TWI602948B - For electroless plating solution and before electroless plating method - Google Patents
For electroless plating solution and before electroless plating method Download PDFInfo
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- TWI602948B TWI602948B TW104122883A TW104122883A TWI602948B TW I602948 B TWI602948 B TW I602948B TW 104122883 A TW104122883 A TW 104122883A TW 104122883 A TW104122883 A TW 104122883A TW I602948 B TWI602948 B TW I602948B
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- electroless plating
- sugar alcohol
- pretreatment liquid
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- gold
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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
- 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
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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
- 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
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- C23C18/1607—Process or apparatus coating on selected surface areas by direct patterning
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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
- 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
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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
- 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
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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
- 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
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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
- 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
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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
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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
- 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
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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
- 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
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- 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
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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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- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2026—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by radiant energy
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Description
本發明係關於一種使用於無電電鍍(Electroless plating)前處理中的前處理液,以及使用該前處理液的無電電鍍方法;特別係關於一種可在非導電性物質表面形成微細之電路以及可大範圍地形成膜厚均勻之薄膜的前處理液,以及使用該前處理液的無電電鍍方法。
以往,電鍍作為在基材表面上直接形成鎳(Ni)、銅(Cu)、鈷(Co)等的卑金屬或卑金屬合金,或是銀(Ag)、金(Au)、鉑(Pt)、鈀(Pd)等的貴金屬或貴金屬合金之被膜的方法,無電電鍍被廣泛地應用於工業上。無電電鍍的基材有金屬、塑膠、陶瓷、有機化合物、纖維素等各種組成物,具體而言,可列舉:纖維素、生絲素或聚酯等的高分子樹脂;三酯酸纖維素(TAC)等的薄膜;聚醯亞胺、聚對苯二甲酸乙二酯(PET)、聚苯胺、光硬化性樹脂等的有機化合物被膜;銅、鎳、不銹鋼等的金屬板;氧化鋁、二氧化鈦、二氧化矽、氮化矽等的陶瓷或石英玻璃等的基體或ITO被膜等各種材料。在該等基材呈現絕緣性而難以析出電鍍被膜的情況中,一般係將絕緣性基材浸漬於前處理液,而使無電電鍍用觸媒附著於基材的必要部分。
作為使用於該前處理液的無電電鍍用觸媒,金(Au)、鈀(Pd)、鉑(Pt)等的貴金屬之化合物鹽、或鎳(Ni)、錫(Sn)等的卑金
屬之化合物鹽,雖作為前處理液中的金屬離子大量使用,但使用金(Au)等的貴金屬膠體之方法亦已為人所知(後述專利文獻1)。
至今為止所使用的貴金屬膠體的前處理液,雖可在絕緣性基材表面形成貴金屬膠體之觸媒核,但在進行無電電鍍的情況中,相較於從前處理液中的離子所還原的貴金屬觸媒核,其具有電鍍厚度不均勻且並未均勻析出這樣的課題。這是因為,相較於來自貴金屬離子的觸媒核,貴金屬膠體的觸媒核與基材的密合性較弱,且相較於從離子還原的貴金屬觸媒核,其觸媒活性較低。
但是,使用金屬離子的方法,具有處理步驟變多,可適應的無電電鍍浴有所限制等的缺點,因此有人考慮在前處理液中還原貴金屬鹽,使所形成之貴金屬膠體粒子吸附於基材上的做法(後述專利文獻2)。
然而,以往的貴金屬膠體溶液,由於容易被酸或鹼影響,貴金屬膠體溶液中的奈米粒子凝集,或是觸媒核脫離至無電電鍍之中,而造成電鍍被膜異常析出的同時,無電電鍍浴1次就失控而毀壞這樣的課題。
[專利文獻1]日本專利4649666號公報
[專利文獻2]日本特開平1-319683號公報
本案發明人,為了解決上述課題,而研究一種前處理液,其可使貴金屬膠體穩定分散於所有的pH值域中,且能夠均勻地吸附於基材表
面,進而可藉由無電電鍍大範圍地形成均勻膜厚的電鍍皮膜。結果發現,糖醇會保護貴金屬奈米粒子而使其在水中可均勻地分散,還可使貴金屬奈米粒子均勻地吸附於基材表面,進而完成本發明。
本發明之目的在於提供一種前處理液,其可相對所有pH值域的無電電鍍浴,作為穩定的觸媒核使用。再者,本發明之目的在於提供一種前處理液,其可形成微細電路以及大範圍地形成膜厚均勻的薄膜,且可使貴金屬奈米粒子均勻地分散於基材。再者,本發明之目的係提供一種使用該前處理液地無電電鍍方法。
作為解決本發明之課題的無電電鍍用前處理液之一,其係貴金屬膠體奈米粒子、糖醇以及水所構成的無電電鍍用前處理液,其中該膠體奈米粒子,係金(Au)、鉑(Pt)、或鈀(Pd)的任一項,係在糖醇的存在下進行化學還原(排除以錫(II)化合物進行的還原)所得者,該膠體奈米粒子的平均粒徑為5~80nm,在該前處理液中含有作為金屬質量的該膠體奈米粒子0.01~10g/L;該糖醇為三醇(tritol)、丁醣醇、戊糖醇、已醣醇、庚醣醇、辛糖醇、肌醇、檞皮醇、或季戊四醇所構成之群組中的至少1種以上,其在該前處理液中共含有0.01~200g/L;剩餘部分為水。
用以解決本發明之課題的另一種無電電鍍用前處理液,係由貴金屬膠體奈米粒子、糖醇、pH值調整劑、以及水所構成的用於無電電鍍之前處理液,其中該膠體奈米粒子為金(Au)、鉑(Pt)、或鈀(Pd)的任一項,係在糖醇的存在下進行化學還原(排除以錫(II)化合物進行的還原)所得者,該膠體奈米粒子的平均粒徑為5~80nm;在該前處理液中含有作為
金屬質量的該膠體奈米粒子0.01~10g/L;該糖醇為三醇、丁醣醇、戊糖醇、已醣醇、庚醣醇、辛糖醇、肌醇、檞皮醇、或季戊四醇所構成的群組之中的至少1種以上,其在該前處理液中共含有0.01~200g/L;並含有該pH值調整劑1g/L以下,且剩餘部分為水。
再者,用以解決本發明之課題的無電電鍍方法,係在使基材浸漬於前處理液之後進行無電電鍍的無電電鍍方法,其特徵為使用下述無電電鍍前處理液:該前處理液係由貴金屬膠體奈米粒子、糖醇、pH值調整劑、以及水所構成,該膠體奈米粒子為金(Au)、鉑(Pt)、或鈀(Pd)的任一項,係在糖醇的存在下進行化學還原(排除以錫(II)化合物進行的還原)所得者,該膠體奈米粒子的平均粒徑為5~80nm;在該前處理液中含有作為金屬質量的該膠體奈米粒子0.01~10g/L;該糖醇為三醇、丁醣醇、戊糖醇、已醣醇、庚醣醇、辛糖醇、肌醇、檞皮醇、或季戊四醇所構成之群組中的至少1種以上,其在該前處理液中共含有0.01~200g/L;並且含有該pH值調整劑1g/L以下,剩餘部分為水。
本發明使用於無電電鍍用前處理液的前處理液中,將既定的糖醇限定於三醇、丁醣醇、戊糖醇、已醣醇、庚醣醇、辛糖醇、肌醇、檞皮醇、或季戊四醇所構成的群組之中的至少1種,係因為其可包覆貴金屬奈米粒子,而在所有pH值域以及經加熱之水溶液中保護貴金屬奈米粒子。該等的糖醇具有耐熱性,且不會因為酸鹼的狀態而使其解離形態有所改變,故可在所有pH值狀態下,使用為貴金屬奈米粒子的保護劑。因此,即使在強酸或強鹼的無電電鍍浴中,亦可保持貴金屬奈米粒子的表面形態直到置入還原劑而開始進行無電電鍍為止。
再者,使前處理液中含有0.01~200g/L的既定糖醇,是為了使貴金屬奈米粒子在基材表面等間隔地配置排列。只要在該範圍內,即使既定糖醇的濃度變得稀薄,或者反覆浸漬數十片基材於相同的前處理液,亦可形成微細電路以及大範圍地形成膜厚均勻的薄膜。因此吾人認為,既定濃度範圍的糖醇,在水溶液中雖然會使固體的基材表面與固體的貴金屬奈米粒子結合,但並不會使固體的貴金屬奈米粒子彼此結合,結果使得貴金屬奈米粒子在基材表面上二維狀且等間隔地配置排列,進而形成觸媒核。
使既定糖醇的下限為0.01g/L,是因為若未滿0.01g/L,則變得難以形成微細電路以及大範圍地形成膜厚均勻的薄膜。再者,使上限為200g/L,是因為若超過該值,則會在無電電鍍浴中形成無用的游離觸媒核,而容易引起失控反應。只要既定糖醇在0.01~200g/L的範圍內,則至無電電鍍開始之前,對於絕緣性基材的投錨效果(anchor effect)便不會消失,而不會失去作為相對於無電電鍍液之觸媒核的活性。
本發明的無電電鍍用前處理液中,使膠體奈米粒子為金(Au)、鉑(Pt)、或鈀(Pd)的任一項,是因為其相對於金(Au)、銀(Ag)、鉑(Pt)、鈀(Pd)等的貴金屬無電電鍍浴,或是鈷(Co)、銅(Cu)、鎳(Ni)、鐵(Fe)等的卑金屬無電電鍍浴,具有作為穩定之觸媒核的作用。由於在該等的電鍍浴中貴金屬奈米粒子的形狀穩定,而顯示均勻的觸媒作用,故可形成微細的電路。
特別是在糖醇中經化學還原之貴金屬奈米粒子,其中於貴金屬奈米粒子的表面,觀察到1nm以下的微細球狀粒子的表面析出形態。具體的表面形態顯示於第一圖。亦即,第一圖的穿透式電子顯微鏡影像中,可
在1個奈米粒子表面觀察到多個如葡萄串的微球狀粒子。此稱為「披叢集(pico cluster)」。奈米粒子表面上的披叢集,與貴金屬的種類互不相關。即使前處理液的貴金屬奈米粒子的濃度稀薄,亦可藉由該模板效應(template effect),更佳地發揮貴金屬奈米粒子作為觸媒核的性能,而可形成更微細的電路。
在前處理液中,含有作為金屬質量的膠體奈米粒子0.01~10g/L。如上所述,即使前處理液的濃度稀薄,貴金屬奈米粒子亦可展現觸媒核的性能。然而,使下限為0.01g/L的原因在於,若未滿0.01g/L,則必須每次重新配置前處理液,導致步驟繁雜。再者,使上限為10g/L的原因在於,該處理劑對於絕緣性基材具有強力的投錨效果,若超過該值,則在浸漬於前處理液之後,需要大量勞力來進行水洗作業。
再者,使該膠體奈米粒子的平均粒徑為5~80nm,是為了配合無電電鍍液的種類及性質使貴金屬奈米粒子之觸媒核的性能在實用上發揮。至此,雖已瞭解使用貴金屬奈米粒子之前處理液,但貴金屬奈米粒子卻在浸漬於無電電鍍浴時消失。亦即,即使將貴金屬奈米粒子均勻地分散於基材表面,但因為貴金屬奈米粒子在無電電鍍開始之前即溶解,而無法發揮作為固體奈米粒子的觸媒核之性能。本發明在無電電鍍中置入還原劑之前,因為殘留有均勻分散的貴金屬奈米粒子群,而可選擇與該無電電鍍液契合的膠體奈米粒子的平均粒徑。
若貴金屬奈米粒子的平均粒徑未滿5nm,則無法定義無電電鍍開始析出的時間點,而導致無電電鍍失控。再者,貴金屬奈米粒子的平均粒徑若超過80nm,則難以使其均勻地分散,而不易形成微細電路。再者,
該膠體奈米粒子的平均粒徑只要在5~80nm的範圍內,則可在糖醇中經化學還原的貴金屬奈米粒子,發現各膠體奈米粒子表面上等間隔排列的球狀披叢集。
本發明用於無電電鍍之前處理液中,為了不使基材表面變質,含有1g/L以下的pH值調整劑。特別是若在有機高分子基材的表面,使用高溫、高濃度的酸或鹼,則會有基材特性受損的情況。即使如此,在本發明中較佳為預先對基材表面進行親水化等前處理,再浸漬於本發明的無電電鍍用前處理液。
吾人認為,本發明中的無電電鍍的反應機轉以下所述。
若在無電電鍍中置入還原劑而開始進行無電電鍍,會因為與還原劑的接觸並反應,而失去糖醇的保護作用,導致包住貴金屬奈米粒子的糖醇在無電電鍍浴中離散。剝離出來的貴金屬奈米粒子的表面具有活性,特別是若具有披叢集面,其活性會變高。於是,在基材的表面上整齊排列的貴金屬奈米粒子群,成為無電電鍍之觸媒核的位置,並以此處作為起點開始無電電鍍的金屬析出。再者,若在貴金屬奈米粒子上形成披叢集面,則可藉由披叢集面的投錨效果提高基材與析出金屬的密合性。
本發明的無電電鍍方法所使用的前處理液中,較佳的實施態樣,亦包含上述情況,其係如以下所述。
該披叢集,以構成其本身之貴金屬元素的原子等級的尺寸等間隔地自動排列較佳。這是因為,當觸媒核表面變得越微細,會因為無電電鍍之金屬開始沿著該模板進行還原、析出而成長,而越能夠形成微細的電路。
再者,該膠體奈米粒子的平均粒徑較佳為10~40nm。若未滿
10nm,則因為過細導致觸媒作用降低,使得相對於電鍍液的活性亦降低,再者,若超過40nm,則變得難以形成微細的電路。
再者,該糖醇較佳為0.1~20g/L。反應結束後,為了避免不必要的糖醇殘留於基材表面,而希望糖醇濃度盡可能稀薄,故其濃度較佳在20g/L以下;再者,若未滿0.1g/L,則重複使用的次數會有所限制,故下限較佳在0.1g/L。
再者,該膠體奈米粒子為鉑(Pt)奈米粒子,且該糖醇宜為丙三醇、赤藻糖醇、木糖醇、肌醇或季戊四醇之中的至少1種以上。根據實驗得知,與鉑(Pt)奈米粒子相容性良好的組合為丙三醇、赤藻糖醇、木糖醇、肌醇或季戊四醇。
再者,該膠體奈米粒子較佳為鈀(Pd),且該糖醇較佳為丙三醇、赤藻糖醇、木糖醇或甘露醇之中的至少1種以上。同樣地,根據實驗得知,與鈀(Pd)奈米粒子相容性良好的組合為丙三醇、赤藻糖醇、木糖醇或甘露醇。
再者,該膠體奈米粒子較佳為金(Au),且該糖醇較佳為丙三醇、赤藻糖醇、木糖醇、甘露醇或季戊四醇之中的至少1種以上。同樣地,根據實驗得知,與金(Au)奈米粒子相容性良好的組合為丙三醇、赤藻糖醇、木糖醇、甘露醇或季戊四醇。
本發明的無電電鍍方法中,上述前處理液藉由既定糖醇的效果,而具有耐熱性以及耐酸鹼性。因此,上述前處理液,並不會被前處理液的pH值所影響。再者,即使在前處理液中添加還原劑並放置數十日,對於基材形成觸媒核的能力不會衰減,且上述前處理液維持於穩定的狀態。
而且,本發明的前處理液中,由於提升了潤濕性,故即使沒有一般使用的界面活性劑,亦可具有貴金屬奈米粒子對於基材的投錨效果。
本發明的前處理液的種類,係由貴金屬奈米粒子、糖醇以及水所構成的最單純的前處理液,且其係在該前處理液中添加有pH值調整劑的前處理液。然而,以還原劑使貴金屬奈米粒子在該糖醇中進行化學還原的情況下,會殘留還原劑。此處,所使用的還原劑,具有檸檬酸三鈉、次亞磷酸鈉、乙二酸、酒石酸等的弱還原劑,以及過氧化氫、聯胺(H2N-NH2)、氫硼化鈉等的還原劑。
本發明的用於無電電鍍之前處理液中使用純水較佳。這是因為,純水不會與糖醇及貴金屬奈米粒子的還原劑互相作用。再者,相較於純水,由於超純水可保持糖醇的保護作用因而較佳。
本發明的無電電鍍方法中,在基材浸漬於前處理液之後,設有洗淨該基材的步驟,這是為了完全去除殘留在基材表面的前處理液。高分子樹脂的基材中,由於糖醇與基材的接合較為牢固,即使進行水洗一天一夜,貴金屬奈米粒子亦會殘留在基材表面。若因為水洗不足導致本發明之前處理液中的不必要的貴金屬奈米粒子殘留,在無電電鍍時會形成不必要的觸媒核,而導致無電電鍍浴失控。洗淨步驟一般係以流水進行水洗步驟,但亦可進行機械的刷洗。
再者,本發明的無電電鍍方法中,無電電鍍浴可使用市售的電鍍浴。因為前處理液吸附於絕緣性基材等的投錨效果強,故即使係經過洗淨步驟的基材,在無電電鍍浴中,直到金屬還原反應開始前,亦呈現穩定的狀態。
再者,本發明的無電電鍍方法中,該披叢集以接近構成其自身之貴金屬元素的原子等級的尺寸等間隔地自動排列較佳。隨著觸媒核變得微細,觸媒活性點也會增加,再者,因為金屬沿著其還原而開始均勻成長,而可形成微細的電路。
再者,本發明的無電電鍍方法中,該前處理液的奈米粒子的成分與該無電電鍍浴的金屬成分一致較佳。藉由使金屬成分一致,可將吸附於基材的膠體奈米粒子之披叢集面作為模板,而使無電電鍍浴的貴金屬成分連續析出並成長。
再者,本發明的無電電鍍方法中,該前處理液的pH值與該無電電鍍浴的pH值一致較佳。藉由使pH值一致,可直接維持吸附於基材之膠體奈米粒子的投錨效果。
再者,本發明的無電電鍍方法中,對該基材照射紫外線以進行表面改質較佳。例如,在以矽烷偶合劑處理矽半導體基材的表面的情況,其形成於表面相同地配置有胺末端基等的陶瓷基材。若以石英光罩在該基材上形成微細電路之後照射紫外線,而能使貴金屬奈米粒子僅吸附於未照射紫外線的部分。再者,亦可相同地對環氧樹脂的印刷電路基材照射紫外線而形成電路。
根據本發明的無電電鍍用前處理液,因為糖醇包覆貴金屬奈米粒子,故貴金屬奈米粒子具有耐熱性以及對強酸或強鹼等的耐藥品性。再者,包覆奈米粒子的既定糖醇,由於並不會改變貴金屬奈米粒子的分散狀態,故可保持膠體狀態。再者,由於包覆奈米粒子的既定糖醇係為穩定,
故本發明的無電電鍍用前處理液具有長期穩定性,在無電電鍍開始前,可維持貴金屬奈米粒子的形狀。再者,由於包覆奈米粒子的既定糖醇對於酸或鹼不會改變其解離狀態,故對於所有pH值範圍的水溶液可維持前處理液。因此,可配合所使用之無電電鍍浴的浴組成,調整前處理液的組成。
再者,無論基材的種類,包覆奈米粒子的既定糖醇皆可使貴金屬奈米粒子強力吸附於任一基材。再者,該糖醇分散性優良,吸附於基材的貴金屬奈米粒子間的間隔寬,再者,於已吸附的貴金屬奈米粒子的表面上,並不會有下一個貴金屬奈米粒子重疊吸附的情況。亦即,只要配合所使用之無電電鍍液去設定作為觸媒核之貴金屬奈米粒子的粒徑,即可使貴金屬奈米粒子在基材上以二維狀整齊排列並分散。
再者,由於在吸附於基材之後,糖醇仍包覆貴金屬奈米粒子,故在浸漬於無電電鍍浴之後會置入還原劑,且貴金屬奈米粒子開始無電電鍍之前可維持該形狀。例如,即使將包覆有該糖醇的貴金屬奈米粒子在吸附於基材後進行乾燥,接著只要將其浸漬於無電電鍍液,即開始無電電鍍反應。再者,包覆有該糖醇的貴金屬奈米粒子,即便進行乾燥亦不會凝集。亦即,即便使含有貴金屬奈米膠體的前處理液乾燥,亦不會凝集而造成金屬塊狀化。因此,即使因為水分蒸發等導致部分濃縮,亦不會在前處理層的液面接觸壁面附近產生金屬塊狀化。而且,由於本發明的用於無電電鍍之前處理液可重複使用,故可重複在多數的基材上形成觸媒核。因此,可將本發明的用於無電電鍍之前處理液應用至無電電鍍的自動化產線。
再者,因為包覆貴金屬奈米粒子的糖醇具有耐熱性以及對強酸或強鹼等的耐藥品性,故可作為市售的所有無電電鍍液的前處理液來使
用。再者,在該糖醇中化學還原的貴金屬奈米粒子會形成披叢集,且由於該貴金屬奈米粒子的披叢集構造具有經化學還原的活性面,故具有高活性,與基材的接合力以及觸媒作用進而變得高活性。
根據本發明的無電電鍍方法,除了上述的無電電鍍用前處理液的效果以外,可得到以下重複或獨立的效果。
由於在無電電鍍開始時可得到固體的貴金屬奈米粒子,故可持續得到固定形狀的觸媒核。因此,可在基材上形成電路寬度微細的電路,再者,可在大範圍面積地形成薄且均勻的被膜。而且,因為該觸媒核的表面離散有糖醇,而使得固體的貴金屬奈米粒子表面露出,故活性高且電鍍膜的品質亦為穩定。
再者,只要貴金屬奈米粒子係在該糖醇中經化學還原者,則於貴金屬奈米粒子表面所形成的披叢集會成為模板,而使得從無電電鍍浴中被還原的金屬在披叢集面析出,故可藉由該模板效應,使邊緣陡峭的電鍍膜成長至次微米為止。
另一方面,因無電電鍍的開始而游離的糖醇,因為在無電電鍍浴中的濃度極薄,故不會與已還原的無電電鍍的金屬原子結合。再者,本發明的貴金屬奈米膠體,由於牢固地吸附於基材,故即使在前處理後進行充分洗淨,亦不會脫離。因此,即使在自動無電電鍍產線上,對大量基材重複進行無電電鍍,游離之糖醇亦不會發生異常析出反應,進而不會導致電鍍浴失控。
第一圖係顯示本發明之粒徑20nm的金(Au)奈米粒子的穿
透式電子顯微鏡影像。
[實施例]
接著,描述本發明的較佳實施例。
[1]前處理液的調製
〔實施例1〕
將在金(Au)換算濃度下為0.1g/L的四氯金(Ⅲ)酸鈉.四水合物以及1.0g/L的木糖醇溶解於90℃的氫氧化鈉水溶液(pH值=12)、並以檸檬酸三鈉.二水合物進行還原,得到金(Au)膠體溶液。金(Au)奈米粒子的平均粒徑為20nm,其90%以上皆在10~30nm的範圍(d=20±10nm)內。以穿透式電子顯微鏡(日本電子公司製JEM-2010)觀察粒徑20nm的金(Au)奈米粒子。第一圖顯示穿透式電子顯微鏡影像。從該圖可明確得知,金(Au)奈米粒子的表面上,披叢集以接近金(Au)原子等級的尺寸等間隔地自動整齊排列。
接著,將所得之金(Au)膠體溶液分散於1規定的鹽酸、硫酸以及氫氧化鉀的80℃水溶液中,同樣以穿透式電子顯微鏡影像進行觀察,並未觀察到金(Au)奈米粒子的表面性狀有所變化。再者,使其分散於30℃的氫氧化鈉水溶液(pH值=12),即使在150小時後,亦同樣地未觀察到金(Au)奈米粒子的表面性狀有所變化。
〔實施例2〕
以與實施例1相同的方式,使四氯金(Ⅲ)酸鈉.四水合物的金(Au)換算濃度變更為1g/L、5g/L以及9g/L,同時使木糖醇的濃度變更為
15g/L、0.5g/L以及150g/L。所得之金(Au)奈米粒子的粒徑,相對於金(Au)換算濃度的1g/L、5g/L以及9g/L,分別為d=20±10nm、d=30±10nm以及d=50±20nm。
〔實施例3〕
使用甘露醇、丙三醇或赤藻糖醇代替木糖醇進行與實施例1相同的實驗,分別得到d=20±10nm、d=20±10nm以及d=20±10nm的金(Au)膠體奈米粒子。以與實施例1相同的方式,將所得之金(Au)膠體溶液分散於1規定的鹽酸、硫酸以及氫氧化鉀的80℃水溶液,與實施例1相同地,未觀察到金(Au)奈米粒子的表面性狀有所變化。
〔實施例4〕
將在鈀(Pd)換算濃度下為0.1g/L的氯化鈀以及50g/L的丙三醇溶解於90℃的鹽酸水溶液(pH值=3),並以次亞磷酸鈉還原,而得到鈀(Pd)膠體溶液。鈀(Pd)奈米粒子為d=30±10nm。
接著,使所得之鈀(Pd)膠體溶液分散於1規定的鹽酸、硫酸以及氫氧化鉀的80℃水溶液,與實施例1相同地,未觀察到鈀(Pd)奈米粒子的表面性狀有所變化。
〔實施例5〕
與實施例4相同地,將氯化鈀的鈀(Pd)換算濃度變更為1g/L、5g/L以及9g/L,同時將丙三醇的濃度變更為0.05g/L、4g/L以及18g/L。所得之鈀(Pd)奈米粒子的粒徑,相對於鈀(Pd)換算濃度的1g/L、5g/L以及9g/L,分別為d=50±20nm、d=30±10nm以及d=30±10nm。
〔實施例6〕
使用甘露醇、木糖醇或赤藻糖醇取代丙三醇而進行與實施例4相同的實驗時,分別得到d=30±10nm、d=40±10nm以及d=30±10nm的鈀(Pd)膠體奈米粒子。與實施例4相同地,將所得之鈀(Pd)膠體溶液分散於1規定的鹽酸、硫酸以及氫氧化鉀的80℃水溶液,與實施例4相同地,未觀察到鈀(Pd)奈米粒子的表面性狀有所變化。
〔實施例7〕
將在鉑(Pt)換算濃度下為0.3g/L的六羥基鉑酸(IV)(Hexahydroxyplatinate(IV))以及1.5g/L的木糖醇溶解於90℃的氫氧化鈉水溶液(pH值=12),並以聯胺還原,得到鉑(Pt)膠體溶液。鉑(Pt)奈米粒子之粒徑為d=30±10nm。在以穿透式電子顯微鏡觀察粒徑30nm的鉑(Pt)奈米粒子時,在鉑(Pt)奈米粒子的表面上,披叢集以接近鉑(Pt)原子等級的尺寸等間隔地自動整齊排列。
接著,使所得之鉑(Pt)膠體溶液分散於1規定的鹽酸、硫酸以及氫氧化鉀的80℃水溶液,同樣地以穿透式電子顯微鏡影像進行觀察時,未觀察到鉑(Pt)奈米粒子的表面性狀有所變化。
〔實施例8〕
與實施例7相同地,將六羥基鉑酸(IV)的鉑(Pt)換算濃度變更為1.5g/L、5g/L以及6.5g/L,同時將木糖醇的濃度變更為4g/L、180g/L以及16g/L。所得之鉑(Pt)奈米粒子的粒徑,相對於鉑(Pt)換算濃度的1.5g/L、5g/L以及6.5g/L,分別為d=30±10nm、d=50±20nm以及d=30±10nm。
〔實施例9〕
使用山梨糖醇、甘露醇、赤藻糖醇、丙三醇或肌醇代替木糖
醇而進行與實施例1相同的實驗時,分別得到d=30±10nm、d=60±10nm、d=20±10nm、d=60±10nm以及d=80±10nm的鉑(Pt)膠體奈米粒子。將所得之鉑(Pt)膠體溶液,與實施例7相同地,分散於1規定的鹽酸、硫酸以及氫氧化鉀的80℃水溶液,與實施例7相同地,未觀察到鉑(Pt)奈米粒子的表面性狀有所變化。
[2]無電電鍍
〔實施例10〕
對於表面上形成SiO2的20mm×20mm的矽晶圓試片,使用信越SILICON股份有限公司製的矽烷偶合劑(3-胺基丙基三乙氧基矽烷(3-Aminopropyltriethoxysilane)(商品名KBE-903)),在大氣壓下,以75℃進行化學蒸鍍5分鐘,以形成具有胺末端基的自我組織化單分子膜(SAM)。
將20片該基材,在25℃下,浸漬於1000mL的實施例1中所製作的金(Au)膠體溶液10分鐘,並以蒸餾水洗淨各基材10分鐘。之後,在65℃下,每5分鐘將一片試片浸漬於Electroplating Engineers of Japan股份有限公司製的自催化型非氰系無電解金電鍍浴(商品名稱Precious fab ACG3000WX,金(Au)濃度(2g/L),pH值=7.5)中,實驗過程中,並無電解金電鍍浴失控的情形,20片的基材皆完成電鍍。
以SII NanoTechnology股份有限公司製的螢光X光膜厚測定器(型號SFT-9550)實際測量所得之金(Au)電鍍的電鍍厚度20片,其平均厚度為50nm(±5nm)。
〔實施例11〕
將長50mm、寬50mm以及厚度1mm的γ-氧化鋁基材10片,於
25℃下,浸漬於1000mL的實施例7中所製作的鉑(Pt)膠體溶液10分鐘,並以蒸餾水洗淨各基材30分鐘。之後,添加3.4g/L的二硝基二胺鉑(II)(Pt(NH3)2(NO2)2)、2莫耳/Pt莫耳的聚乙烯吡咯烷酮(Polyvinylpyrrolidone),以及1.0g/L的氫硼化鉀(KBH4)、每三十分鐘將一片試片浸漬於pH值=12、浴溫90℃的無電解鉑電鍍浴中,實驗過程中,並無電解金電鍍浴失控的情形,10片的基材皆完成電鍍。
所得之鉑(Pt)電鍍的電鍍厚度,平均厚度為1μm±0.3μm,膜厚僅些微不均勻,而可得到均勻的膜。
〔實施例12〕
將20片長60mm、寬30mm以及厚度0.3mm的金試片浸漬於實施例4的鈀(Pd)膠體溶液500mL,並以活水清洗各基材10分鐘。之後,在85℃下,每20分鐘將一片試片浸漬於Electroplating Engineers of Japan股份有限公司製的無電解鎳電鍍浴(商品名稱LECTROLESS NP7600,鎳(Ni)濃度(4.8g/L),pH值=4.6)之中,於實驗過程中,並無電解鎳電鍍浴失控的情形,20片的基材皆完成電鍍。
以SII NanoTechnology股份有限公司製的螢光X光膜厚測定器(型號SFT-9550)實際測量所得之鎳(Ni)電鍍的電鍍厚度20片,平均厚度為1.0μm±0.2μm,膜厚僅些微不均勻,而可得到均勻的膜。
〔比較例1〕
除了使四氯金(Ⅲ)酸鈉.四水合物在金(Au)換算濃度下為12g/L以外,以與實施例1相同的方式得到金(Au)膠體溶液。該金(Au)奈米粒子的粒徑為d=80±50nm。該金(Au)膠體溶液在製作完成後1小時左
右發生凝集的現象,而未顯現作為無電電鍍用觸媒核的活性。
〔比較例2〕
除了使四氯金(Ⅲ)酸鈉.四水合物在金(Au)換算濃度下為0.005g/L以外,以與實施例1相同的方式得到金(Au)膠體溶液。該金(Au)奈米粒子粒徑雖為d=40±20nm,但在金(Au)奈米粒子的表面未觀察到披叢集。將該金(Au)膠體溶液在實施例10的電鍍浴中進行無電電鍍時,並無法啟動無電電鍍。
〔比較例3〕
除了使丙三醇為250g/L以外,與實施例4相同地,得到鈀(Pd)膠體溶液。
鈀(Pd)奈米粒子的粒徑雖為d=40±20nm,但在鈀(Pd)奈米粒子的表面上並未觀察到披叢集。將該鈀(Pd)膠體溶液在實施例12的電鍍浴中進行無電電鍍時,並無法啟動無電電鍍。
〔比較例4〕
除了使木糖醇為0.005g/L以外,與實施例7相同地,得到鉑(Pt)膠體溶液。該鉑(Pt)奈米粒子的粒徑為d=20±40nm,在鉑(Pt)奈米粒子的表面並未觀察到披叢集。使該鉑(Pt)膠體溶液在實施例11的電鍍浴中進行無電電鍍時,並無法啟動無電電鍍。
〔習知例1〕
將包含0.05g/L的聚乙烯吡咯烷酮K25、0.1g/L(Au換算濃度)的四氯金(Ⅲ)酸.四水合物以及0.5g/L的檸檬酸鈉.二水合物之水溶液在90℃下攪拌30分鐘,得到以聚乙烯吡咯烷酮為分散劑的Au膠體。在以實施
例10的方法對該Au膠體溶液進行無電解金電鍍時,並無法啟動無電電鍍。
【產業上的利用可能性】
本發明的用於無電電鍍之前處理液,可應用於所有市售的無電電鍍液。再者,無電電鍍方法,可使用於光偵測器、氫氣檢測偵測器、氣壓偵測器、水深偵測器等的各種偵測器及配線基材的電極等。
Claims (16)
- 一種用於無電電鍍(Electroless plating)之前處理液,其係由貴金屬膠體奈米粒子、糖醇、及水所構成,其中該膠體奈米粒子為金(Au)、鉑(Pt)、或鈀(Pd)的任一項,係在糖醇的存在下進行化學還原(排除以錫(II)化合物進行的還原)所得者,該膠體奈米粒子的平均粒徑為5~80nm,於該前處理液中含有作為金屬質量的該膠體奈米粒子0.01~10g/L;該糖醇為三醇(tritol)、丁醣醇、戊糖醇、已醣醇、庚醣醇、辛糖醇、肌醇、檞皮醇、或季戊四醇所構成的群組之中的至少1種以上,在該前處理液中含有該糖醇共0.01~200g/L;剩餘部分為水。
- 一種用於無電電鍍之前處理液,其係由貴金屬膠體奈米粒子、糖醇、pH值調整劑、及水所構成,其中該膠體奈米粒子為金(Au)、鉑(Pt)、或鈀(Pd)的任一項,其係在糖醇的存在下進行化學還原(排除以錫(II)化合物進行的還原)所得者,該膠體奈米粒子的平均粒徑為5~80nm,於該前處理液中含有作為金屬質量的該膠體奈米粒子0.01~10g/L;該糖醇為三醇、丁醣醇、戊糖醇、已醣醇、庚醣醇、辛糖醇、肌醇、檞皮醇、或季戊四醇所構成的群組之中的至少1種以上,在該前處理液中含有該糖醇共0.01~200g/L;並且含有該pH值調整劑1g/L以下;剩餘部分為水。
- 如申請專利範圍第1或2項之用於無電電鍍之前處理液,其中該膠體奈米粒子為鉑(Pt)奈米粒子,且該糖醇為丙三醇、赤藻糖醇、木糖醇、肌醇、或季戊四醇之中的至少1種以上。
- 如申請專利範圍第1或2項之用於無電電鍍之前處理液,其中該膠體 奈米粒子為鈀(Pd),且該糖醇為丙三醇、赤藻糖醇、木糖醇、或甘露醇之中的至少1種以上。
- 如申請專利範圍第1或2項之用於無電電鍍之前處理液,其中該膠體奈米粒子為金(Au),且該糖醇為丙三醇、赤藻糖醇、木糖醇、甘露醇、或季戊四醇之中的至少1種以上。
- 如申請專利範圍第1或2項之用於無電電鍍之前處理液,其中金(Au)膠體奈米粒子的表面上,披叢集以接近金(Au)原子等級的尺寸等間隔地自動整齊排列。
- 一種無電電鍍方法,其係將基材浸漬於前處理液後進行無電電鍍的無電電鍍方法,該前處理液係由貴金屬膠體奈米粒子、糖醇、pH值調整劑、及水所構成,其中該膠體奈米粒子為金(Au)、鉑(Pt)、或鈀(Pd)的任一項的膠體奈米粒子,其係在糖醇的存在下進行化學還原(排除以錫(II)化合物進行的還原)所得者,該膠體奈米粒子的平均粒徑為5~80nm;於該前處理液中含有作為金屬質量的該膠體奈米粒子0.01~10g/L;該糖醇為三醇、丁醣醇、戊糖醇、已醣醇、庚醣醇、辛糖醇、肌醇、檞皮醇、或季戊四醇所構成的群組之中的至少1種以上,在該前處理液中含有該糖醇共0.01~200g/L;並且含有該pH值調整劑1g/L以下;剩餘部分為水。
- 如申請專利範圍第7項之無電電鍍方法,其中在將基材浸漬於該前處理液後洗淨該基材,再進行無電電鍍。
- 如申請專利範圍第7或8項之無電電鍍方法,其中該前處理液的奈米粒子的成分與無電電鍍浴的金屬成分一致。
- 如申請專利範圍第7或8項之無電電鍍方法,其中該前處理液的pH值與該無電電鍍浴的pH值一致。
- 如申請專利範圍第9項之無電電鍍方法,其中該前處理液的pH值與該無電電鍍浴的pH值一致。
- 如申請專利範圍第7或8項之無電電鍍方法,其中對該基材照射紫外線。
- 如申請專利範圍第9項之無電電鍍方法,其中對該基材照射紫外線。
- 如申請專利範圍第10項之無電電鍍方法,其中對該基材照射紫外線。
- 如申請專利範圍第11項之無電電鍍方法,其中對該基材照射紫外線。
- 如申請專利範圍第7或8項之無電電鍍方法,其中金(Au)膠體奈米粒子的表面上,披叢集以接近金(Au)原子等級的尺寸等間隔地自動整齊排列。
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