的無電解鍍鎳(S15)為止之步驟，而在銅墊片表面成膜形成鍍鎳皮膜。另一方面，在參考例1及參考例2的無電解電鍍製程，係進行至無電解鍍鎳(S15)為止之步驟，但是鎳完全未析出至銅墊片表面而無法成膜形成鍍鎳皮膜。
將所得到的鍍鎳皮膜使用金屬顯微鏡(倍率1000倍)進行觀察，來計算鎳析出能夠正常地進行之銅墊片的數目。在此，所謂鎳析出能夠正常地進行，係意味著銅墊片的表面全體係經鍍鎳皮膜被覆且藉由金屬顯微鏡無法觀察到未經被覆的部分。將結果顯示在表1。表1中的○記號、△記號及×記號的判斷基準係如以下。 ○：鎳析出能夠正常地進行的銅墊片為30個。 △：鎳析出能夠正常地進行的銅墊片為15~29個。 ×：鎳不能夠完全析出的銅墊片為30個。
[表1]
如表1所顯示，將比較例1與參考例1進行比較，同時將比較例2與參考例2進行比較時，能夠理解為了使用在比較例1及比較例2的無電解鍍鎳(S15)所使用的無電解鎳電鍍液而成膜形成鍍鎳皮膜，必須在進行無電解鍍鎳(S15)之前進行鈀觸媒賦予處理(S14)。
而且，雖然比較例1的無電解鍍鎳(S15)係經常能夠正常地進行鎳析出，但是能夠理解比較例2的無電解鍍鎳(S15)係有無法正常地進行鎳析出之情形且鎳析出性較差。相對於此，能夠理解實施例1的無電解觸擊鍍鎳步驟(S4)係經常能夠正常地進行鎳析出且具有優異的鎳析出性。
1-2.表面形態 為了進行評價在銅墊片表面成膜形成的鍍鎳皮膜之表面形態，係藉由掃描電子顯微鏡(SEM)以倍率5000倍及3萬倍拍攝鍍鎳皮膜表面而得到反射電子組成影像(COMPO影像)。將結果顯示在第2圖~第4圖。第2圖係顯示藉由實施例1的無電解觸擊鍍鎳步驟(S4)而得到的鍍鎳皮膜之COMPO影像，第3圖係顯示藉由比較例1的無電解鍍鎳(S15)而得到的鍍鎳皮膜之COMPO影像，第4圖係顯示藉由比較例2的無電解鍍鎳(S15)而得到的鍍鎳皮膜之COMPO影像，第2圖(a)、第3圖(a)及第4圖(a)為倍率5000倍，第2圖(b)、第3圖(b)及第4圖(b)為倍率3萬倍。
相較於藉由比較例1及比較例2的無電解鍍鎳(S15)而得到的鍍鎳皮膜，從第2圖~第4圖，能夠確認藉由實施例1的無電解觸擊鍍鎳步驟(S4)而得到的鍍鎳皮膜，係黑色部分較少。黑色部分係表示在鍍鎳皮膜上存在原子號碼較小的碳等元素。因此，相較於藉由比較例1及比較例2的無電解鍍鎳(S15)而得到的鍍鎳皮膜，能夠理解藉由實施例1的無電解觸擊鍍鎳步驟(S4)而得到的鍍鎳皮膜，係缺陷部分較少且為緻密的膜。又，因為藉由比較例2的無電解鍍鎳(S15)而得到的鍍鎳皮膜係黑色部分為特別多，所以能夠理解是缺陷部分較多且不是緻密的膜。
而且，藉由比較例1及比較例2的無電解鍍鎳(S15)而得到的鍍鎳皮膜係在表面存在較大的凹凸，藉由實施例1的無電解觸擊鍍鎳步驟(S4)而得到的鍍鎳皮膜，係能夠確認在表面不存在較大的凹凸而只存在細小的凹凸。因此，相較於藉由比較例1及比較例2的無電解鍍鎳(S15)而得到的鍍鎳皮膜，能夠理解藉由實施例1的無電解觸擊鍍鎳步驟(S4)而得到的鍍鎳皮膜係具有較優異的平滑性。又，能夠理解因為比較例2的鍍鎳皮膜係較大的凹凸存在特別多，所以平滑性較差。
從上述情形，相較於比較例1及比較例2的無電解電鍍製程的無電解鍍鎳(S15)，能夠理解藉由實施例1的無電解電鍍製程的無電解觸擊鍍鎳步驟(S4)，能夠得到緻密且具有優異的平滑性之鍍鎳皮膜。
1-3.表面元素分析 針對在銅墊片表面成膜形成的鍍鎳皮膜，係使用歐傑電子能譜(Auger electron spectroscopy)分析裝置而進行表面元素分析。如上述，因為比較例2的鍍鎳皮膜之性能較差，係以只有將實施例1及比較例1的鍍鎳皮膜作為對象。
對鍍鎳皮膜進行回流處理3次。回流處理係藉由將鍍鎳皮膜於230℃進行預熱之後，在250℃加熱來進行。而且，在進行回流處理之前、及進行回流處理且使其自然冷卻至常溫為止之後，進行表面元素分析。表面元素分析的測定條件係設為加速電壓10kV、探針電流值10nA、測定直徑50μm、掃描範圍30：~2400eV。將結果顯示在表2。表2的數值係從所得到的能譜之尖峰強度比將元素定量化而成之數值(單位：原子%)。表2中的-記號係意味著完全未檢測出該元素。
[表2]
藉由實施例1的無電解觸擊鍍鎳步驟(S4)而得到的鍍鎳皮膜，被認為含有源自二甲胺硼烷之硼，但是實際上無法檢測出硼，清楚明白實質上是由純鎳所構成。另一方面，藉由比較例1的無電解鍍鎳(S15)而得到的鍍鎳皮膜，係如表2所顯示，由含有源自次磷酸鈉之磷所構成之物。
從表2，能夠理解實施例1之藉由無電解觸擊鍍鎳步驟(S4)而得到的鍍鎳皮膜，係即便在第2次的回流處理後，銅未擴散至其表面而具有優異的阻障性能。另一方面，藉由比較例1的無電解鍍鎳(S15)而得到的鍍鎳皮膜，在第1次的回流處理後，雖然銅未擴散至其表面，但是在第2次回流處理後，銅擴散至其表面而能夠理解阻障性能較差。
1-4.低電位電解 在此，使用銅板代替上述測試板，在銅板表面成膜形成膜厚0.01μm的鍍鎳皮膜。然後，針對所得到的鍍鎳皮膜，在0.5體積%硫酸溶液中以50mV進行低電位電解且進行評價阻障特性。將結果顯示在第5圖。圖中的橫軸為電解時間，縱軸為電流密度。電流密度的上升係表示銅從鍍鎳皮膜下層之銅材溶出。
如第5圖顯示，相較於藉由比較例1的無電解鍍鎳(S15)而得到的鍍鎳皮膜，因為藉由實施例1的無電解觸擊鍍鎳步驟(S4)而得到的鍍鎳皮膜之電流密度的上升較小，能夠理解具有優異的阻障特性。
從以上的鎳析出性、表面形態、表面元素分析及低電位電解的結果，相較比較例1及比較例2的無電解電鍍製程的無電解鍍鎳(S15)，能夠理解實施例1的無電解電鍍製程的無電解觸擊鍍鎳步驟(S4)係具有優異的鎳析出性，並且緻密且平滑而能夠得到具有優異的阻障性之鍍鎳皮膜。而且，能夠理解實施例1之藉由無電解電鍍製程的無電解觸擊鍍鎳步驟(S4)而得到的鍍鎳皮膜，係相較於與其相同膜厚且藉由比較例1及比較例2的無電解電鍍製程的無電解鍍鎳(S15)而得到的鍍鎳皮膜，包括更優異的性能。
2.對Ni/Pd/Au皮膜之評價 在此，係使用將配線寬度/配線間隔(L/S)為30~100μm/30~100μm之銅的微細配置在絕緣基材上，同時將微細配線為直徑0.45mm的銅墊片以0.45μm間隔配置成為格子狀而成之測試板。藉由對該測試板，進行實施例1的無電解電鍍製程的全部6步驟或比較例1的無電解電鍍製程的全部7步驟，而在銅材(微細配線及墊片)表面成膜形成Ni/Pd/Au皮膜。
在實施例1的無電解電鍍製程，係得到由膜厚0.01μm的鍍鎳皮膜、膜厚0.1μm的鍍鈀皮膜、及膜厚0.1μm的鍍金皮膜所構成之Ni/Pd/Au皮膜。在比較例1的無電解電鍍製程，係得到由膜厚0.5μm的鍍鎳皮膜、膜厚0.1μm的鍍鈀皮膜、及膜厚0.1μm的鍍金皮膜所構成之Ni/Pd/Au皮膜。而且，針對所得到的Ni/Pd/Au皮膜進行以下的評價。
2-1.焊料擴大性 對Ni/Pd/Au皮膜表面進行焊接，隨後進行焊料擴大試驗。使用千住金屬工業股份公司的ECO SOLDER(註冊商標)M770作為焊球，而且焊球直徑D係設為700μm。焊料擴大試驗係使用焊料回流爐(股份公司日本脈衝技術研究所、RF-330)，而且設為預熱溫度230℃、回流溫度250℃且使用股份公司ASAHI化學研究所的AGF-780DS-AA作為助焊劑。然後，測定回流後的焊球高度H(μm)，而且依照以下的公式計算擴大率S且求取其最大值、最小值及平均值。而且，針對在進行焊接之前，於溫度250℃施行熱處理4小時後之Ni/Pd/Au皮膜，亦同樣地進行焊料擴大試驗。將結果顯示在第6圖。第6圖的「無熱處理」係顯示在實施例1或比較例1的無電解電鍍製程之後，不施行上述熱處理而進行焊接之Ni/Pd/Au皮膜的焊料擴大試驗的結果，「有熱處理」係顯示在上述無電解電鍍製程後，緊接著施行上述熱處理之後，進行焊接之Ni/Pd/Au皮膜的結果。 擴大率S=(D-H)/D×100(%)
從第6圖，能夠理解在無熱處理、有熱處理之雙方，藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，係相較於藉由比較例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，具有更優異的焊料擴大性。又，將無熱處理與有熱處理進行比較時，相對於藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，係平均值及最小值之差為較小，藉由比較例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜係平均值大幅度地降低。因此，能夠理解藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，抑制因熱處理而銅和鎳擴散至鍍金皮膜之效果較高，即便進行熱處理時亦能夠維持具有優異的焊料擴大性且具有優異的耐熱性。
2-2.焊球剪切強度 對Ni/Pd/Au皮膜表面進行焊接，隨後測定焊球剪切強度。焊球剪切強度係使用Dage公司製(Series 4000)焊球剪切測試器，在剪切高度20μm、剪切速度500μm/秒的條件下進行測定，來求取其最大值、最小值及平均值。而且，針對在進行焊接之前，於溫度250℃施行4小時的熱處理之Ni/Pd/Au皮膜，亦同樣地測定焊球剪切強度。將結果顯示在第7圖。第7圖的「無熱處理」，係顯示在實施例1或比較例1的無電解電鍍製程之後，不施行上述熱處理而進行焊接後之Ni/Pd/Au皮膜的焊球剪切強度，「有熱處理」係顯示在上述無電解電鍍製程後，緊接著施行上述熱處理之後，進行焊接後之Ni/Pd/Au皮膜的結果。
從第7圖，在無熱處理、有熱處理之雙方，能夠理解相較於藉由比較例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，雖然藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜之數值本身為較低，但是亦具有優異的焊球剪切強度。又，將無熱處理與有熱處理進行比較時，相對於藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，係平均值及最小值之差為較小，藉由比較例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，係在熱處理的前後之平均值及最小值大幅度地降低。因此，能夠理解相較於藉由比較例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，係抑制因熱處理而銅和鎳擴散至鍍金皮膜之效果較高，而且即便進行熱處理時亦能夠維持優異的焊球剪切強度且包括優異的耐熱性。
2-3.引線接合強度及斷裂模式 將線徑25μm的金線接合在Ni/Pd/Au皮膜表面之後，使用拉力測試器測定將金線進行拉伸時之接合強度亦即引線接合強度。而且，求取其最大值、最小值及平均值。而且，針對在進行焊接之前於溫度250℃施行4小時的熱處理後之Ni/Pd/Au皮膜，亦同樣地測定引線接合強度。將結果顯示在第8圖。而且，將金線斷裂時的斷裂模式顯示在第9圖。第8圖及第9圖的「無熱處理」，係顯示在實施例1或比較例1的無電解電鍍製程之後，不施行上述熱處理而進行焊接之Ni/Pd/Au皮膜的引線接合強度或斷裂模式，「有熱處理」係顯示上述無電解電鍍製程後，緊接著施行上述熱處理之後，進行焊接後之Ni/Pd/Au皮膜的結果。
從第8圖，能夠理解藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，係在無熱處理、有熱處理的雙方，包括與藉由比較例1的無電解電鍍製程而得到的無熱處理之Ni/Pd/Au皮膜同等水準的引線接合強度。又，將無熱處理與有熱處理進行比較時，藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，係平均值及最小值之差較小，藉由比較例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，係平均值及最小值大幅度地降低。
而且，如第9圖顯示，藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，係在無熱處理、有熱處理之雙方，金線斷裂時的斷裂模式係全部為C模式。另一方面，藉由比較例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，在無熱處理係全部為C模式，另一方面在有熱處理係45%為C模式且55%為E模式。
從該等結果，能夠理解相較於藉由比較例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，藉由實施例1的無電解電鍍製程所得到的Ni/Pd/Au皮膜，抑制因熱處理而銅和鎳擴散至鍍金皮膜之效果較高，即便進行熱處理時亦能夠維持引線接合強度及斷裂模式且包括優異的耐熱性。
從以上的焊料擴大性、焊球剪切強度、引線接合強度及斷裂模式的結果，能夠理解相較於藉由比較例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，藉由實施例1的無電解電鍍製程而得到的Ni/Pd/Au皮膜，儘管鍍鎳皮膜的膜厚為1/50，但是包括同等以上之優異的封裝特性。認為該情形係因為藉由實施例1的無電解電鍍製程的無電解觸擊鍍鎳步驟(S4)而成膜形成之鍍鎳皮膜，係緻密且平滑而具有優異的阻障性能。 產業上之可利用性
如以上說明，依照本發明的無電解電鍍製程，能夠在銅材表面成膜形成Ni/Au皮膜或Ni/Pd/Au皮膜。因為所得到的鍍鎳皮膜，即便膜厚較薄，亦能夠確實地將銅材表面被覆，所以依照本發明的無電解電鍍製程能夠實現鍍鎳皮膜的薄膜化。因為所得到的Ni/Au皮膜或Ni/Pd/Au皮膜，即便鍍鎳皮膜的膜厚較薄亦能夠得到優異的封裝特性，所以本發明的無電解電鍍製程係能夠因應複雜的配線圖案和狹窄的間距配線且能夠實現高密度封裝。又，因為所得到的Ni/Au皮膜或Ni/Pd/Au皮膜，係全體膜厚較薄且具有優異的柔軟性，所以適合作為可撓性基板。
而且，依照本發明的無電解電鍍製程，因為即便不進行在先前的無電解電鍍製程所進行的鈀觸媒賦予處理(S14)亦能夠成膜形成鍍鎳皮膜，所以能夠提升生產性。
S1‧‧‧脫脂
S2‧‧‧蝕刻
S3‧‧‧去沾污
S4‧‧‧無電解觸擊鍍Ni
S5‧‧‧無電解鍍Pd
S6‧‧‧無電解鍍Au
S11‧‧‧脫脂
S12‧‧‧蝕刻
S13‧‧‧去沾污
S14‧‧‧Pd觸媒賦予
S15‧‧‧無電解鍍Ni
S16‧‧‧無電解鍍Pd
S17‧‧‧無電解鍍Au
第1圖係顯示本實施形態的無電解電鍍製程之流程圖。 第2圖係在實施例1的無電解電鍍製程所得到的鍍鎳皮膜之SEM照相。 第3圖係在比較例1的無電解電鍍製程所得到的鍍鎳皮膜之SEM照相。 第4圖係在比較例2的無電解電鍍製程所得到的鍍鎳皮膜之SEM照相。 第5圖係顯示對在實施例1及比較例1的無電解電鍍製程所得到的鍍鎳皮膜進行低電位電解的結果之圖表。 第6圖係顯示在實施例1及比較例1的無電解電鍍製程所得到的Ni/Pd/Au皮膜之焊料擴大性之圖表。 第7圖係顯示在實施例1及比較例1的無電解電鍍製程所得到的Ni/Pd/Au皮膜之焊球剪切強度之圖表。 第8圖係顯示在實施例1及比較例1的無電解電鍍製程所得到的Ni/Pd/Au皮膜之引線接合強度之圖表。 第9圖係顯示在實施例1及比較例1的無電解電鍍製程所得到的Ni/Pd/Au皮膜之金引線斷裂模式之圖表。 第10圖係顯示先前技術的無電解電鍍製程之流程圖。

Claims (5)

  1. 一種無電解電鍍製程，係使用無電解電鍍法而將依照順序成膜形成鍍鎳皮膜及鍍金皮膜在銅材表面之無電解電鍍製程，其特徵在於包括：使用無電解觸擊電鍍法而直接成膜形成鍍鎳皮膜在銅材表面之步驟；及使用還原型無電解電鍍法而成膜形成鍍金皮膜之步驟。
  2. 如申請專利範圍第1項所述之無電解電鍍製程，其中前述無電解觸擊電鍍法係使用含有鎳換算為0.002~1g/L的水溶性鎳鹽、羧酸或其鹽、及選自二甲胺硼烷、三甲胺硼烷、肼、肼衍生物的群組之1種以上的還原劑且調整成為pH為6~10、浴溫為20~55℃之無電解觸擊鍍鎳液，藉由將前述銅材浸漬在該無電解觸擊鍍鎳液而進行。
  3. 如申請專利範圍第2項所述之無電解電鍍製程，其中前述無電解觸擊鍍鎳液，係藉由將前述水溶性鎳鹽、前述羧酸或其鹽及水混合且攪拌而調製含有鎳錯合物之水溶液之後，將前述還原劑混合在該水溶液且攪拌來調製。
  4. 如申請專利範圍第1項所述之無電解電鍍製程，其中成膜形成前述鍍鎳皮膜之步驟，係成膜形成膜厚為0.005~0.3μm之鍍鎳皮膜。
  5. 如申請專利範圍第1項所述之無電解電鍍製程，其中前述無電解電鍍製程，係在銅材表面依照順序成膜形成鍍鎳皮膜、鍍鈀皮膜及鍍金皮膜，在成膜形成前述鍍鎳皮膜之步驟與成膜形成前述鍍金皮膜之步驟之間，包括使用還原型無電解電鍍法而成膜形成鍍鈀皮膜之步驟。
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