TWI651432B - 用於基材表面金屬化之新穎黏著促進劑 - Google Patents

用於基材表面金屬化之新穎黏著促進劑 Download PDF

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TWI651432B
TWI651432B TW103133644A TW103133644A TWI651432B TW I651432 B TWI651432 B TW I651432B TW 103133644 A TW103133644 A TW 103133644A TW 103133644 A TW103133644 A TW 103133644A TW I651432 B TWI651432 B TW I651432B
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Taiwan
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metal
substrate
compound
oxide
plating
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TW103133644A
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TW201516181A (zh
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志明 劉
付海羅
沙拉 漢格那
拉茲 布雷登
塔發瓦 馬格亞
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德商德國艾托特克公司
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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
    • 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
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1851—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material
    • C23C18/1872—Pretreatment of the material to be coated of surfaces of non-metallic or semiconducting in organic material by chemical pretreatment
    • C23C18/1886—Multistep pretreatment
    • C23C18/1893—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3607—Coatings of the type glass/inorganic compound/metal
    • C—CHEMISTRY; METALLURGY
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    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3618—Coatings of type glass/inorganic compound/other inorganic layers, at least one layer being metallic
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/36—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal
    • C03C17/3602—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer
    • C03C17/3649—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer made of metals other than silver
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    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
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    • C03C17/3697—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions at least one coating being a metal the metal being present as a layer one metallic layer at least being obtained by electroless plating
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    • C04B41/5072—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with oxides or hydroxides not covered by C04B41/5025
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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    • C04B41/5072—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials with oxides or hydroxides not covered by C04B41/5025
    • C04B41/5074—Copper oxide or solid solutions thereof
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
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    • C04B41/50—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with inorganic materials
    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
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    • C04B41/51—Metallising, e.g. infiltration of sintered ceramic preforms with molten metal
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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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    • C23C18/00—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
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    • 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
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    • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
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    • C23C18/02—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 thermal decomposition
    • C23C18/12—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 thermal decomposition characterised by the deposition of inorganic material other than metallic material
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    • 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
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Abstract

本發明提供一種用於非導電基材金屬化之方法，其提供沈積金屬對於基材材料之高黏著性且由此形成持久黏結。該方法施用促進黏著之金屬氧化物化合物與促進金屬層形成之過渡金屬鍍敷催化劑化合物之新穎組合。

Description

用於基材表面金屬化之新穎黏著促進劑
本發明係關於藉由施用催化活性金屬氧化物組合物使如玻璃、陶瓷及矽基半導體類型表面之非導電基材金屬化之新穎方法。該方法產生在玻璃或陶瓷基材與鍍敷金屬之間展示高黏著性、而同時使光滑基材表面保持完整之金屬鍍敷表面。
本發明可適用於印刷電子電路(諸如用於信號分佈之在玻璃及陶瓷上之細線電路(覆晶玻璃中介層))、平板顯示器及射頻識別(RFID)天線之領域。又，其可適用於矽基半導體基材之金屬鍍敷。
此項技術中已知用於使基材金屬化之各種方法。
可藉由各種濕式化學鍍敷方法(例如電鍍或無電電鍍)以另一種金屬直接鍍敷導電性基材。該等方法在此項技術中已完全得到確認。通常對表面進行清潔預處理，之後進行濕式化學鍍敷製程以確保可靠之鍍敷結果。
已知用於塗佈非導電表面之各種方法。在濕式化學方法中，將欲金屬化之表面在適當初步處理後首先進行催化，且隨後以無電方式金屬化，且此後若必要，則進行電解金屬化。
通常藉由機械錨定來將金屬層黏著至非導電基材。然而，此要求基材表面劇烈粗糙化，此將不利影響金屬化表面之功能，例如在印 刷電子電路或RFID天線中。
可以含有HF之酸性介質或含有熱NaOH、KOH或LiOH之鹼性介質進行濕式化學蝕刻來對非導電基材，尤其玻璃或陶瓷類型基材進行清潔及粗糙化。隨後藉由粗糙化表面之其他錨定位點來提供黏著。
在EP 0 616 053 A1中，揭示一種用於使非導電表面直接金屬化之方法，其中表面首先以清潔劑/調節劑溶液進行處理、其後以活化劑溶液(例如膠狀鈀溶液)進行處理、以錫化合物穩定且隨後以含有比錫更貴之金屬化合物以及鹼金屬氫氧化物與成錯合物劑之溶液進行處理。此後，可在含有還原劑之溶液中處理表面，且最後可電解金屬化。
WO 96/29452涉及一種用於選擇性或部分電解金屬化由非導電材料製得之基材表面的方法，為達成塗佈方法之目的該等非導電材料緊固於塑料塗佈之固持元件。提出之方法包涵以下步驟：a)以含有氧化鉻(VI)之蝕刻溶液初步處理表面；繼而即刻b)以鈀/錫化合物之膠狀酸性溶液處理表面，謹慎防止與吸收促進溶液提前接觸；c)以含有能被錫(II)化合物還原之可溶性金屬化合物、鹼金屬或鹼土金屬氫氧化物及金屬之錯合物形成劑的溶液以至少足以防止金屬氫氧化物沈澱之量處理表面；d)以電解金屬化溶液處理表面。
US 3,399,268報導一種以包含熱固性樹脂、可撓性黏著性樹脂及精細分散於其中之金屬或金屬氧化物組分的催化性油墨在陶瓷上無電沈積金屬的方法。尤其較佳係氧化亞銅，尤其當其經酸至少部分還原為金屬銅時。油墨沈積之後，可藉由高溫固化。在無電沈積金屬之前，固化油墨必須摩擦或機械粗糙化以在其表面上提供足夠量之催化位點。此係一種費力方法，因為其首先要求將粒子分散於油墨調配物中，且其次要求機械粗糙化表面以達成最佳結果。
WO 2003/021004係關於對表面賦予催化性之方法。其中一個實 例涉及製備塗銅玻璃。首先在玻璃表面上沈積另外含有鈀作為催化劑之烷氧基化鋯與烷氧基化鋁的混合物，且經簡單固化以在基材上形成有機金屬膜。此後，藉由無電電鍍在其上形成銅層。然而，文獻未教示經此處理之基材的任何其他情及應用。
US 6,183,828 B1教示一種製造剛性記憶碟之方法。在此方法中，以在與基材接觸時分解且形成各別氧化物之金屬醇鹽處理熱基材。為了對表面賦予催化性以用於後續之塗鎳步驟，在其上沈積鈀催化劑。
JP H05-331660揭示一種用於諸如陶瓷及玻璃之非導電基材金屬化之方法。此方法包含以下步驟：將乙酸鋅溶液噴霧至基材上及將其加熱以形成氧化鋅層，在其上沈積鈀作為催化劑，之後鍍銅。
US 4,622,069係關於一種無電電鍍陶瓷之方法，其中在陶瓷基材上沈積由鈀及/或銀有機金屬化合物製得之催化劑，之後進行金屬化步驟。
US 2006/0153990 A1報導UV可固化鍍敷催化劑組合物，其在金屬化之前可用於諸如塑料、玻璃、陶瓷及其類似物之非催化性基材上。此等組合物包含催化性活性金屬(較佳為銀)之金屬氫氧化物或金屬水合氧化物、惰性載體(諸如矽酸鹽、金屬氧化物及多價陽離子與陰離子對)、UV固化劑及有助於自鍍敷溶液結合氫之聚合物。
此項技術中亦報導溶膠-凝膠衍生之塗層。溶膠-凝膠係一種包含以下步驟之方法：首先將適合之金屬前驅體在溶劑中水解，繼而係反應產物之縮合反應，之後將由此形成之溶液塗覆在表面上。
US 5,120,339涉及一種在玻璃織物上塗覆醇性二氧化矽溶膠-凝膠，之後進行無電金屬鍍敷且與可額外含有還原性催化劑(例如，銅或鈀鹽)之熱固性聚合物層壓。US 6,344,242 B1揭示一種溶膠-凝膠組合物，其包含金屬醇鹽、有機溶劑、氯離子來源及催化性金屬，較佳 為在金屬鍍敷之前可用在基材上之鈀。
或者，可在非導電表面上形成導電聚合物以提供用於表面之後續金屬鍍敷的第一導電層。
US 2004/0112755 A1描述非導電基材表面之直接電解金屬化，其包含使基材表面與水溶性聚合物(例如，噻吩)接觸；以高錳酸鹽溶液處理基材表面；以含有至少一種噻吩化合物及至少一種選自包含甲烷磺酸、乙烷磺酸及乙烷二磺酸之群之烷磺酸的含水基質之酸性水溶液或酸性微乳液處理基材表面；電解金屬化基材表面。
US 5,693,209係關於一種使具有非導體表面之電路板直接金屬化的方法，其包括使非導體表面與鹼性高錳酸鹽溶液反應以形成在非導體表面上化學吸收之二氧化錳；形成弱酸與吡咯或吡咯衍生物及其可溶性寡聚物之水溶液；使含有吡咯單體及其寡聚物之水溶液與其上化學吸附有二氧化錳之非導體表面接觸以在非導體表面上沈積黏附性、導電之不溶性聚合物產物；及在其上形成有不溶性黏附性聚合物產物之非導體表面上直接電沈積金屬。在室溫與溶液凝固點之間的溫度下，在含有0.1至200g/l吡咯單體之水溶液中有利地形成寡聚物。
Ren-De Sun等人(Journal of the Electrochemical Society,1999,146：2117-2122)教示藉由噴霧熱解、繼而進行濕式化學Pd活化且無電沈積Cu來在玻璃上沈積薄ZnO層。其報導在沈積銅層與玻璃基材之間的適度黏著。沈積銅之厚度為約2μm。
視基材表面之化學性質、鍍敷金屬之類型及金屬鍍層之厚度而定，金屬鍍層與該表面之黏著可能呈現問題。舉例而言，黏著性可能過低而無法在金屬層與下層基材之間提供可靠黏結。
本發明的目標
總而言之，工業上強烈驅使陶瓷及玻璃基材用於電子應用，其需要不會不利地改變基材特性且在經濟上可行之用於鍍Cu的合適黏 著促進劑。
就經濟觀點而言，可能另外高度需要藉由較廉價之替代物來替代已得到認可但昂貴之Pd鍍敷催化劑，包括減少所需加工步驟的數目。
因此，本發明之目標在於提供一種用於基材金屬化之方法，其提供沈積金屬對於基材材料之高黏著性且由此形成持久黏結。本發明之另一目標在於提供一種在陶瓷與玻璃基材表面之金屬化中提供用於同時促進黏著且催化無電電鍍之塗層-而實質上不增加或粗糙化表面之方法。
此外，本發明之目標在於能夠完全或選擇性地使基材表面金屬化。
該等目標藉由用於向非導電基材上鍍敷金屬之濕式化學方法而得以解決，其包含以下步驟：i. 在非導電基材表面之至少一部分上沈積選自由氧化鋅、氧化鈦、氧化鋯、氧化鋁、氧化矽及氧化錫或前述各物之混合物組成之群之金屬氧化物化合物及選自由氧化銅、氧化鎳及氧化鈷及前述各物之混合物組成之群之過渡金屬鍍敷催化劑化合物，且其後ii. 在350℃至1200℃範圍內之溫度下熱處理非導電基材且由此在基材表面之至少一部分上形成金屬氧化物化合物與過渡金屬鍍敷催化劑化合物之黏著性催化層；且其後iii. 藉由應用濕式化學無電電鍍方法至少金屬鍍敷具有過渡金屬鍍敷催化劑化合物之基材表面，其中用於鍍敷之組合物包含待鍍敷之金屬離子的來源及還原劑。
此方法提供在非導電基材上展示沈積金屬對於基材材料之高黏著性且由此形成持久黏結之金屬沈積物。
尤其適用的係本發明之方法不需要任何其他加工步驟，諸如溶膠-凝膠方法或機械粗糙化步驟所需要之沈積物質的合成。
本發明提供一種用於非導電基材金屬化之金屬鍍敷方法。
適合經本發明之鍍敷方法處理之非導電基材包含玻璃、陶瓷及矽基半導體材料(亦表示為晶圓基材)。玻璃基材之實例包含二氧化矽玻璃(非晶形二氧化矽材料)、鹼石灰玻璃、漂浮玻璃、氟化物玻璃、鋁矽酸鹽、磷酸鹽玻璃、硼酸鹽玻璃、硼矽酸玻璃、硫屬玻璃、氧化鋁、具有氧化表面之矽。此類型之基材例如用作微晶片封裝及其類似物之中介層。矽基半導體材料用於晶圓工業中。
陶瓷基材包含工業陶瓷(如基於氧化物之氧化鋁、氧化鈹、二氧化鈰、二氧化鋯氧化物)或基於鋇之陶瓷(如BaTiO3)及非氧化物(如碳化物、硼化物、氮化物及矽化物)。
該等非導電基材(尤其玻璃及晶圓基材)常具有光滑表面。非導電基材之「光滑表面」在本文中根據ISO 25178，由如光學干擾顯微法所測定之表面的平均表面粗糙度Sa來定義。
對於玻璃基材而言，「光滑表面」之參數Sa的值較佳在0.1至200nm、更佳在1至100nm且甚至更佳在5至50nm之範圍內。對於陶瓷基材而言，表面粗糙度常更高。其可高達1000nm之Sa值，例如在400至600nm之間的範圍內。
具有Sa值在0.1至200nm範圍內之光滑表面的基材(諸如玻璃及晶圓基材)係較佳的，根據本發明玻璃係最佳的。
非導電基材較佳在與金屬氧化物前驅體化合物接觸前經清潔。適合之清潔方法包含將基材浸沒於包含表面活性物質之溶液中、將基 材浸沒於極性有機溶劑或極性有機溶劑之混合物中、將基材浸沒於鹼性溶液中及兩種或兩種以上前述清潔方法之組合。
玻璃基材例如可藉由浸沒於30wt.% NH4OH、30wt.% H2O2與水之混合物中歷時30分鐘，繼而浸沒於35wt.% HCl、30wt.% H2O2與水之混合物中歷時30min來進行清潔。此後，將基材在去離子水(DI water)中沖洗並乾燥。
如本文所定義之金屬氧化物化合物係選自由氧化鋅、氧化鈦、氧化鋯、氧化鋁、氧化矽及氧化錫或前述各物之混合物組成之群之化合物。金屬離子之價數可變化。然而，一些金屬主要以一種價數出現，例如鋅幾乎總是鋅(II)，因此形成Zn(II)O氧化物物質。
金屬氧化物前驅體化合物在本文中定義為充當相應金屬氧化物來源之化合物。前驅體化合物在熱處理時能夠在非導電基材表面上形成金屬氧化物薄層。通常，在熱處理時形成相應金屬氧化物之所有金屬鹽均適合。熱處理較佳在氧氣存在下。通常不直接施用相應金屬氧化物本身，因為其在水溶液以及有機溶劑中僅具較差之可溶性，且因此難以均勻塗覆至基材表面。
相應氧化物最常藉由熱處理金屬氧化物前驅體化合物來獲得。熱解係一種在氧氣存在下之熱處理過程。金屬氧化物前驅體化合物之熱解導致形成相應金屬氧化物化合物。
典型之金屬氧化物前驅體化合物包含各別金屬之可溶性鹽。金屬氧化物前驅體化合物可為有機金屬鹽且例如為烷氧基化物，例如甲氧基化物、乙氧基化物、丙氧基化物及丁氧基化物、乙酸鹽及乙醯基丙酮酸鹽。或者，金屬氧化物前驅體化合物可為無機金屬鹽，且例如為硝酸鹽、鹵化物，尤其為氯化物、溴化物及碘化物。
金屬氧化物前驅體之金屬選自由鋅、鈦、鋯、鋁、矽及錫或前述各物之混合物組成之群。
如前文提及形成之金屬氧化物選自由ZnO、TiO2、ZrO2、Al2O3、SiO2、SnO2或前述各物之混合物組成之群。
氧化鋅係欲應用於本發明方法中之最佳氧化物化合物。典型之氧化鋅前驅體化合物係乙酸鋅、硝酸鋅、氯化鋅、溴化鋅及碘化鋅。另一種較佳氧化物係氧化鋁。典型之氧化鋁前驅體化合物係鋁之乙酸鹽、硝酸鹽、氯化物、溴化物及碘化物。
金屬氧化物前驅體化合物通常溶解於適合溶劑中，之後塗覆至非導電基材表面。此有利於化合物在基材表面上之均勻表面分佈。適合溶劑包含極性有機溶劑，尤其醇類，如乙醇、丙醇、異丙醇、甲氧基-乙醇或丁醇。
其他極性有機溶劑包含諸如1-甲氧基-2-丙醇之二醇類的烷基醚，乙二醇、二乙二醇、丙二醇之單烷基醚、酮類(諸如甲基乙基酮、甲基異丁基酮、異佛爾酮)；酯類及醚類(諸如乙酸2-乙氧基乙酯、2-乙氧基乙醇)、芳族物(諸如甲苯及二甲苯)、含氮溶劑(諸如二甲基甲醯胺及N-甲基吡咯啶酮)及前述各物之混合物。
或者，溶劑可為水基溶劑。其亦可為水與有機溶劑之混合物。
尤其在使用水基溶劑時，溶液可另外含有一或多種潤濕劑以改良非導電基材表面之潤濕。適合之潤濕劑或其混合物包括非離子劑，諸如非離子性烷基酚聚乙氧基加合物或烷氧基化聚伸烷基類及陰離子性潤濕劑(諸如有機磷酸酯或膦酸酯)以及以雙十三烷基磺基丁二酸鈉為代表之二酯磺基丁二酸鹽。至少一種潤濕劑之量在溶液之0.0001至5wt.%、更佳在0.0005至3wt.%之範圍內。
金屬乙酸鹽之乙醇溶液係根據本發明之一種較佳實施例，以乙酸鋅之乙醇溶液為最佳。金屬氧化物前驅體化合物可包含不同鹽之混合物，但較佳為僅一種鹽。
或者，金屬氧化物化合物可直接沈積至非導電基材之表面上。 有機溶劑與水性介質均可使用。金屬氧化物化合物通常不易溶解於大多數常用溶劑或水中且因此通常以膠狀分散液之形式塗覆至表面。該等膠狀分散液一般由界面活性劑或聚合物穩定化。熟習此項技術者已知如何製備該等膠狀分散液。
在根據本發明之方法中，較佳沈積金屬氧化物前驅體化合物，因為將前驅體化合物塗覆至表面通常可以更佳地得到控制。隨後將前驅體化合物轉化為相應之金屬氧化物。
至少一種金屬氧化物化合物或金屬氧化物前驅體化合物之濃度較佳在0.005mol/l至1.5mol/l、更佳在0.01mol/l至1.0mol/l且最佳在0.1mol/l至0.75mol/l之範圍內。
根據本發明之含有金屬氧化物化合物或金屬氧化物前驅體化合物之溶液或分散液可藉由諸如浸塗、旋塗、噴塗、簾式塗佈、輥塗、印刷、絲網印刷、噴墨印刷及刷塗之方法塗覆至非導電基材。該等方法在此項技術中已知且可適用於根據本發明之鍍敷方法。該等方法在非導電基材表面上產生具有確定厚度之均勻膜。
金屬氧化物層之厚度較佳為5nm至500nm、更佳為10nm至300nm且最佳為20nm至200nm。
塗覆可進行一次或數次，例如兩次、三次、四次、五次或多達十次。塗覆步驟的數目可變且取決於所需金屬氧化物化合物層之最終厚度。通常三至五個塗覆步驟應足夠。建議在塗覆下一層之前至少部分乾燥由溶液或分散液製成之塗層。適合溫度取決於所用溶劑及其沸點以及層厚度且可由熟習此項技術者藉由常規實驗來選擇。通常150℃至高達350℃之間、較佳200℃與300℃之間的溫度應足夠。在個別塗覆步驟之間對塗層進行此乾燥或部分乾燥係有利的，因為形成了穩定之非晶金屬氧化物以防溶解於含有金屬氧化物化合物或金屬氧化物前驅體化合物及過渡金屬鍍敷催化劑前驅體化合物或過渡金屬鍍敷催化 劑化合物之溶液或分散液的溶劑中。
在步驟i.中與溶液或分散液之接觸時間係歷時10秒鐘至20分鐘、較佳30秒鐘與5分鐘之間且甚至更佳1分鐘與3分鐘之間的時間。塗覆溫度取決於所用之塗覆方法。舉例而言，對於浸塗、輥塗或旋塗方法而言，塗覆溫度一般在5℃至90℃之間、較佳在10℃與80℃之間且甚至更佳在20℃與60℃之間的範圍內。對於噴霧熱解方法而言，溫度一般在200℃至800℃之間、較佳在300℃至600℃之間且最佳在350℃至500℃之間的範圍內。
在步驟ii)中進行加熱。此加熱可在一或多個步驟中進行。在某一階段，需要溫度大於350℃，較佳大於400℃。高溫加熱導致金屬氧化物冷凝而在基材表面上形成機械穩定之金屬氧化物層。此金屬氧化物通常為結晶狀態。對於ZnO而言，此加熱步驟中之溫度較佳等於或超過400℃。
加熱步驟ii)有時亦稱為燒結。燒結係藉由加熱但不使材料熔化至液化點來形成材料之固態機械穩定層的過程。加熱步驟ii)在350℃至1200℃、更佳在350℃至800℃且最佳在400℃至600℃範圍內之溫度下進行。
處理時間較佳為1分鐘至180分鐘、更佳為10分鐘至120分鐘且最佳為30分鐘至90分鐘。
在本發明之一個實施例中，可能使用溫度斜坡進行加熱。此溫度斜坡可為線性或非線性的。線性溫度斜坡在本發明之上下文中應理解為自較低溫度開始連續加熱且使溫度穩定上升直至達到最終溫度。根據本發明之非線性溫度斜坡可包括改變溫度上升速度(亦即，隨時間改變溫度)且可包括無溫度變化之時間且由此使基材保持同一溫度持續一定時間。非線性溫度斜坡亦可包括線性溫度斜坡。無論何種類型之溫度斜坡，其後均可進行無任何溫度變化之最終加熱步驟。在溫 度斜坡之後，可使基材例如在500℃下保持1h。
在一個實施例中，非線性溫度斜坡可包括如本文所述之若干個加熱步驟，諸如可選之乾燥步驟及必需之燒結步驟，在彼等步驟之間存在溫度上升。
若將金屬氧化物化合物直接沈積至表面上，則熱處理主要用以將金屬氧化物層轉變為牢固之黏著層，其可另外經燒結以形成非導電基材之相應金屬氧化物緻密層。
不受此理論約束，咸信在金屬氧化物前驅體化合物轉化為相應金屬氧化物後，可能發生金屬氧化物相互擴散至基材中且形成金屬氧化物與基材之橋黏結。亦觀測到金屬氧化物之部分燒結。所形成之金屬氧化物(以金屬氧化物化合物之形式直接塗覆時以及以金屬氧化物前驅體化合物之形式塗覆且在步驟ii.中轉變為相應氧化物化合物時)良好黏附至非導電基材表面。舉例而言，若非導電基材係玻璃基材，則經由OH基團縮合在玻璃基材與金屬氧化物之間形成共價鍵。
非導電基材表面亦與過渡金屬鍍敷催化劑化合物接觸。過渡金屬鍍敷催化劑化合物係金屬氧化物鹽，其中金屬選自銅、鎳及鈷。
過渡金屬鍍敷催化劑化合物最佳為氧化銅。
通常，在熱處理時形成相應金屬氧化物之所有金屬鹽均適合：較佳在氧氣存在下進行熱處理。
過渡金屬鍍敷催化劑化合物之相應金屬氧化物最通常藉由熱處理過渡金屬鍍敷催化劑前驅體化合物來獲得。熱解係最常見的且係一種在氧氣存在下之熱處理。熱解過渡金屬鍍敷催化劑前驅體化合物導致形成各別之金屬氧化物。
典型之過渡金屬鍍敷催化劑前驅體化合物包含各別金屬之可溶性鹽。過渡金屬鍍敷催化劑前驅體化合物可為有機金屬鹽且例如為烷氧基化物(例如甲氧基化物、乙氧基化物、丙氧基化物及丁氧基化 物)、乙酸鹽及乙醯基丙酮酸鹽。或者，過渡金屬鍍敷催化劑前驅體化合物可為無機金屬鹽且例如為硝酸鹽、鹵化物，尤其為氯化物、溴化物及碘化物。
步驟ii.中形成之金屬氧化物較佳選自由CuO、Cu2O、NiO、Ni2O3、CoO、Co2O3或前述各物之混合物組成之群。
在氧化性環境中，更可能存在更高之氧化態。
氧化銅與氧化鎳係應用於根據本發明之方法中的最佳過渡金屬鍍敷催化劑化合物，以氧化銅尤其較佳。典型之銅及鎳前驅體化合物係以下金屬鹽：乙酸鹽、硝酸鹽、氯化物、溴化物、碘化物。
過渡金屬鍍敷催化劑前驅體化合物通常溶解於適合之極性溶劑中，之後塗覆至非導電基材表面。此有利於化合物在基材表面上之均勻表面分佈。適合溶劑包含有機溶劑，尤其醇類，如乙醇、丙醇、異丙醇、甲氧基-乙醇或丁醇。
其他極性有機溶劑包含諸如1-甲氧基-2-丙醇之二醇類的烷基醚，乙二醇、二乙二醇、丙二醇之單烷基醚、酮類(諸如甲基乙基酮、甲基異丁基酮、異佛爾酮)；酯類及醚類(諸如2-乙氧基乙酸乙酯、2-乙氧基乙醇)、芳族物(諸如甲苯及二甲苯)、含氮溶劑(諸如二甲基甲醯胺及N-甲基吡咯啶酮)及前述各物之混合物。
或者，溶劑可為水基溶劑，包括水與有機溶劑之混合物。
尤其在使用水基溶劑時，溶液可另外含有一或多種潤濕劑以改良非導電基材表面之潤濕。適合之潤濕劑或其混合物包括非離子劑，諸如非離子性烷基酚聚乙氧基加合物或烷氧基化聚伸烷基類及陰離子性潤濕劑(諸如有機磷酸酯或膦酸酯)以及以雙十三烷基磺基丁二酸鈉為代表之二酯磺基丁二酸鹽。至少一種潤濕劑之量在溶液之0.0001至5wt.%、更佳在0.0005至3wt.%之範圍內。
金屬乙酸鹽之乙醇溶液係根據本發明之一種較佳實施例，以乙 酸銅及乙酸鎳之乙醇溶液為最佳。過渡金屬氧化物前驅體化合物可包含不同鹽之混合物，但較佳為僅一種鹽。
或者，過渡金屬鍍敷催化劑化合物可直接沈積至非導電基材之表面上。有機溶劑與水性介質均可使用。過渡金屬鍍敷催化劑化合物通常不容易溶解於大多數常用溶劑中且因此通常以膠狀分散液之形式塗覆至表面。該等膠狀分散液一般由界面活性劑或聚合物穩定化。熟習此項技術者已知如何製備該等膠狀分散液。
在根據本發明之方法中，較佳沈積過渡金屬鍍敷催化劑前驅體化合物。
至少一種過渡金屬鍍敷催化劑化合物或過渡金屬鍍敷催化劑前驅體化合物之濃度較佳在0.005至1.5mol/l、更佳在0.01至1.0mol/l且最佳在0.1至0.75mol/l之範圍內。
本發明含義內之過渡金屬鍍敷催化劑化合物意謂可由如甲醛、次磷酸鹽、乙醛酸、DMAB(二甲胺基硼烷)或NaBH4之還原劑還原為其金屬形式的含金屬離子化合物。本發明者已發現，該等金屬氧化物化合物可例如由上文提及之還原劑還原為其金屬形式。因此，金屬氧化物較佳作為根據本發明之方法中之過渡金屬鍍敷催化劑化合物。
在使用過渡金屬鍍敷催化劑前驅體化合物之實施例2中，根據本發明用於在非導電基材表面之至少一部分上沈積金屬氧化物化合物及過渡金屬鍍敷催化劑化合物之方法包含：2.i. 使基材與適合於在熱處理時形成金屬氧化物化合物及過渡金屬鍍敷催化劑化合物之金屬氧化物前驅體化合物及過渡金屬鍍敷催化劑前驅體化合物接觸；且其後2.ii. 如上所述熱處理非導電基材且由此在基材表面之至少一部分上形成來自金屬氧化物前驅體化合物之金屬氧化物化合物與來自過渡金屬鍍敷催化劑前驅體化合物之過渡金屬鍍敷催化劑化合物的黏著 性催化層；且其後2.iii. 藉由應用濕式化學無電電鍍方法至少金屬鍍敷具有過渡金屬鍍敷催化劑化合物之基材表面，其中用於鍍敷之組合物包含待鍍敷之金屬離子的來源及還原劑。
在本發明之一個實施例中，向非導電基材上沈積金屬氧化物化合物作為第一層且其後沈積過渡金屬鍍敷催化劑化合物作為第二層。在此實施例中，重要的係過渡金屬鍍敷催化劑形成頂層，因為在後續金屬鍍敷步驟iii.中，無電金屬層僅沈積至過渡金屬鍍敷催化劑層之層上。
在本發明之實施例3中，如下進行金屬氧化物化合物與過渡金屬鍍敷催化劑化合物之沈積：3.i. 在非導電基材表面之至少一部分上較佳以分散液之形式沈積選自由氧化鋅、氧化鈦、氧化鋯、氧化鋁、氧化矽及氧化錫或前述各物之混合物組成之群之金屬氧化物化合物，3.ii. 視情況如上所述熱處理非導電基材且由此形成金屬氧化物化合物之黏著層；3.iii. 在非導電基材表面之至少一部分上沈積選自由氧化銅、氧化鎳、氧化鈷及前述各物之混合物組成之群之過渡金屬鍍敷催化劑化合物，且其後3.iv. 如上所述熱處理非導電基材且由此形成金屬氧化物化合物之黏著層(若上文之步驟ii.省略)及過渡金屬鍍敷催化劑化合物之催化層；且其後3.v. 藉由應用濕式化學無電電鍍方法至少金屬鍍敷具有過渡金屬鍍敷催化劑化合物之基材表面，其中用於鍍敷之組合物包含待鍍敷之金屬離子的來源及還原劑。
在實施例4中，根據本發明之方法包含在非導電基材表面之至少 一部分上沈積金屬氧化物化合物及過渡金屬鍍敷催化劑化合物，其中：4.i. 使至少一部分基材與選自由氧化鋅、氧化鈦、氧化鋯、氧化鋁、氧化矽及氧化錫或前述各物之混合物組成之群之金屬氧化物化合物或適合於在熱處理時形成金屬氧化物化合物之金屬氧化物前驅體接觸；且其後4.ii. 視情況如上所述熱處理非導電基材且由此在基材表面之至少一部分上形成金屬氧化物化合物之黏著層；且其後4.iii. 使基材與選自由氧化銅、氧化鎳及氧化鈷及前述各物之混合物組成之群之過渡金屬鍍敷催化劑化合物或適合於在熱處理時形成過渡金屬鍍敷催化劑化合物之過渡金屬鍍敷催化劑前驅體化合物接觸；且其後4.v. 如上所述熱處理非導電基材且由此在基材表面之至少一部分上形成金屬氧化物化合物之黏著層(若上文之步驟ii.省略)及過渡金屬鍍敷催化劑化合物之催化層；且其後4.vi. 藉由應用濕式化學無電電鍍方法至少金屬鍍敷具有過渡金屬鍍敷催化劑化合物之基材表面，其中用於鍍敷之組合物包含待鍍敷之金屬離子的來源及還原劑。
如上所述之熱處理可個別地在實施例3或4中之每一接觸步驟i.及iii.之後進行或在將過渡金屬鍍敷催化劑化合物塗覆至非導電基材之後進行。
在本發明之另一實施例中，使非導電基材同時與含有金屬氧化物化合物或金屬氧化物化合物前驅體化合物及過渡金屬鍍敷催化劑化合物或過渡金屬鍍敷催化劑前驅體化合物之溶液或分散液接觸。其後，如上所述進行熱處理並轉化為相應之金屬氧化物。
金屬氧化物化合物與過渡金屬鍍敷催化劑化合物之比率可在寬 範圍內變化且取決於如電導率、所用金屬等諸多因素。熟習此項技術者可經常規實驗確定最佳比率。在所形成之組合物中具有小於50wt.%之過渡金屬鍍敷催化劑化合物常已足夠。金屬氧化物化合物與過渡金屬鍍敷催化劑化合物之比率的典型範圍在5至95wt.%金屬氧化物化合物之間變化且其餘為過渡金屬鍍敷催化劑化合物，更佳在20至90wt.%之間且甚至更佳在40與75wt.%之間。ZnO(金屬氧化物化合物)與CuO(過渡金屬鍍敷催化劑化合物)之典型混合物含有5至95wt.%之間的金屬氧化物化合物，其餘為過渡金屬鍍敷催化劑化合物，更佳為20至90wt.%之間的ZnO且甚至更佳40與75wt.%之間的ZnO，其餘為CuO。
該方法視情況可包含在方法步驟ii之後進行之另一步驟。
iia. 使基材與酸性水溶液或鹼性水溶液接觸。
此額外步驟使平均表面粗糙度(Sa)增加約10nm至50nm，但不超過增加100nm。所增加之粗糙度在一定範圍內以增加金屬層對於非導電基材表面之黏著性，但不負面影響其功能。
酸性水溶液較佳為pH值在pH=1至5之間的酸性水溶液。可使用各種酸，例如硫酸、鹽酸或如乙酸之有機酸。
或者，鹼性水溶液係pH值在pH=10至14之間的鹼性水溶液。可使用各種鹼性來源，例如氫氧化物鹽，如氫氧化鈉、氫氧化鉀、氫氧化鈣或碳酸鹽。
其後，在步驟iii.中應用濕式化學鍍敷方法對具有催化層之非導電基材表面進行金屬鍍敷。
濕式化學鍍敷方法為熟習此項技術者所熟知。典型之濕式化學鍍敷方法係施用外電路電流之電解電鍍、使用待沈積金屬與基材表面上之金屬之氧化還原電勢差異之浸漬電鍍或使用鍍敷溶液中所含化學還原劑之無電電鍍方法。
在本發明之一較佳實施例中，濕式化學鍍敷方法係一種無電電鍍方法，其中用於鍍敷之組合物包含待鍍敷之金屬離子的來源及還原劑。
對於無電電鍍而言，使基材與例如含有Cu-、Ni-、Co-或Ag-離子之無電電鍍浴接觸。典型還原劑包含甲醛、如次磷酸鈉之次磷酸鹽、乙醛酸、DMAB(二甲胺基硼烷)或NaBH4。
該鍍敷溶液將與非導電基材表面上之過渡金屬鍍敷催化劑化合物反應。若過渡金屬鍍敷催化劑化合物係非導電基材表面上所含之金屬氧化物，則其將由無電電鍍溶液中所含之還原劑還原。熟習此項技術者將選擇能夠還原金屬氧化物形式之過渡金屬鍍敷催化劑化合物的適合試劑。藉由此還原反應，在非導電基材表面上形成第一薄層金屬。此層充當所謂成核位點。來自無電電鍍浴之其他金屬離子經浴中所含之還原劑還原且由此沈積在成核位點上，致使金屬層厚度增長。
藉由錨定在塗層本身中，此等成核位點為後續鍍敷之無電金屬層提供強黏著性。
無電金屬鍍敷溶液較佳為包含適合於沈積相應金屬或金屬合金之組合物的銅、銅合金、鎳或鎳合金浴。
銅或銅合金最佳在濕式化學沈積期間沈積，無電電鍍係用於濕式化學金屬沈積之最佳方法。
銅無電電鍍電解質通常包含銅離子來源、pH改質劑、錯合劑(諸如EDTA)、烷醇胺或酒石酸鹽、加速劑、穩定劑添加劑及還原劑。在大多數情形下，使用甲醛作為還原劑，其他常用還原劑為次磷酸鹽、二甲胺基硼烷及硼氫化物。用於無電鍍銅電解質之典型穩定劑添加劑係諸如以下之化合物：巰基苯并噻唑、硫脲、各種其他硫化合物、氰化物及/或亞鐵氰化物及/或鈷氰化物鹽、聚乙二醇衍生物、雜環氮化合物、甲基丁炔醇及丙腈。另外，通常藉由使穩定空氣流穿過銅電解 質而使用分子氧作為穩定劑添加劑(ASM手冊，第5卷：Surface Engineering，第311至312頁)。
用於無電金屬及金屬合金鍍敷電解質之另一重要實例係用於沈積鎳及其合金之組合物。該等電解質常基於作為還原劑之次磷酸鹽化合物且另外含有選自包含VI族元素(S、Se、Te)化合物、含氧陰離子(AsO2 -、IO3 -、MoO4 2-)、重金屬陽離子(Sn2+、Pb2+、Hg+、Sb3+)及不飽和有機酸(順丁烯二酸、衣康酸)之群的穩定劑添加劑之混合物(Electroless Plating：Fundamentals and Applications，編者：G.O.Mallory,J.B.Hajdu,American Electroplaters and Surface Finishers Society，翻印版，第34至36頁)。
在後續加工步驟中，無電沈積之金屬層可進一步結構化至電路中。
在本發明之一個實施例中，藉由在步驟iii中獲得之第一金屬或金屬合金層之上電鍍來沈積至少另一層金屬或金屬合金。
應用濕式化學鍍敷方法對基材進行金屬鍍敷之一種尤其較佳之實施例包含：iiib. 使基材與無電金屬鍍敷溶液接觸；及iiic. 使基材與電解金屬鍍敷溶液接觸。
對於電解金屬化而言，在步驟iiic.中可能使用任何需要之電解金屬沈積浴，例如用於沈積鎳、銅、銀、金、錫、鋅、鐵、鉛或其合金。該等沈積浴為熟習此項技術者所熟悉。
一般使用瓦特鎳浴(Watts nickel bath)作為亮鎳浴，此浴包含硫酸鎳、氯化鎳及硼酸，且亦包含糖精作為添加劑。用作亮銅浴之組合物的實例係包含硫酸銅、硫酸、氯化鈉及有機硫化合物(其中硫為低氧化態，例如有機硫化物或二硫化物)作為添加劑之組合物。
本發明者已發現，熱處理沈積金屬層極大地增加了金屬層與下 層非導電基材之剝離強度(PS)。增加程度令人驚訝。該熱處理亦稱作退火。退火係一種改變金屬之材料特性的已知處理方法，且例如增加其延展性、釋放內部應力且藉由使其均勻而改進金屬結構。不明顯的係該退火亦導致沈積金屬層與非導電基材表面之間的剝離強度大幅增加。
根據本發明之方法，在最後之金屬鍍敷步驟之後，在步驟iv.中進行該熱處理：iv. 將金屬鍍層加熱至150℃與500℃之間的溫度。
對於此熱處理而言，將基材緩慢加熱至150℃與500℃之間的最大溫度，較佳高達400℃之最大溫度且甚至更佳高達350℃之最大溫度。處理時間視基材材料、鍍敷金屬及鍍敷金屬層之厚度而變化且可由熟習此項技術者由常規實驗來確定。處理時間通常在5分鐘與120分鐘之間、較佳在10分鐘與60分鐘之間的範圍內，且甚至更佳至多20分鐘、30分鐘或40分鐘之處理時間即足夠。
甚至更有利的係在兩個、三個或甚至更多個步驟中進行熱處理，相繼增加在個別步驟期間之保持溫度。該逐步處理導致鍍敷金屬層與非導電基材之間的剝離強度值尤其高。
典型溫度概況可如下：a)100℃至200℃歷時10分鐘至60分鐘，且其後150℃至400℃歷時10分鐘至120分鐘，或b)100℃至150℃歷時10分鐘至60分鐘，且其後視情況150℃至250℃歷時10分鐘至60分鐘，且其後230℃至500℃歷時10分鐘至120分鐘。
若根據本發明之方法包含無電金屬鍍敷步驟及電解金屬鍍敷步驟，則建議在每一金屬鍍敷步驟後應用熱處理步驟。無電金屬鍍敷步驟後之熱處理可如上所述進行。通常在高達100℃與250℃之間的最大 溫度下進行單步驟熱處理歷時10分鐘至120分鐘已足夠。
實例
以下實驗欲說明本發明之益處，而不限制其範疇。術語基材與樣品在本文中可互換使用。
通用程序：對於黏著性測試目的而言，以15μm銅進一步電解鍍敷無電金屬層且其後在180℃溫度下加熱30分鐘。使鍍銅層經受90°角剝離強度測試。在黏著性不足之情形下，額外之銅厚度強烈增加黏著性界面破壞之可能性。
在實例中，採用如表1中列舉及識別之金屬氧化物前驅體化合物(MO)及鍍敷催化劑(MeO)。
實例1(比較性)
此實例中使用以下三種市售樣品(全部：1.5×4.0cm載片)：
●硼矽酸玻璃(Sa<10nm)。
●晶圓基材，Si/SiO2(Sa<10nm)，表面覆蓋有厚度為約75至85nm之SiO2層，
●陶瓷基材，Al2O3(Sa=450nm)。
如下文所述清潔及處理樣品。
使基材與含有50ppm Pd離子及2.5g/L SnCl2之市售Pd/Sn催化劑(Adhemax® Activator,Atotech Deutschland GmbH)在25℃之溫度下接觸5分鐘，繼而進行去離子水沖洗及加速步驟(Adhemax® Accelerator,Atotech Deutschland GmbH)用於增加Pd催化劑之催化活性。
此後，在37℃下將樣品完全浸沒於含有硫酸銅作為銅離子來源及甲醛作為還原劑之無電鍍Cu浴中歷時4分鐘，產生約0.25μm銅金屬之鍍敷厚度。使樣品在120℃下乾燥10分鐘且隨後在180℃之溫度下加熱30分鐘。
藉由使Scotch膠帶(剝離強度為約2N/cm)附著於無電銅層來測試 鍍層之黏著性。若可自銅金屬層移除膠帶而不剝除金屬層，則金屬層之黏著強度超過2N/cm。
在藉由快速移動剝除沈積銅金屬層之彼等情形下，該層與下層基材之黏著強度低於2N/cm。對於所有三種樣品類型而言，均觀測到無電銅層與基材完全分離(參見表1，第6行)。
如上所述製備第二樣品且藉由電解(酸性)鍍銅沈積另一銅金屬層。
為此，使用含有硫酸銅作為銅離子來源及硫酸以及專用勻塗劑及增亮劑化合物之酸性鍍銅浴(Cupracid,Atotech Deutschland GmbH)。在1.5ASD之電流密度下進行鍍敷，產生具有15μm厚度之鍍銅層。在基材材料上基本上不形成導致鍍敷金屬層完全分層之黏著性金屬層。
實例2
使用以下三種市售樣品(全部：1.5×4.0cm載片)：
●玻璃(Sa<10nm)。
●晶圓基材，Si/SiO2(Sa<10nm)，表面覆蓋有厚度為約75至85nm之SiO2層，
●陶瓷基材，Al2O3(Sa=450nm)。
清潔後，樣品藉由噴霧熱解相繼塗有ZnO及CuO層。首先，藉由手持式氣刷裝置向在400℃溫度下加熱之基材上噴射含有0.05mol/l Zn(OAc)2×2H2O之金屬氧化物前驅體化合物之EtOH溶液(噴霧熱解)。隨後，在400℃溫度下進行含有0.05mol/l Cu(OAc)2×H2O之過渡金屬鍍敷催化劑前驅體化合物之EtOH溶液的另一噴霧熱解。
隨後使基材在500℃溫度下在空氣中加熱60分鐘。所形成之ZnO金屬氧化物層之厚度為約150nm，所形成之CuO層之厚度為約30nm。
燒結後，在37℃溫度下將樣品在含有硫酸銅作為銅離子來源且含有甲醛作為還原劑之無電鍍Cu浴中處理15分鐘。選擇性地在覆蓋有ZnO及CuO之非導電基材部分上形成厚度為1μm之銅層。
逐步使樣品在120℃溫度下加熱(退火)10分鐘，且隨後在180℃溫度下加熱(退火)30分鐘。藉由使PI膠帶(剝離強度為約5N/cm)附著於無電Cu層且藉由快速移動將其剝除來測試鍍層之黏著性。無電銅層未與經塗佈之基材分離。在所有情形下，銅層與下層基材之黏著性均超過5N/cm(參見表1，第7行)。
其後，在1.5ASD之電流密度下鍍敷酸銅(Cupracid,Atotech Deutschland GmbH)直至厚度為15μm。逐步使樣品首先在120℃溫度下加熱(退火)10分鐘，且隨後在180℃溫度下加熱(退火)30分鐘。
未觀測到銅與基材分離(諸如起泡)。玻璃基材之剝離強度為0.7N/cm，對於Si/SiO2基材而言為0.8N/cm且對於Al2O3而言為6.7N/cm(參見表1，第8行)。
在260℃下回焊處理所有基材之後，所有基材均未起泡且保持初始之剝離強度值。進行此回焊測試來模擬回焊期間之組件附著熱應力。由於未發生起泡且保持初始之剝離強度，故測試通過(參見表1，第9行)。
實例3
使用以下三種市售樣品(全部：1.5×4.0cm載片)：
●玻璃(Sa<10nm)。
●晶圓基材，Si/SiO2(Sa<10nm)，表面覆蓋有厚度為約75至85nm之SiO2層，
●陶瓷基材，Al2O3(Sa=450nm)。
清潔後，樣品藉由噴霧熱解塗有混合之ZnO/CuO膜。
藉由手持式氣刷裝置向加熱至400℃溫度之非導電基材上噴射 0.025mol/l Zn(OAc)2×2H2O(金屬氧化物前驅體化合物)與0.025mol/l Cu(OAc)2×H2O(過渡金屬鍍敷催化劑前驅體化合物)之EtOH溶液。
隨後使基材在500℃溫度下在空氣中燒結60分鐘。由此獲得之混合ZnO/CuO金屬氧化物層之厚度為約100nm。
燒結後，在37℃溫度下將樣品浸沒於無電鍍Cu浴(含有硫酸銅作為銅離子來源且含有甲醛作為還原劑)中歷時15分鐘。選擇性地在覆蓋有ZnO及CuO層之非導電基材部分上形成厚度為1μm之銅層。
逐步使樣品首先加熱(退火)至120℃之溫度歷時10分鐘，且隨後加熱(退火)至180℃之溫度歷時30分鐘。藉由使PI膠帶(剝離強度為約5N/cm)附著於無電Cu層且藉由快速移動將其剝除來測試鍍層之黏著性。無電銅層未與經塗佈之基材分層。銅層與下層基材之黏著性超過5N/cm(參見表1，第7行)。
其後，在1.5ASD之電流密度下鍍敷酸銅(Cupracid,Atotech Deutschland GmbH)直至厚度為15μm。逐步使樣品首先加熱(退火)至120℃之溫度歷時10分鐘，且隨後加熱(退火)至180℃之溫度歷時30分鐘。
未觀測到銅與基材分離(諸如起泡)。玻璃基材之剝離強度為0.5N/cm，對於Si/SiO2基材而言為0.5N/cm且對於Al2O3而言為2.0N/cm(參見表1，第8行)。
在260℃下回焊處理所有基材之後，無起泡且保持初始之剝離強度值。因此，當該等要求均滿足時，測試通過(參見表1，第9行)。
表1展示實例中獲得之結果。MeO催化性/黏著性類型與基材上之金屬氧化物化合物及過渡金屬鍍敷催化劑化合物(第2行)相關。第4行中之MO厚度提供第二行中所列組合層的總厚度。由根據本發明之方法鍍金屬之所有樣品均展示金屬層與下層非導電或半導體基材之良好黏著性，而實質上不增加基材在金屬化前之粗糙度。
表1第7行中之術語「通過」代表黏著強度等於或超過5N/cm。第6行中之術語「失敗」應理解為黏著強度值小於2N/cm。
由來自IMADA之數位測力計及剝離強度測試儀進行90°剝離強度量測。所有樣品之黏著值在表1第8行中描繪。
藉由Olympus LEXT 4000共焦雷射顯微鏡上之梯級高度來確定金屬與金屬氧化物膜之層厚度。在120μm×120μm之表面積上收集粗糙度值。

Claims (13)

  1. 一種用於向非導電基材上鍍敷金屬之濕式化學方法，其包含以下步驟：i.在該非導電基材表面之至少一部分上沈積選自由氧化鋅、氧化鈦、氧化鋯、氧化鋁、氧化矽及氧化錫或前述各物之混合物組成之群之金屬氧化物化合物及選自由氧化銅、氧化鎳及氧化鈷及前述各物之混合物組成之群之過渡金屬鍍敷催化劑化合物，且其後ii.在350℃至1200℃範圍內之溫度下熱處理該非導電基材且由此在該基材表面之至少一部分上形成該金屬氧化物化合物與該過渡金屬鍍敷催化劑化合物之黏著性催化層；且其後iii.藉由應用濕式化學無電電鍍方法至少金屬鍍敷該具有該過渡金屬鍍敷催化劑化合物之基材表面，其中該用於鍍敷之組合物包含待鍍敷之金屬離子的來源及還原劑；且其後iv.將金屬鍍層加熱至150℃與500℃之間的溫度。
  2. 如請求項1之方法，其中該金屬氧化物化合物係選自由ZnO、TiO2、ZrO2、Al2O3、SiO2、SnO2或前述各物之混合物組成之群。
  3. 如請求項1或2之方法，其中該過渡金屬鍍敷催化劑化合物係選自由CuO、Cu2O、NiO、Ni2O3、CoO、Co2O3或前述各物之混合物組成之群。
  4. 如請求項1或2之方法，其中該金屬氧化物化合物與該過渡金屬鍍敷催化劑化合物係同時沈積至該基材表面上。
  5. 如請求項1或2之方法，其中該金屬氧化物化合物與該過渡金屬鍍敷催化劑化合物係以膠狀分散液之形式沈積至該基材表面 上。
  6. 如請求項1或2之方法，其中該非導電基材係陶瓷、半導體或玻璃基材。
  7. 如請求項1之方法，其中在該非導電基材表面之至少一部分上沈積金屬氧化物化合物及該過渡金屬鍍敷催化劑化合物包含：i.使該基材與適於在熱處理時形成該金屬氧化物化合物及該過渡金屬鍍敷催化劑化合物之金屬氧化物前驅體化合物及過渡金屬鍍敷催化劑前驅體化合物接觸，且其後ii.在350℃至1200℃範圍內之溫度下熱處理該非導電基材且由此在該基材表面之至少一部分上形成來自該金屬氧化物前驅體化合物之金屬氧化物化合物與來自該過渡金屬鍍敷催化劑前驅體化合物之過渡金屬鍍敷催化劑化合物的黏著性催化層。
  8. 如請求項7之方法，其中該金屬氧化物前驅體化合物及該過渡金屬鍍敷催化劑前驅體化合物係選自由金屬甲氧基化物、乙氧基化物、丙氧基化物、丁氧基化物、乙酸鹽、乙醯基丙酮酸鹽硝酸鹽、氯化物、溴化物及碘化物組成之群。
  9. 如請求項1或7之方法，其中在方法步驟ii.之後進行另一方法步驟：iia.使該基材與酸性水溶液或鹼性水溶液接觸。
  10. 如請求項1或7之方法，其中該基材係非導電或半導體基材且該步驟iii.應用濕式化學鍍敷方法金屬鍍敷該基材；包含：iiib.使該基材與包含待鍍敷之金屬離子的來源及還原劑之無電金屬鍍敷水溶液接觸；及iiic.使該基材與電解金屬鍍敷溶液接觸。
  11. 如請求項1或7之方法，其中該無電金屬鍍敷溶液係鍍鎳或鍍銅溶液。
  12. 如請求項10之方法，其中該電解金屬鍍敷溶液係鍍鎳或鍍銅溶液。
  13. 如請求項1之方法，其中該步驟iv.中之加熱時間在5至120分鐘之範圍內。
TW103133644A 2013-09-26 2014-09-26 用於基材表面金屬化之新穎黏著促進劑 TWI651432B (zh)

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