TW201520382A - 用於基材表面金屬化之新穎黏著促進方法 - Google Patents

用於基材表面金屬化之新穎黏著促進方法 Download PDF

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TW201520382A
TW201520382A TW103133645A TW103133645A TW201520382A TW 201520382 A TW201520382 A TW 201520382A TW 103133645 A TW103133645 A TW 103133645A TW 103133645 A TW103133645 A TW 103133645A TW 201520382 A TW201520382 A TW 201520382A
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Taiwan
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substrate
metal
plating
metal oxide
layer
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TW103133645A
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English (en)
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TWI631241B (zh
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Zhiming Liu
Hai-Luo Fu
Sara Hunegnaw
Lutz Brandt
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Atotech Deutschland Gmbh
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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
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
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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
    • C03C17/3642—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 the multilayer coating containing a metal layer
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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
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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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    • 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
    • C23C18/1229—Composition of the substrate
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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
    • 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
    • C23C18/02—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
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1258—Spray pyrolysis
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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
    • 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
    • C23C18/02—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
    • C23C18/125—Process of deposition of the inorganic material
    • C23C18/1295—Process of deposition of the inorganic material with after-treatment of the deposited inorganic 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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    • 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。該方法施用經活化且隨後鍍敷金屬之金屬氧化物黏著促進劑。該方法提供非導電基材對於鍍敷金屬層之高黏著性。

Description

用於基材表面金屬化之新穎黏著促進方法
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。一種典型應用領域係高級封裝工業。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。通常對基材表面進行清潔預處理，之後進行濕式化學鍍敷方法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。隨著引入更高級之技術，迄今所用之有機基材因其相對較差之尺寸穩定性及共面性而不太 適合，此就輸入/輸出(I/O)間距而言使其受限。由矽或玻璃製得之無機中介層使得中介層之熱膨脹係數與矽晶片可直接匹配。矽具有成熟之製造基地，但與玻璃相比仍具有一些不利情況。特定而言，玻璃本身具有比矽優越之電學特性且提供了使用較大面積面板尺寸的可能性，此導致相對於基於晶圓之平台而言顯著節約成本。用於使銅與玻璃良好黏著之可靠鍍敷技術係在電子封裝市場上使用玻璃基材之重要先決條件。
然而，此存在挑戰性，因為使表面粗糙度<10nm之極光滑玻璃金屬化比在有機基材上鍍敷顯著更具挑戰性。測試僅取決於自基材粗糙化進行機械錨定之方法的黏著效能。
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射頻識別(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。
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。
EP 2 602 357 A1係關於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。該方法在金屬化之前施用包含奈米尺寸氧化物粒子之新穎黏著促進劑。該等粒子係選自具有至少一個帶有適合於與基材結合之化學官能基之連接基團的二 氧化矽、氧化鋁、二氧化鈦、氧化鋯、氧化錫及氧化鋅粒子中之一或多者。該等粒子藉由具有至少一個帶有適合於與基材結合之化學官能基之連接基團而官能化。此等奈米尺寸粒子附著至基材且在後續金屬鍍層附著至基材表面之前保持化學性質不變。
JP H05-331660 A係關於在具有氧化鋅層之基材上形成氧化銅膜。該方法包含以下步驟：i)向基材表面塗覆乙酸鋅溶液，ii)向基材表面上沈積銅層，iii)在約300至500℃溫度下在含氧氛圍中使鍍銅層氧化以形成氧化銅，iv)部分還原銅表面及v)形成電解銅塗層。該方法並非係針對形成用於促進黏著之金屬氧化物層。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。
此外，該等方法傾向於在基材製備中需要額外步驟，該等步驟對於均勻之表面粗糙度而言一般不容易控制。
此外，玻璃(CTE=3-8ppm)與後續鍍敷之金屬(一般為銅(CTE=約16ppm))之間的較大CTE(熱膨脹係數)失配問題尚未解決，此通常導致與裸玻璃分層。
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銅的合適黏著促進劑。
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(較佳為銅)對於基材材料之高黏著性且由此形成持久黏結，而實質上不增加表面之粗糙度。
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。
該等目標藉由一種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一層選自由氧化鋅、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，且其後ii.加熱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iii.藉由應用濕式化學鍍敷方法至少金屬鍍敷具有金屬氧化物化合物之黏著層的基材表面；且其後iv.將金屬鍍層加熱至150與500℃之間的最大溫度。
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。根據本發明之方法獲得金屬氧化物薄層，其可用作牢固之具有成本效益之黏著層，尤其適合極光滑之玻璃基材。
圖1展示具有根據本發明方法獲得之氧化鋅層之玻璃基材的FIB影像。在FEI Helios NanoLab 650 Dual Beam FIB上進行FIB/SEM分析。用於FIB切割之所關注區域濺塗有約10nm鈀(Pd，其為進行FIB量測所需)。
圖2展示具有根據本發明方法獲得之氧化鋅層及後續無電電鍍銅層之玻璃基材的FIB影像。圓圈指示銅滲透氧化鋅層之奈米孔，此使得玻璃基材與金屬層之間可強烈化學黏結。在FEI Helios NanoLab 650 Dual Beam FIB上進行FIB/SEM分析。用於FIB切割之所關注區域濺塗有約10nm鈀(Pd，其為進行FIB量測所需)。
圖3展示玻璃基材上之金屬鍍層之黏著強度相對於根據本發明之 方法(具有氧化鋅金屬層)及對照例實例(無氧化鋅金屬層)處理之基材的表面粗糙度之關係曲線。柱狀體中展示最大值(上線)及平均值(下線)。
圖4以示意圖形式展示界面層形成。金屬氧化物已沈積於玻璃基材上且隨後進行後續燒結。金屬氧化物由此變成結晶且在基材與金屬氧化物層之間形成金屬、二氧化矽與氧化物之三元合金的界面層。
圖5展示鍍銅層之黏著強度與金屬氧化物層厚度之依賴性。
圖6展示對於分別在步驟ii)中在300℃下加熱3h(圖底部)、在400℃下加熱1h(圖中間)及在500℃下加熱1h(圖頂部)之三種不同基材而言，在具有Cu k-α輻射源(波長1.54A)之SIEMENS D500儀器(現為Bruker AXS)上獲得之正入射X光繞射(XRD)光譜。該等信號係指分別在31.8、34.5及36.3 2θ下之ZnO平面定向100、002及101。在300℃下燒結3h之基材不展示結晶且允許0N/cm之剝離強度。在400℃下燒結1h之基材產生1.5N/cm之剝離強度且展示一定程度之結晶，而在500℃下燒結1h之基材大部分結晶且產生6N/cm之剝離強度。
然而，相對強度與關於「非定向」ZnO粉末之JCPDS(粉末繞射標準聯合委員會，joint committee of powder diffraction standards)資料庫中所引用之彼等強度不同，其中101信號展示最高強度。在本發明中，總是002信號具有最高強度之事實表示結晶之較佳定向。
信號強度隨燒結溫度增加而增加亦指示ZnO層之結晶度的增加程度。因此，燒結溫度與結晶度及可達成之剝離強度直接相關。對於此組實驗條件而言，建議約400℃之較佳燒結溫度用於形成機械穩定ZnO層。根據實例3c，使用不同之ZnO燒結溫度來加工樣品。
本發明提供一種用於非導電基材金屬化之金屬鍍敷方法。
適合以根據本發明之鍍敷方法進行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、玻璃-陶瓷材料、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。以根據本發明之方法處理玻璃基材尤其較佳，尤其處理表面粗糙度小於50nm之光滑玻璃。
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。
具有該光滑表面且Sa值為0.1至200nm之基材(諸如玻璃及晶圓基材)尤其較佳。最佳為玻璃基材。
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30min，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。前驅體化合物在加熱時能夠在非導電基材表面上形成金屬氧化物薄層。通常，在加熱時形成相應金屬氧化物之所有金屬鹽均適合。加熱較佳在氧氣存在下。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加熱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。
金屬氧化物前驅體化合物與根據EP 2 602 357 A1之奈米尺寸氧化物粒子之不同之處在於未經具有至少一個帶有適合於與基材結合之化學官能基之連接基團官能化。
金屬氧化物前驅體化合物之金屬係選自由鋅、鈦、鋯、鋁、矽及錫或前述各物之混合物組成之群。
金屬氧化物化合物或金屬氧化物前驅體化合物可通常以10-9至10wt.%之含量摻雜有鍺、鋁、硼、砷或磷。該摻雜為熟習此項技術者所 熟知且使金屬氧化物層之電導率增加。當電導率足夠高時，金屬氧化物層可由此項技術中已知且在本文中描述之濕式化學鍍敷方法直接電鍍。
在上述步驟ii.中形成之金屬氧化物化合物較佳選自由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金屬氧化物化合物。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。適合溶劑包含水、極性有機溶劑，尤其醇類，如乙醇、丙醇、異丙醇、甲氧基-乙醇或丁醇以及二醇類。
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)以及二酯。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，以乙酸鋅或乙酸鋁為最佳。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。有機溶劑以及水性介質均可使用。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。
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0.005至1.5mol/l、更佳在0.01至1.00mol/l且最佳在0.1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。
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。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藉由移除溶劑至少部分乾燥塗層。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之溶液或分散液的溶劑中。
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(亦參見圖6)。對於ZnO而言，此加熱步驟中之溫度等於或超過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1min至180min、更佳為10至120min且最佳為30至90min。
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到達最終溫度。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。
在塗覆金屬氧化物前驅體化合物來形成金屬氧化物層時，該等步驟較佳包含：
ia.使基材與適合於在加熱時形成金屬氧化物化合物之金屬氧化物前驅體化合物接觸，且其後
ib.加熱非導電基材且由此在基材表面之至少一部分上自金屬氧化物前驅體化合物形成金屬氧化物化合物之黏著層。
在步驟ia)中加熱金屬氧化物前驅體化合物導致轉化為相應金屬氧化物。有時此加熱亦稱為熱解。熱解係在具有或不具有氧氣之情形下，材料在高溫下之熱化學分解。
若金屬氧化物前驅體化合物係含氧化合物，如乙酸鹽，則加熱步驟ia)不必要求存在含氧氛圍，但可以在含氧氛圍中進行。若金屬氧化物前驅體化合物非含氧化合物，如鹵化物，則加熱步驟ia)要求存在含氧氛圍。
若將金屬氧化物前驅體化合物塗覆至基材，則第一次加熱較佳在高溫下(步驟ia)且通常在低於燒結溫度之溫度下進行。溫度範圍取決於欲形成之金屬氧化物、塗覆模式及所用之前驅體化合物。熟習此項技術者將根據此項技術中已知之方法選擇用於特定金屬氧化物及前驅體化合物之適當溫度範圍。
舉例而言，加熱步驟ia)在100至600℃、更佳在150至400℃且最佳在200至300℃之範圍中進行。
處理時間較佳為1min至180min，更佳為10至120min且最佳為20至60min。
以如上所述之溫度及時間進行加熱步驟ii)。
或者，熱解及燒結可在加熱步驟ii中單步驟進行。通常在此情形下，使溫度緩慢增加以在熱解步驟期間例如藉由應用如上所述之溫度斜坡，繼而燒結首先自金屬氧化物前驅體化合物形成金屬氧化物化合物。
非導電基材上之金屬氧化物膜之厚度較佳為5nm至500nm，更 佳為10nm至300nm，最佳為20nm至200nm。
根據本發明方法獲得之金屬氧化物膜之厚度可經優化以例如在具有15μm厚度之鍍銅層上達成約10至12N/cm之極高黏著性。在較低膜厚度(10至50nm)下觀測到對膜厚度之相當依賴性，在約75nm厚度以上可見穩定效能(圖5)。然而，甚至極薄之膜仍提供4至5N/cm以上之黏著值，發現其對於在諸如通孔填充與細線圖案化之下游步驟中之良好效能而言已足夠。
金屬氧化物之結晶尺寸通常具有5至40nm範圍內之平均直徑，較厚之膜傾向於較大尺寸。
不受此理論約束，感信在金屬氧化物前驅體化合物轉化為相應金屬氧化物時，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。
燒結之金屬氧化物層在玻璃上形成機械穩定之多孔層。如由影像處理軟體(ImageJ 1.44o)識別之孔隙率在20-40vol%之範圍內，個別孔之直徑在5至30nm範圍內。孔尺寸通常隨層厚度而增加。此外，多孔結構為電鍍銅提供機械錨定。此強烈相互作用係後續鍍敷之金屬塗層在玻璃上良好黏著之基礎。圖1展示玻璃基材上之金屬氧化物層具有允許後續鍍敷之金屬層(例如，銅)形成機械黏結之奈米多孔結構。此使得玻璃基材與金屬層之間的黏著性增加。此外，銅與金屬氧化物層之產生之相互滲透充當CTE緩衝，克服銅與基材之間的CTE失配。
在分析根據實例5獲得之氧化鋅層時，藉由使SiO2(玻璃基材)擴散至氧化鋅層中形成約10至20nm之相互擴散層，其中形成新物質 ZnSiO3及ZnSiO4(圖4)。藉由此相互擴散，金屬氧化物層與基材共價鍵結。
如下文論述，儘管存在此強烈相互作用，但金屬氧化物層仍可容易在蝕刻劑溶液中自基材移除且與圖案化應用相容。
由此獲得之表面的平均表面粗糙度Sa視加工條件而定在5nm與60nm之間的範圍內。
測試10nm至1000nm之玻璃基材機械粗糙化對玻璃與銅之間的黏著強度的影響。在塗覆金屬氧化物層之前進行粗糙化。對於根據本發明之方法而言，由此預期極有限之影響，因為良好黏著之主要機制並非基於玻璃界面之機械錨定。根據本發明方法處理之樣品展示高於8N/cm之極高剝離強度，無需基材粗糙化(圖3)。該等測試之加工次序係根據實例5中所用及下文描述之次序。在高於8N/cm時，可見剝離強度隨粗糙度升高而適度增加，可能係由於較高之玻璃表面積導致更多用於共價鍵結之位置。未經根據本發明之方法處理且在玻璃基材與金屬層之間不具有金屬氧化物層之對照樣品展示極少黏著至無黏著，而與基材粗糙度無關。
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。
此額外步驟使表面粗糙度增加約10至50nm，但不超過200nm。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。
金屬氧化物層係根據本發明之方法獲得且形成可催化向如玻璃之基材上無電及電解金屬鍍敷(例如)銅之多孔膜。其利用化學及機械錨定來充當例如玻璃與銅之間的中間層。此中間層：(a)在玻璃界面處形成足夠牢固以使鍍敷金屬膜錨定至該界面之強共價鍵；(b)在銅界面處充當多孔機械錨定站以供在上面以高黏著性鍍銅；(c)自金屬氧化物部分至銅界面逐漸增加CTE而充當CTE緩衝區。
其後，在上述步驟iii.中應用濕式化學鍍敷方法對具有黏著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，濕式化學鍍敷方法包含具有以下步驟之無電電鍍方法：
iiia.使基材與包含催化性金屬之水溶液接觸，且其後
iiib.使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。
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。
在步驟iiia中，使具有金屬氧化物化合物黏著層之非導電基材與包含催化性金屬之水溶液接觸。需要催化性金屬(步驟iiia.)來引發根據步驟iiib對金屬層之無電電鍍。
金屬氧化物化合物之黏著層經選自包含銅、銀、金、釕、銠、 鈀、鋨、銥及鉑之群之催化性金屬活化。最佳之催化性金屬係鈀。
催化性金屬可以離子形式或以膠狀體形式沈積至金屬氧化物化合物之黏著層上。
在使用離子形式之催化性金屬時，基材表面僅經活化用於在由金屬氧化物化合物層組成之彼等基材表面區域上進行連續無電電鍍。因此，不需要諸如圖案化光阻劑之遮罩用於步驟iiib.中根據本發明之鍍敷方法的選擇性無電沈積。
在單獨步驟中，藉由使基材與包含還原劑(諸如次磷酸根離子及/或硼烷化合物(諸如硼烷-烷基胺加合物或硼氫化鈉))之溶液(較佳為水溶液)接觸使離子形式之該催化性金屬還原為其金屬狀態。
包含離子形式催化性金屬之活化劑及其用途在此項技術中已知且因此可用於根據本發明之鍍敷方法中。
以膠狀體形式提供之催化性金屬係藉由吸附而沈積至整個基材表面上。若金屬層欲在步驟iiib.中藉由無電電鍍選擇性沈積，則在沈積膠狀體形式之催化性金屬之前，在步驟iiib.中不應沈積金屬層之彼等基材表面部分應以諸如圖案化光阻劑之遮罩遮蓋。若該等部分基材未被遮蓋，則在步驟iiib.中將向整個基材表面上沈積金屬層。在此情形下，在無電電鍍後需要應用蝕刻方法來獲得圖案化之金屬層。
提供離子形式或膠狀體形式之催化性金屬的適用活化劑組合物例如揭示於ASM手冊，第5卷：Surface Engineering，第317至318頁中。
步驟iiib.中之無電金屬鍍敷溶液較佳為適合於沈積相應金屬或金屬合金之銅、銅合金、鎳或鎳合金浴組合物。
銅或銅合金最佳在濕式化學金屬沈積期間沈積，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、二甲基胺硼烷及硼氫化物。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其他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。
在本發明之一替代性實施例中，可在UV光下由無電金屬鍍敷水溶液來沈積金屬層，由此避免催化劑活化步驟且包含以下步驟：
iiia.使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以沈積金屬層且在鍍敷過程期間以UV光照射基材一段時間。
在鍍敷過程期間以UV光照射基材一段時間可意謂照射可在整個鍍敷過程期間或僅在鍍敷過程之初始階段。一般而言，僅在鍍敷過程之第一階段期間照射基材即足夠，例如在鍍敷過程之首個1至5、10、 20或30分鐘期間直至形成金屬之首個成核位點。
UV光之波長可在200nm與450nm之間、較佳在300nm與400nm之間變化。UV光之能量可針對基材來調節且可在寬範圍內變化，例如在0.1至300mW/cm2之間、較佳在1至100mW/cm2之間且最佳在2至75mW/cm2之間。
在本發明之一個實施例中，藉由在步驟iiib.中獲得之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。
在又一實施例中，當沈積之黏著性金屬氧化物層固有地具高導電性時(諸如ZnO/Al2O3)，金屬氧化物層可直接電解電鍍而無需中間無電金屬化步驟：
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，且其後
ii.加熱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；其其後直接
iii.應用濕式化學電解電鍍方法至少金屬鍍敷帶有金屬氧化物化合物黏著層之基材表面，且其後
iv.將金屬鍍層加熱至150與500℃之間的最大溫度。
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移除揮發物及缺陷來純化各層而改進金屬結構。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。另外，本發明亦允許沈積具有良好剝離強度之較厚金屬層，此另外將導致分層。
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℃之間的最大溫度。
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與120分鐘之間、較佳在10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至60min，且其後150至400℃歷時10至120min，或
b)100至150℃歷時10至60min，且其後視情況150至250℃歷時10 至60min，且其後230至500℃歷時10至120min。
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。
處理以下三種市售樣品(全部：1.5×4.0cm載片)：硼矽酸玻璃(Sa<10nm)。
陶瓷基材，Al2O3(Sa=450nm)。
如下文所述清潔及處理樣品。
在實驗中，在表1中列舉且識別不同之實驗條件。
實例1(對照例)
製備連續濺塗有20nm Ti黏著層及400nm Cu晶種層之玻璃樣品(如上所述)。
使Cu濺鍍玻璃樣品在180℃溫度下退火30分鐘且在周圍溫度下以稀硫酸(5%)自氧化物清潔1分鐘。
在1.5 ASD之電流密度下自市售之電解鍍銅浴(Cupracid,Atotech Deutschland GmbH)鍍敷電解(酸)銅直至厚度為15μm且在120℃溫度下歷時10min且其後在180℃溫度下歷時30min逐步退火。對第二基材同樣鍍敷金屬且其後在120℃溫度下歷時10min、其後在180℃下歷時30min且最後在250℃溫度下歷時30min逐步退火。
未觀測到銅與基材分離(諸如起泡)。加熱至180℃溫度之第一樣品展示0.69N/cm之PS(剝離強度或黏著強度)。加熱至250℃溫度之樣品展示1.00N/cm之PS。
實例2(對照例)
如實例1中所述清潔兩種樣品玻璃及陶瓷(Al2O3)。
其後在25℃之溫度下以膠狀體形式之含有50ppm Pd及2.5g/L SnCl2之市售Pd/Sn催化劑(Adhemax Activator,Atotech Deutschland GmbH)處理基材歷時5分鐘，繼而進行去離子水沖洗及典型地用於增加Pd催化劑之催化活性加速步驟(Adhemax Accelerator,Atotech Deutschland GmbH)。
此後，在37℃溫度下將基材完全浸沒於無電鍍Cu浴(含有硫酸銅作為銅離子來源及甲醛作為還原劑)中歷時4分鐘，產生約0.25μm Cu之鍍敷厚度。使樣品首先在120℃溫度下退火10分鐘且隨後在180℃溫度下退火30分鐘。
藉由使Scotch膠帶(約2N/cm)附著於無電Cu層且以90°角快速移動將其剝除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。對於所有樣品類型而言，無電銅層均與基材完全分離，PS低於2N/cm(「失敗」)。
在1.5 ASD之電流密度下，將電解銅(來自可購自Atotech Deutschland GmbH,Cupracid之市售酸性電解鍍銅浴)鍍敷至15μm Cu厚度且導致鍍層完全分層。因此，不進行額外之退火實驗。
實例3
如上所述清潔玻璃基材且以ZnO浸塗。
對於浸塗而言，在周圍溫度下將基材垂直浸沒於0.5mol/l Zn(OAc)2×2H2O之EtOH溶液中且以10cm/min之速度垂直移除。接著將其在250℃之溫度下乾燥15分鐘。重複此過程3次。隨後使基材經受4℃/min之加熱斜坡直至達到500℃之最終溫度。隨後使其在空氣中在500℃之溫度下燒結一小時。ZnO層之厚度為約150nm。
冷卻至周圍溫度後，繼而以含有Na2PdCl4(100ppm)之水溶液處理30秒鐘。此溶液充當無電催化劑溶液。不需要將鈀離子還原為鈀金 屬之還原步驟。
隨後在37℃溫度下使基材完全浸沒於可購自Atotech Deutschland GmbH之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浴中歷時5分鐘，僅在塗佈區域(結構化之基材表面)產生400nm之無電銅層。未塗佈之載片部分保持未鍍敷。
使無電電鍍之樣品首先在120℃溫度下退火10分鐘，且其後在180℃下退火30分鐘。
其後，在1.5 ASD之電流密度下將電解銅(可購自Atotech Deutschland GmbH,Cupracid之市售電解鍍銅浴)鍍敷至15μm之厚度。在退火及不退火之情形下評估黏著性。
對三種樣品以不同之溫度概況逐步進行退火：
a)120℃/10min及180℃/30min
b)120℃/10min、180℃/30min及250℃/30min，及
c)120℃/10min、180℃/30min及350℃/30min。
在電解銅沈積後不退火之情形下，PS僅為約0.3N/cm(量測下限)。使退火樣品冷卻至周圍溫度。在根據概況a)退火後，獲得PS為1.1N/cm之沈積金屬層，在根據概況b)退火後，獲得PS為2.7N/cm之沈積金屬層且在根據概況c)退火後，獲得PS為5.5N/cm之沈積金屬層。此證實退火對剝離強度(PS)之有益作用。
在260℃溫度下回焊後，退火樣品不分層且保持初始之PS。進行此回焊測試來模擬回焊期間之組件附著熱應力。
實例4(UV-活化)
如上所述清潔玻璃基材且以ZnO浸塗。
對於浸塗而言，在周圍溫度下將基材垂直浸沒於0.5mol/l Zn(OAc)2×2H2O之EtOH溶液中且以10cm/min之速度垂直移除。接著將其在250℃之溫度下乾燥15分鐘。重複此過程3次。隨後使基材自室 溫開始經受4℃/min加熱斜坡之加熱步驟直至達到500℃。最後，使其熱解且在空氣中在500℃之溫度下燒結一小時。ZnO層之厚度為約150nm。
隨後在37℃溫度下使基材完全浸沒於可購自Atotech Deutschland GmbH之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，同時以UV光(波長365nm，能量2.65mW/cm2)照射以供活化。10分鐘後關閉UV光。照射期間，在基材上沈積具有足以促進進一步鍍敷之厚度的無電銅薄層。再繼續進行無電鍍Cu 15min，僅在塗佈區域中產生1μm之無電銅層。未塗佈之載片部分保持未鍍敷。
使無電電鍍之樣品首先在120℃溫度下退火10分鐘，且隨後在180℃溫度下退火30分鐘。
其後，在1.5 ASD之電流密度下將電解銅(可購自Atotech Deutschland GmbH,Cupracid之市售電解鍍銅浴)鍍敷至15μm之厚度。在退火及不退火之情形下評估黏著性。
對三種樣品以不同之溫度概況逐步進行退火：
a)120℃/10min及180℃/30min，及
c)120℃/10min、180℃/30min及350℃/30min。
在電解銅沈積後不退火之情形下，PS為約0.3N/cm(量測下限)。
在根據概況a)退火後，獲得PS為1.6N/cm之沈積金屬層，在根據概況c)退火後，獲得PS為6.3N/cm之沈積金屬層。此證實退火對剝離強度(PS)之有益作用。
在260℃溫度下回焊後，退火樣品不分層且保持初始之PS。進行此回焊測試來模擬回焊期間之組件附著熱應力。
實例5
如上所述清潔玻璃基材且以ZnO浸塗。
對於浸塗而言，在周圍溫度下將基材垂直浸沒於0.5mol/l Zn(OAc)2×2H2O之EtOH溶液中且以10cm/min之速度垂直移除。接著將其在250℃之溫度下乾燥15分鐘。重複此過程3次。隨後使基材熱解且在空氣中在500℃之溫度下燒結一小時。ZnO層之厚度為約150nm。
隨後在37℃溫度下使基材完全浸沒於可購自Atotech Deutschland GmbH之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，同時以UV光(波長365nm，能量2.65mW/cm2)照射以供活化。10分鐘後關閉UV光。在此時間期間，在基材上沈積具有足以促進進一步鍍敷之厚度的無電銅薄層。再繼續進行無電鍍Cu 15min，僅在塗佈區域中產生1μm之無電銅層。未塗佈之載片部分保持未鍍敷。
使無電電鍍之樣品首先在120℃溫度下退火10分鐘，且隨後在180℃溫度下退火30分鐘。
其後，在1.5 ASD之電流密度下將電解銅(可購自Atotech Deutschland GmbH,Cupracid之市售電解鍍銅浴)分別鍍敷至15μm與30μm之厚度。此時，具有30μm Cu之基材展示分層且不進一步加工。
以如下溫度概況對具有15μm Cu之基材進行退火：
c)120℃/10min、180℃/30min及350℃/30min。
將其冷卻至周圍溫度且在上文提及之電解鍍銅浴中進一步鍍敷至30μm之總厚度。
未觀測到銅與基材分離(起泡)。測量到7.8N/cm之高PS。此實驗明確證實退火之有益作用且其使得可進一步鍍敷至退火之金屬層上。
在260℃溫度下回焊後，退火樣品不分層且保持初始之PS。進行此回焊測試來模擬回焊期間之組件附著熱應力。
此實驗證實根據本發明之方法能夠在不分層之情形下沈積具有 高於15μm之厚度值(例如30μm)及高剝離強度值之銅金屬。
實例6
如上所述清潔Al2O3陶瓷基材且藉由噴霧熱解以ZnO塗佈。
為此，藉由手持式氣刷裝置向預熱至400℃溫度之陶瓷基材上噴射0.05mol/l Zn(OAc)2×2H2O(金屬氧化物前驅體化合物)之EtOH溶液。
隨後使基材熱解且在空氣氛圍中在500℃溫度下燒結1h。ZnO金屬氧化物層之厚度為約200nm。
隨後在37℃溫度下使基材完全浸沒於可購自Atotech Deutschland GmbH之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，同時以UV光(波長365nm，能量2.65mW/cm2)照射以供活化。10分鐘後關閉UV光。在此時間期間，在基材上沈積具有足以促進進一步鍍敷之厚度的無電銅薄層。再繼續進行無電鍍Cu 15min，僅在塗佈區域中產生1μm之無電銅層。未塗佈之載片部分保持未鍍敷。
使無電電鍍之樣品首先在120℃溫度下退火10分鐘，且其後在180℃下退火30分鐘。
其後，在1.5 ASD之電流密度下將電解銅(可購自Atotech Deutschland GmbH之市售電解鍍銅浴)鍍敷至15μm之厚度。在退火及不退火之情形下評估黏著性。
以不同溫度概況對樣品逐步進行退火：
a)120℃/10min及180℃/30min
c)120℃/10min、180℃/30min及350℃/30min。
在電解銅沈積後不退火之情形下，PS僅為約0.5N/cm(量測下限)。使退火樣品冷卻至周圍溫度。在根據概況a)退火後，獲得PS為4.2N/cm之沈積金屬層，在根據概況c)退火後，獲得PS為8.0N/cm之 沈積金屬層。此證實退火對PS之有益作用。
MO金屬氧化物化合物
通過：PS(剝離強度，亦表示黏著強度)等於或超過2N/cm
失敗：PS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(PS)量測。所有樣品之PS值在表1，PS行7至9中描繪，且該等值另外在實例1至6中提供。
藉由使Scotch膠帶(約2N/cm)附著於Cu層且以90°角快速移動將其剝除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(表1中之「通過」)。若金屬層剝除，則黏著強度低於2N/cm(表1中之「失敗」)。
由根據本發明之方法鍍敷金屬之所有樣品均展示金屬層對於下層非導電基材之良好黏著性。藉由Olympus LEXT 4000共焦雷射顯微鏡上之梯級高度來確定氧化物膜之層厚度。在120μm×120μm之表面積上收集粗糙度值。

Claims (15)

  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一層選自由氧化鋅、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；且其後ii.加熱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之黏著層；且其後iii.藉由應用濕式化學鍍敷方法至少金屬鍍敷該具有該金屬氧化物化合物黏著層之基材表面；且其後iv.將該金屬鍍層加熱至150與500℃之間的最大溫度。
  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，其中該金屬氧化物化合物以10-9至10wt.%之含量摻雜有鍺、鋁、硼、砷或磷。
  4. 如請求項1或2之方法，其中步驟ii.中之該熱處理係在350與1200℃之間的溫度下進行。
  5. 如請求項1或2之方法，其中步驟ii.中之該熱處理係在400與600℃之間的溫度下進行。
  6. 如請求項1或2之方法，其中步驟iv.中之該加熱係在兩個步驟中進行且其中該第一加熱步驟係在高達最大在100與200℃之間的溫度下且該第二加熱步驟係在高達最大在200與500℃之間的溫度下。
  7. 如請求項1或2之方法，其中該步驟 iii.應用濕式化學鍍敷方法金屬鍍敷該基材包含：iiia.使該基材與包含催化性金屬之水溶液接觸，且其後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。
  8. 如請求項1或2之方法，其中該步驟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以沈積金屬層且在該鍍敷過程期間以UV光照射該基材一段時間。
  9. 如請求項8之方法，其中該UV光之波長在200nm與450nm之間的範圍內。
  10. 如請求項1或2之方法，其中該步驟iii.應用濕式化學鍍敷方法金屬鍍敷該基材除步驟iiia.及iiib.以外進一步包含：iiic.使該基材與電解金屬鍍敷溶液接觸。
  11. 如請求項1或2之方法，其中該非導電基材係陶瓷、矽基半導體或玻璃基材。
  12. 如請求項1或2之方法，其中在該非導電基材表面之至少一部分上沈積一層金屬氧化物化合物包含：ia.使該基材與適合於在加熱時形成該金屬氧化物化合物之金屬氧化物前驅體化合物接觸，且其後ib.在150與400℃之間的溫度下加熱該非導電基材且由此在該基材表面之至少一部分上自該金屬氧化物前驅體化合物形成該金屬氧化物化合物。
  13. 如請求項1或2之方法，其中該金屬氧化物前驅體化合物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。
  14. 如請求項1或2之方法，其中在方法步驟ii.之後進行另一方法步驟：ii.a.使該基材與酸性水溶液或鹼性水溶液接觸。
  15. 如請求項1或2之方法，其中該濕式化學金屬鍍敷溶液係鍍鎳或鍍銅溶液。
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US10487404B2 (en) 2019-11-26
KR102531793B1 (ko) 2023-05-12
JP2016533429A (ja) 2016-10-27
EP3049555A1 (en) 2016-08-03
KR20160062067A (ko) 2016-06-01
TWI631241B (zh) 2018-08-01
KR20220040512A (ko) 2022-03-30
CN105593410A (zh) 2016-05-18
CN114107984A (zh) 2022-03-01

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