TW201732080A - 具有離子催化劑的基板的無電金屬鍍覆的水平方法 - Google Patents

具有離子催化劑的基板的無電金屬鍍覆的水平方法 Download PDF

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TW201732080A
TW201732080A TW106103743A TW106103743A TW201732080A TW 201732080 A TW201732080 A TW 201732080A TW 106103743 A TW106103743 A TW 106103743A TW 106103743 A TW106103743 A TW 106103743A TW 201732080 A TW201732080 A TW 201732080A
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substrate
acid
catalyst
horizontal method
solution
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TW106103743A
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TWI606138B (zh
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劉風
瑪麗亞 雷茲尼克
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羅門哈斯電子材料有限公司
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Abstract

在離子催化劑下無電金屬鍍覆的水平方法已藉由減少不希望有的起泡而改善鍍覆效能。減少起泡防止催化劑浴損失離子催化劑且防止抑制催化劑效能的浮渣形成。水平方法亦抑制離子催化劑沈澱且改善離子催化劑對基板的黏著性。水平方法可用於鍍覆不同類型基板的通孔及通道。

Description

具有離子催化劑的基板的無電金屬鍍覆的水平方法
本發明係關於具有離子催化劑的基板的無電金屬鍍覆的水平方法，以維持或改善催化劑在無電金屬鍍覆期間的效能且提供對基板的良好金屬黏著性。更確切而言，本發明係關於具有離子催化劑的基板的無電金屬鍍覆的水平方法，以維持或改善催化劑在無電金屬鍍覆期間的效能，且藉由減少或抑制在水平無電金屬鍍覆方法期間不希望有的起泡及浮渣形成而提供對基板的良好金屬黏著性。
無電鍍覆為印刷電路板行業中最重要的金屬化技術之一。近年來，高密度印刷電路板(諸如具有微通道及通孔的那些高密度印刷電路板)更經常以使用離子催化劑的水平方法模式來加工。此部分歸因於更有利的流體動力學使得金屬化化學物質到達微通道(尤其具有1：1及更高的高縱橫比的那些微通道)的底部。
基於離子溶液的催化劑在水平鍍覆系統中具有數個優於膠態催化劑的重要優勢。離子催化劑錯合物由於不存在外來金屬離子(諸如錫(II)離子)而本質上對氧化環境(諸如通常在水平傳送帶化設備中所見的高速攪拌)具有優良的 穩定性。此外，離子催化劑錯合物能夠實現高縱橫比微通道底部的滲透及表面活化，同時維持易於方法控制的寬操作參數。最後，這些催化劑提供降低的殘餘導電性，此為這些複雜設計中存在的細線技術所必需的。對於高密度互連件，鑒於傳送帶化系統可更易於操縱薄核心加工，水平加工為較佳的技術。此外，改善的溶液流動可易於經由恆定的催化劑應用及化學處理而滿足複雜微結構在印刷電路板面板兩側上的均一性要求。然而，水平系統中的高速溶液攪拌使得含有界面活性劑的溶液起泡且可能導致氣泡及界面活性劑分子截留在微通道底部內，從而產生可靠性問題。
界面活性劑，諸如烷基苯氧基聚乙氧基乙醇、聚氧化乙烯聚合物及直鏈烷基苯磺酸鹽，已作為濕潤劑用於處理電路板以便較佳吸附離子催化劑以及膠態催化劑。在水平方法鍍覆模式中，這些界面活性劑水溶液在空氣鼓泡穿過其時起泡。當其用作催化劑步驟之前的預浸溶液時，界面活性劑及泡沫可被拖入催化劑浴中。離子催化劑，諸如離子鈀催化劑，包含鈀離子及有機螯合劑。離子催化劑浴亦由於催化劑部分的寡聚物或聚合物性質而在水平方法模式中起泡。拖入離子催化劑浴模塊中的預浸界面活性劑可使得催化劑泡沫消散更慢且保持更久，從而在催化劑溶液表面上形成浮渣。此類起泡及浮渣形成可導致催化劑浴損失催化劑。另外，泡沫及浮渣可填塞微通道及通孔，從而產生有缺陷的電路板。因此，需要一種減少或抑制起泡及浮渣形成且同時使得催化劑能夠良好吸附於基板表面以便無電金屬化的預浸調配物。
無電鍍覆基板的水平方法包含：清潔及調節基板；微蝕刻基板；提供水性酸性預浸組合物，其由一或多種具有下式的化合物：
其中R1、R2、R3、R4及R5獨立地選自氫、直鏈或分支鏈(C1-C4)烷基、鹵化物、NH2、NO2、SO3H、OH、醯基、(C1-C4)烷氧基及苯甲醯基，且Z為OY或苯甲醯基，其中Y為氫、鹵化物、直鏈或分支鏈(C1-C4)烷基、苯基或鹼金屬陽離子；及視情況選用的一或多種緩衝劑組成；將水性酸性預浸組合物施用於基板；將離子催化劑施用於基板；將還原劑施用於具有離子催化劑的基板；且將無電金屬鍍覆浴施用於具有催化劑的基板以便金屬鍍覆基板。
水平方法的預浸減少或防止離子催化劑溶液在水平無電金屬鍍覆方法期間起泡及浮渣形成，由此防止離子催化劑損失。浮渣可污染且造成催化劑損失。另外，泡沫及浮渣可阻塞通孔及通道，由此抑制此類特徵的金屬化。在離子催化劑施用於基板期間，較佳向催化劑浴及基板施加劇烈溶液攪拌以促使離子催化劑滲透至基板的任何通孔及通道中。一般而言，用於印刷電路板金屬化的離子催化劑易於起泡，因此劇烈攪拌加重起泡。預浸減少或預防催化劑浴中不希望有的起泡及隨後浮渣形成。另外，水平方法的預浸液不包含出於改善離子催化劑吸附於基板的目的而包含於許多習 知預浸調配物中的界面活性劑。此類界面活性劑通常起泡或誘導起泡。除減少或抑制起泡以外，預浸液亦使得離子催化劑能夠良好吸附於基板。離子催化劑的良好吸附為在基板上以及基板的任何特徵(諸如通孔及通道)中實現良好無電金屬鍍覆必不可少的。
圖1為多個基板的通孔無電鍍銅背光效能的標繪圖，其中使用含有2,4-二羥基苯甲酸或抗壞血酸的水性酸性預浸溶液製備通孔。
圖2為多個基板的通孔無電鍍銅背光效能的標繪圖，其中使用含有鞣酸的水性酸性預浸溶液製備通孔。
如本說明書通篇所使用，除非上下文另外明確指示，否則下文給出的縮寫具有以下含義：g=公克；mg=毫克；mL=毫升；L=公升；cm=公分；mm=毫米；ppm=百萬分率=mg/L；mol=莫耳；℃=攝氏度；g/L=公克/公升；DI=去離子；wt%=重量百分比；Tg=玻璃轉移溫度；鹵化物=氯、溴及氟。
術語「鍍覆」及「沈積」在本說明書通篇可互換地使用。術語特徵意思指基板表面上或基板中的結構，諸如通孔、通道或微通道。術語「通道」包含印刷電路板中存在的任何尺寸的通道，包含微通道。術語「水平方法」意思指印刷電路板的面板在無電金屬化方法期間通過包含鍍覆溶液的不同溶液時在傳送機上以水平位置加工，且溶液攪拌通常 由溢流/噴桿提供且比垂直金屬化方法中的機架攪拌更劇烈。術語「垂直方法」意思指印刷電路板的面板在機架上夾緊且垂直浸入準備用於金屬化的溶液(包含金屬鍍覆溶液)中。術語「立即(immediate或immediately)」意思指不存在插入步驟。除非另外指出，否則所有量均為重量百分比。不定冠詞「一(a及an)」指代單數以及複數。所有數值範圍均包含端點在內且可按任何次序組合，但邏輯上此類數值範圍被限制於總計共100%。
本發明係關於無電金屬鍍覆的水平方法，其中水性酸性預浸液具有下式之化合物：
其中R1、R2、R3、R4及R5獨立地選自氫、直鏈或分支鏈(C1-C4)烷基、鹵化物(諸如氯化物、氟化物或溴化物)、NH2、NO2、SO3H、OH、醯基、(C1-C4)烷氧基及苯甲醯基，且Z為OY或苯甲醯基，其中Y為氫、鹵化物(諸如氯化物、氟化物或溴化物)、直鏈或分支鏈(C1-C4)烷基、苯基或鹼金屬陽離子(諸如鈉或鉀)。
較佳地，R1、R2、R3、R4及R5獨立地選自氫、直鏈或分支鏈(C1-C4)烷基、氯化物、NH2、SO3H、OH，Z較佳為OY且Y較佳為氫、氯化物、直鏈或分支鏈(C1-C4)烷基或鈉。更佳地，R1、R2、R3、R4及R5獨立地選自氫、甲基、第三丁基、NH2、SO3H及OH且Y更佳為氫、甲基或鈉。最 佳地，R1、R2、R3、R4及R5獨立地選自氫及OH，且Y最佳為氫或鈉。
此類化合物包含(但不限於)苯甲酸及苯甲酸鹽，諸如苯甲酸鈉及苯甲酸鉀；苯甲酸酯，諸如苯甲酸甲酯、苯甲酸正丁酯、苯甲酸苯酯；苯甲酸的烷基類似物，諸如2-甲基苯甲酸、3-甲基苯甲酸、4-甲基苯甲酸及4-第三丁基苯甲酸；苯甲酸的醯基類似物，諸如2-苯甲醯苯甲酸；氯苯甲酸，諸如2-氯苯甲酸、3-氯苯甲酸、4-氯苯甲酸、2,4-二氯苯甲酸及2,5-二氯苯甲酸；胺基苯甲酸，諸如2-胺基苯甲酸、3-胺基苯甲酸及4-胺基苯甲酸；硝基苯甲酸，諸如2-硝基苯甲酸、3-硝基苯甲酸及4-硝基苯甲酸；羥基苯甲酸，諸如2-羥基苯甲酸、3-羥基苯甲酸及4-羥基苯甲酸；二羥基苯甲酸，諸如3,5-二羥基苯甲酸、2,4-二羥基苯甲酸、2,5-二羥基苯甲酸、2,6-二羥基苯甲酸、2,4-二羥基-6-甲基苯甲酸、2,3-二羥基苯甲酸、3,4-二羥基苯甲酸；三羥基苯甲酸，諸如3,4,5-三羥基苯甲酸及2,4,6-三羥基苯甲酸；3,4,5-三甲氧基苯甲酸及4-羥基-3,5-二甲氧基苯甲酸。最佳化合物為二羥基苯甲酸、三羥基苯甲酸及其鈉鹽。
式(I)化合物以5ppm至30g/L、較佳10ppm至20g/L、更佳20ppm至10g/L且甚至更佳30ppm至3g/L的量包含於水性酸性預浸液中。
視情況，水性酸性預浸溶液可包含一或多種緩衝劑。此類緩衝劑選自鹼金屬氫氧化物，諸如氫氧化鈉或氫氧化鉀；及無機酸，諸如硫酸、硝酸或鹽酸。較佳地，硝酸為所用酸。水性酸性預浸液中所包含的緩衝劑不包含可干擾離 子催化劑效能的酸及鹼。緩衝劑係以使pH值維持在7或更低、較佳2至4的量包含於預浸液中。
除了水性酸性預浸溶液不包含可干擾離子催化劑穩定性及效能的酸及鹼以外，亦不包含界面活性劑。水性酸性預浸溶液由一或多種式(I)化合物、水及視情況選用的一或多種緩衝劑構成。較佳地，水性酸性預浸溶液由一或多種式(I)化合物、水及一或多種緩衝劑構成。較佳地，緩衝劑為氫氧化鈉及硝酸，其量提供所期望的酸性pH值。
在微蝕刻基板之後，將水性酸性預浸溶液施用於基板及基板中的任何特徵。可藉由噴塗基板或藉由將基板浸沒於預浸液中來施用預浸液。預浸液維持在室溫至60℃、較佳室溫至30℃的溫度下。
在施用離子催化劑之前，基板與水性酸性預浸溶液保持接觸30秒至3分鐘。在基板與水性酸性預浸溶液接觸的期間，攪拌預浸溶液以促使預浸溶液進入且集中在基板特徵(諸如通孔及通道)內部及各處以確保預浸液在整個基板的均一分佈。可使用任何適用於攪拌溶液的習知設備(諸如溢流桿及噴桿)進行攪拌。攪拌速率可視基板的尺寸及基板上的特徵的數目而改變。泡沫產生受到抑制或不顯著。
經水性酸性預浸的基板接著與離子催化劑水溶液接觸而在預浸溶液施用於基板與離子催化劑施用於基板之間無任何沖洗步驟。在先前速率下繼續攪拌或可視需要增加或降低速率以促使催化劑均一地分佈在整個基板及特徵中。泡沫產生受到抑制或不顯著，使得所形成的浮渣(若存在)的量不在無電金屬鍍覆期間造成催化劑損失。
離子催化劑包含錯合劑或螯合劑及金屬離子。較佳地，離子催化劑為水性及鹼性的。鹼性催化劑水溶液較佳包含選自金、鉑、鈀的金屬離子及一或多種作為錯合或螯合劑的雜環氮化合物的錯合物。較佳地，雜環氮化合物選自吡啶、嘧啶及吡嗪衍生物。
吡啶衍生物包含(但不限於)4-二甲胺基吡啶、4-胺基吡啶、2-胺基吡啶、4-(甲胺基)吡啶、2-(甲胺基)吡啶、2-胺基-4,6-二甲基吡啶、2-二甲胺基-4,6-二甲基吡啶、4-二乙胺基吡啶、2-(吡啶-3-基)-乙酸、2-胺基-3-(吡啶-3-基)-丙酸、2-胺基-3-(吡啶-2-基)-丙酸、3-(吡啶-3-基)-丙烯酸、3-(4-甲基吡啶-2-基)丙烯酸及3-(吡啶-3-基)-丙烯醯胺。
嘧啶衍生物包含(但不限於)尿嘧啶、巴比妥酸(barbituric acid)、乳清酸、胸腺嘧啶、2-胺基嘧啶、6-羥基-2,4-二甲基嘧啶、6-甲基尿嘧啶、2-羥基嘧啶、4,6-二氯嘧啶、2,4-二甲氧基嘧啶、2-胺基-4,6-二甲基嘧啶、2-羥基-4,6-二甲基嘧啶及6-甲基異胞嘧啶。
吡嗪衍生物包含(但不限於)2,6-二甲基吡嗪、2,3-二甲基吡嗪、2,5-二甲基吡嗪、2,3,5-三甲基吡嗪、2-乙醯基吡嗪、胺基吡嗪、乙基吡嗪、甲氧基吡嗪及2-(2'-羥乙基)吡嗪。
金屬離子源包含本領域及文獻中已知的任何鈀、金及鉑的習知水溶性金屬鹽。可使用一種類型的催化金屬離子或可使用兩種或更多種催化金屬離子的混合物。包含此類鹽以便以20ppm至2000ppm、較佳25ppm至500ppm的量提供金屬離子。鈀鹽包含(但不限於)氯化鈀、乙酸鈀、 氯化鉀鈀、氯化鈉鈀、四氯鈀酸鈉、硫酸鈀及硝酸鈀。金鹽包含(但不限於)氰化金、三氯化金、三溴化金、氯化鉀金、氰化鉀金、氯化鈉金及氰化鈉金。鉑鹽包含(但不限於)氯化鉑及硫酸鉑。較佳地，金屬離子為鈀及金離子。更佳地，金屬離子為鈀。
鹼性催化劑水溶液中所包含的雜環錯合或螯合劑及一或多種金屬離子的量使得錯合或螯合劑與金屬離子的莫耳比為1：1至4：1、較佳1：1至2：1。催化劑水溶液的pH值用諸如四硼酸鈉、碳酸鈉、碳酸氫鈉、磷酸鈉或鹼金屬氫氧化物(諸如氫氧化鉀或鈉)或其混合物的鹽調節至鹼性pH值。鹼性催化劑水溶液的pH值範圍為8及更大、較佳9及更大、更佳9至13、最佳9至12。鹼性催化劑水溶液不含錫、錫離子及抗氧化劑。
在催化劑施用於基板之後且在金屬化之前，將一或多種還原劑施用於經催化的基板以使金屬離子還原成其金屬態。可使用已知使金屬離子還原成金屬的習知還原劑。此類還原劑包含(但不限於)二甲胺硼烷、硼氫化鈉、抗壞血酸、異抗壞血酸、次磷酸鈉、水合肼、甲酸及甲醛。較佳地，還原劑為次磷酸鈉及二甲胺硼烷。更佳地，還原劑為二甲胺硼烷。包含使實質上全部金屬離子還原成金屬的量的還原劑。此類量一般為習知量且為本領域中熟習此項技術者所熟知的。
本發明的使用水性酸性預浸液的水平金屬化方法可用於無電金屬鍍覆各種基板，諸如半導體、金屬包覆及未包覆基板，諸如印刷電路板。此類金屬包覆及未包覆印刷 電路板可包含熱固性樹脂、熱塑性樹脂及其組合，包含纖維(諸如玻璃纖維)，及上述的浸漬實施例。較佳地，基板為金屬包覆印刷電路或佈線板。
本發明的水平金屬化方法可用於無電金屬鍍覆基板的特徵，諸如通孔及通道。習知歐洲背光方法可用於測定金屬鍍覆通孔及通道的壁面的效能。在歐洲背光方法中，基板在儘可能最接近通孔或通道中心處橫切以暴露金屬鍍覆的壁面。截取每個基板的橫截面以測定通孔或通道壁面覆蓋率。將橫截面置於習知光學顯微鏡下，使得光源在樣品後面。藉由在顯微鏡下可見(亦即透射穿過樣品)的光量來測定金屬沈積物的品質。透射光僅在存在不完全無電金屬覆蓋的經鍍覆通孔或通道區域中可見。若沒有光透射且截面呈現完全黑色，則其在歐洲背光標度上評級為5，表明壁面上的完全金屬覆蓋。若光通過整個截面而無任何黑暗區域，則此表明壁面上存在極少至無金屬沈積且截面評級為0。若截面具有一些黑暗區域以及光亮區域，則壁面上存在部分金屬鍍覆且樣品評級在0與5之間。
使用含有苯甲酸衍生物的水性酸性預浸液的本發明的水平方法使得平均歐洲背光值大於4至5、較佳4.3至5、更佳4.5至5。在更佳範圍內，4.6至4.7的平均歐洲背光值為典型的。在無電金屬鍍覆行業中，大於4的平均歐洲背光值為所期望的且4.5至5的平均值為較佳的。
熱塑性樹脂包含(但不限於)縮醛樹脂、丙烯酸樹脂(諸如丙烯酸甲酯)、纖維素樹脂(諸如乙酸乙酯、丙酸纖維素、乙酸丁酸纖維素及硝酸纖維素)、聚醚、耐綸(nylon)、 聚乙烯、聚苯乙烯、苯乙烯摻合物(諸如丙烯腈苯乙烯及共聚物及丙烯腈-丁二烯苯乙烯共聚物)、聚碳酸酯、聚氯三氟乙烯及乙烯基聚合物及共聚物(諸如乙酸乙烯酯、乙烯醇、乙烯基縮丁醛、氯乙烯、氯乙烯-乙酸酯共聚物、偏二氯乙烯及乙烯基縮甲醛)
熱固性樹脂包含(但不限於)鄰苯二甲酸烯丙酯、呋喃、三聚氰胺-甲醛、酚-甲醛及酚-糠醛共聚物(單獨的或與丁二烯丙烯腈共聚物或丙烯腈-丁二烯-苯乙烯共聚物複合)、聚丙烯酸酯、矽酮、脲甲醛、環氧樹脂、烯丙基樹脂、鄰苯二甲酸甘油酯及聚酯。
水平方法可用於鍍覆具有低及高Tg樹脂的基板。低Tg樹脂的Tg低於160℃且高Tg樹脂的Tg為160℃及更高。通常，高Tg樹脂的Tg為160℃至280℃或諸如170℃至240℃。高Tg聚合物樹脂包含(但不限於)聚四氟乙烯(PTFE)及聚四氟乙烯摻合物。此類摻合物包含例如具有聚苯醚及氰酸酯的PTFE。其他類型的包含具有高Tg的樹脂的聚合物樹脂包含(但不限於)環氧樹脂，諸如雙官能及多官能環氧樹脂、雙馬來醯亞胺/三嗪及環氧樹脂(BT環氧樹脂)、環氧樹脂/聚苯醚樹脂、丙烯腈丁二烯苯乙烯、聚碳酸酯(PC)、聚苯醚(PPO)、聚亞苯基醚(PPE)、聚苯硫醚(PPS)、聚碸(PS)、聚醯胺、聚酯(諸如聚對苯二甲酸乙二酯(PET)及聚對苯二甲酸丁二酯(PBT))、聚醚酮(PEEK)、液晶聚合物、聚胺基甲酸酯、聚醚醯亞胺、環氧樹脂及其複合物。
使用水性酸性預浸溶液的水平方法可使用習知水性鹼性無電金屬鍍覆浴。雖然據設想催化劑可用於無電沈 積可無電鍍覆的任何金屬，但金屬較佳選自銅、銅合金、鎳或鎳合金。更佳地，金屬選自銅及銅合金，最佳地，銅為金屬。可商購的無電鍍銅浴的實例為CIRCUPOSITTM 6550無電銅浴(可購自馬薩諸塞州馬波羅的陶氏先進材料(Dow Advanced Materials,Marlborough,MA))。
通常，銅離子源包含(但不限於)銅的水溶性鹵化物、硝酸鹽、乙酸鹽、硫酸鹽及其他有機及無機鹽。可使用此類銅鹽中的一或多者的混合物提供銅離子。實例包含硫酸銅(諸如五水合硫酸銅)、氯化銅、硝酸銅、氫氧化銅及胺基磺酸銅。組合物中可使用習知量的銅鹽。一般而言，組合物中的銅離子濃度可以在0.5g/L至30g/L範圍內。
一或多種合金金屬亦可以包含於無電組合物中。此類合金金屬包含(但不限於)鎳及錫。銅合金的實例包含銅/鎳及銅/錫。通常，銅合金為銅/鎳。
鎳及鎳合金無電浴的鎳離子源可包含鎳的一或多種習知水溶性鹽。鎳離子源包含(但不限於)硫酸鎳及鹵化鎳。鎳離子源可以習知量包含於無電合金組合物中。通常，包含0.5g/L至10g/L的量的鎳離子源。
較佳地，有待金屬鍍覆的基板為具有介電材料及多個通孔、通道或其組合的金屬包覆基板，諸如印刷電路板。所述板用水沖洗且清潔及去除油污，接著將通孔壁面或通道除膠渣。通常，準備或軟化介電質或通孔或通道除膠渣在施用溶劑溶脹劑時開始。
可使用任何習知溶劑溶脹劑。具體類型視介電材料的類型而改變。上文揭示介電質的實例。可進行少量實驗 以確定何種溶劑溶脹劑適用於特定介電材料。介電質的Tg常常決定所用溶劑溶脹劑的類型。溶劑溶脹劑包含(但不限於)二醇醚及其相關醚乙酸酯。可使用習知量的二醇醚及其相關醚乙酸酯。可商購的溶劑溶脹劑的實例為CIRCUPOSITTM Conditioner 3302、CIRCUPOSITTM Hole Prep 3303及CIRCUPOSITTM Hole Prep 4120溶液(可購自陶氏先進材料)。
在溶劑溶脹之後，視情況施用促進劑。可使用習知促進劑。此類促進劑包含(但不限於)硫酸、鉻酸、鹼性高錳酸鹽或等離子蝕刻。通常，使用鹼性高錳酸鹽作為促進劑。可商購的促進劑的實例為CIRCUPOSITTM Promoter 4130及CIRCUPOSITTM MLB Promoter 3308溶液(可購自陶氏先進材料)。視情況，基板及通孔或通道用水沖洗。
接著施用中和劑以中和促進劑殘留的任何殘餘物。可使用習知中和劑。通常，中和劑為含有一或多種胺的酸性水溶液或3wt%至25wt%過氧化氫及3wt%硫酸的溶液。可商購的中和劑的實例為CIRCUPOSITTM MLB Neutralizer 216-5(可購自陶氏先進材料)。視情況，基板及通孔或通道用水沖洗且隨後乾燥。
在中和之後，接著施用調節劑。當鍍覆通孔或通道或包含兩種類型特徵的基板時，施用酸性或鹼性調節劑。可使用習知調節劑。此類調節劑包含一或多種陽離子界面活性劑、非離子界面活性劑、錯合劑及pH調節劑或緩衝劑。可商購的酸性調節劑的實例為CIRCUPOSITTM Conditioners 3320A及3327溶液(可購自陶氏先進材料)。適合的鹼性調節劑包含(但不限於)含有一或多種四級胺及聚胺的鹼性界 面活性劑水溶液。可商購的鹼性界面活性劑的實例為CIRCUPOSITTM Conditioner 231、3325、813及860調配物。視情況，基板及通孔用水沖洗。
調節後較佳立即進行微蝕刻。可使用習知微蝕刻組合物。微蝕刻經設計以在暴露的金屬上提供微粗糙化金屬表面(例如內層及表面蝕刻)，以便增強後續鍍覆的無電金屬及稍後電鍍的黏著性。微蝕刻劑包含(但不限於)60g/L至120g/L過硫酸鈉或氧代單過硫酸鈉或鉀及硫酸(2%)混合物，或一般硫酸/過氧化氫。可商購的微蝕刻組合物的實例為CIRCUPOSITTM Microetch 3330蝕刻溶液及PREPOSITTM 748蝕刻溶液(均可購自陶氏先進材料)。視情況，基板用水沖洗。
接著，在微蝕刻之後，較佳在微蝕刻之後立即施用本發明的預浸液。上文描述水性苯甲酸及苯甲酸衍生物預浸溶液。在施用預浸溶液之後且在施用離子催化劑之前，不存在水沖洗。預浸溫度為室溫至60℃、較佳室溫至30℃。
離子催化劑接著施用於基板而無任何插入方法步驟。可商購的離子催化劑的實例為CIRCUPOSITTM 6530催化劑(可購自陶氏先進材料)。可藉由本領域中所用的習知方法進行施用，諸如將基板浸沒於催化劑溶液中或藉由使用習知設備噴塗。水平設備的催化劑停留時間可在25秒至120秒範圍內。催化劑可在室溫至80℃、較佳30℃至60℃的溫度下施用。在施用催化劑之後且在後續方法步驟之前，沖洗基板及通孔及任何通道。
接著，將還原溶液施用於基板以使催化劑的金屬離子還原成其金屬態。可藉由將基板浸沒於還原溶液中或將 還原溶液噴塗於基板上來施用還原溶液。溶液的溫度可在室溫至65℃、較佳30℃至55℃範圍內。在施用無電金屬鍍覆浴之前，還原溶液與經催化的基板之間的接觸時間可在30秒至2分鐘範圍內。
接著使用無電浴用金屬(諸如銅、銅合金、鎳或鎳合金)無電鍍覆基板及通孔與通道的壁面。較佳地，銅鍍覆於通孔與通道的壁面上。鍍覆時間及溫度可為習知的。通常，在20℃至80℃、更通常30℃至60℃的溫度下進行金屬沈積。可將基板浸沒於無電鍍覆浴中或可將無電浴噴塗於基板上。通常，可進行無電鍍覆5分鐘至30分鐘；然而，鍍覆時間可視所期望的金屬厚度而改變。在具有甲醛或其他還原劑(諸如基於乙醛酸的還原劑)的鹼性環境中進行鍍覆。通常，鍍覆溶液的pH值為10及更高，較佳地，pH值為11及更高，更佳地，pH值為12至13.5，最佳地，pH值為12.5至13.5。
視情況，可將抗變色劑施用於金屬。可使用習知抗變色組合物。抗變色劑的實例為ANTI TARNISH 7130溶液(可購自陶氏先進材料)。基板可視情況用水沖洗且隨後可乾燥基板。
其他加工可包含藉由光成像及在基板上的進一步金屬沈積(諸如例如銅、銅合金、錫及錫合金的電解金屬沈積)而進行的習知加工。
包含以下實例以進一步說明本發明，但並不意欲限制本發明的範圍。
實例1
基於3,5-二羥基苯甲酸的預浸液及十二烷基苯磺酸鹽預浸水溶液的起泡高度比較
製備200ppm CIRCUPOSITTM 6530離子鈀催化劑的一公升鹼性水溶液作為工作浴。將200mL催化劑溶液添加至兩個一公升玻璃杯中。在攪拌棒混合下，將10ppm 3,5-二羥基苯甲酸預浸溶液添加至一個燒杯中。將硝酸及氫氧化鈉添加至3,5-二羥基苯甲酸溶液中以提供pH 2。接著將此溶液添加至催化劑溶液中。將10ppm十二烷基苯磺酸鈉陰離子界面活性劑預浸溶液添加至第二燒杯中。將預浸溶液添加至催化劑浴模擬在沒有水沖洗的情況下將預浸溶液拖入催化劑的水平方法。
來自經由塑膠管連接至玻璃管的設備壓縮空氣出口的淨化空氣以2公升/分鐘施用至每個具有催化劑及預浸液的溶液20分鐘以誘導溶液鼓泡，從而模擬水平無電金屬鍍覆方法的典型攪拌。在20分鐘之後，停止空氣且立即使用鄰近每個燒杯的習知厘米校準尺量測每個溶液的起泡高度。包含3,5-二羥基苯甲酸及離子催化劑的溶液的起泡高度為7cm。相比之下，包含十二烷基苯磺酸鈉及離子催化劑的溶液的起泡高度為13cm。在5分鐘空閒之後，再次量測起泡高度。包含3,5-二羥基苯甲酸及離子催化劑的溶液的起泡高度為0.5cm。相比之下，包含十二烷基苯磺酸鈉及離子催化劑的溶液的起泡高度為6cm。結果顯示含有3,5-二羥基苯甲酸的溶液與包含十二烷基苯磺酸鹽的溶液相比，顯著減少離子催化劑溶液中的泡沫形成量。
實例2
含有2,4-二羥基苯甲酸及抗壞血酸的預浸溶液的鍍覆效能
製備兩種預浸溶液。一種溶液係藉由將2.5g/L2,4-二羥基苯甲酸添加至去離子水來製備。第二溶液係藉由將3g/L抗壞血酸添加至去離子水來製備。每種溶液中的酸濃度為0.016mol/L。用稀的氫氧化鈉及硝酸水溶液將每種溶液的pH值調節至2。提供以下含有多個通孔的銅包覆環氧樹脂層壓物，每種各兩個：來自Taiwan Union Technology Corporation的TUC-662、來自Shengyi Technology的SY-1141、來自Nanya Plastics的NPGN-150、來自Isola的370HR及來自Elite Material,Co.,Ltd的EM-355。每個層壓物的厚度為2mm且通孔的直徑為1mm。每個層壓物用含有2,4-二羥基苯甲酸的水性酸性預浸溶液或含有抗壞血酸的水性酸性預浸液處理。根據以下方法準備每個層壓物且用無電銅鍍覆：1.藉由施用CIRCUPOSITTM 211膨脹劑、CIRCUPOSITTM 213高錳酸鹽氧化劑及硫酸/過氧化氫中和劑浴而將每個銅包覆層壓物除膠渣；2.層壓物接著藉由在40℃下浸沒於含有陽離子界面活性劑、非離子界面活性劑及緩衝劑的4% CIRCUPOSITTM Conditioner-Cleaner 231的調節劑水溶液中2分鐘來調節，接著用流動的自來水沖洗每個層壓物2分鐘；3.層壓物接著在室溫下浸沒於基於硫酸及過硫酸鈉的PREPOSITTM 748蝕刻溶液中1.5分鐘以微蝕刻層壓物的通孔，且隨後用流動的去離子水沖洗2分鐘；4.每個層壓物在室溫下浸沒於包含2,4-二羥基苯甲酸或抗壞血酸的預浸液中45秒，緊接在預浸溶液施用之後且在後 續步驟之前不進行水沖洗。任一預浸液均未觀察到起泡；5.每個層壓物接著在40℃下浸沒於200ppm CIRCUPOSITTM 6530離子鈀催化劑的鹼性離子催化劑水溶液中90秒，接著流動的自來水沖洗2分鐘；6.層壓物接著在30℃下浸沒於基於二甲胺硼烷的CIRCUPOSITTM 6540還原劑溶液中90秒以使鈀離子還原成鈀金屬，且隨後用流動的去離子水沖洗1.5分鐘；7.經活化的層壓物在42℃下浸沒於CIRCUPOSITTM 6550無電銅浴中6分鐘以便在通孔中鍍銅；8.在鍍銅之後，層壓物用流動的自來水沖洗4分鐘且隨後藉由空氣吹掃而乾燥。
每個層壓物在儘可能最接近通孔中心處橫切以暴露鍍銅的壁面。截取每塊板的橫截面以測定通孔壁面覆蓋率。使用歐洲背光分級標度。將每塊板的橫截面置於50X放大倍率的習知光學顯微鏡下，使得光源在樣品後面。藉由在顯微鏡下可見(亦即透射穿過樣品)的光量來測定銅沈積物的品質。透射光僅在存在不完全無電銅覆蓋的經鍍覆通孔區域中可見。若沒有光透射且截面呈現完全黑色，則其在背光標度上評級為5，表明通孔壁面的完全銅覆蓋。若光通過整個截面而無任何黑暗區域，則此表明壁面上存在極少至無銅金屬沈積且截面評級為0。若截面具有一些黑暗區域以及光亮區域，則其評級在0與5之間。每塊板最少檢查且評級十個通孔。
圖1為比較用含有2,4-二羥基苯甲酸(2,4-DHBA)的預浸液處理的層壓物與用抗壞血酸預浸液處理 的層壓物的通孔無電鍍覆的背光效能標繪圖。標繪圖顯示每個層壓物的背光值範圍及每個層壓物的平均背光值。背光值亦記錄在下表中。
除EM-355層壓物以外，鍍覆結果顯示用2,4-二羥基苯甲酸處理的層壓物與用抗壞血酸處理的層壓物相比在通孔鍍覆覆蓋率方面具有顯著改善。結果表明2,4-二羥基苯甲酸與抗壞血酸相比在通孔上具有較佳吸附。
實例3
鞣酸作為預浸溶液用於無電銅金屬化
鞣酸的預浸溶液係藉由將22g/L鞣酸添加至去離子水來製備。溶液中的鞣酸濃度為0.016mol/L。用稀的氫氧化鈉及硝酸水溶液將溶液的pH值調節2。提供以下含有多個通孔的銅包覆環氧樹脂層壓物：來自Taiwan Union Technology Corporation的TUC-662、來自Shengyi Technology 的SY-1141、來自Nanya Plastics的NPGN-150、來自Isola的370HR及來自Elite Material,Co.,Ltd.的EM-355。每個層壓物用水性鞣酸預浸溶液處理。觀察到一些起泡。根據實例2中的方法準備每個層壓物且用無電銅鍍覆。
每個層壓物在儘可能最接近通孔中心處橫切以暴露鍍銅的壁面。截取每塊板的橫截面以測定通孔壁面覆蓋率。使用歐洲背光分級標度。將每塊板的橫截面置於50X放大倍率的習知光學顯微鏡下，使得光源在樣品後面。藉由在顯微鏡下可見(亦即透射穿過樣品)的光量來測定銅沈積物的品質。透射光僅在存在不完全無電銅覆蓋的經鍍覆通孔區域中可見。每塊板最少檢查且評級十個通孔。若沒有光透射且截面呈現完全黑色，則其在背光標度上評級為5，表明通孔壁面的完全銅覆蓋。若光通過整個截面而無任何黑暗區域，則此表明壁面上存在極少至無銅金屬沈積且截面評級為0。若截面具有一些黑暗區域以及光亮區域，則其評級在0與5之間。
圖2為顯示用含有鞣酸的預浸液處理的層壓物的通孔無電鍍覆的背光效能標繪圖。標繪圖顯示每個層壓物的背光值範圍及每個層壓物的平均背光值。背光值亦記錄在下表中。
無電銅鍍覆的平均背光值在低至2.7至僅3.7的範圍內。與包含2,4-二羥基苯甲酸的預浸液相比，使用鞣酸預浸液的無電銅鍍覆較差。2,4-二羥基苯甲酸與鞣酸相比在通孔壁面上具有較佳吸附。

Claims (11)

  1. 一種無電鍍覆基板的水平方法，其包括：a)清潔及調節所述基板；b)微蝕刻所述基板；c)提供水性酸性預浸組合物，所述組合物由一或多種具有下式的化合物： 其中R1、R2、R3、R4及R5獨立地選自氫、直鏈或分支鏈(C1-C4)烷基、鹵化物、NH2、NO2、SO3H、OH、醯基、(C1-C4)烷氧基及苯甲醯基，且Z為OY或苯甲醯基，其中Y為氫、鹵化物或鹼金屬陽離子；及視情況選用的一或多種緩衝劑組成；d)將所述水性酸性預浸組合物施用於所述基板；e)將離子催化劑施用於所述基板；f)將還原劑施用於具有所述離子催化劑的所述基板；及g)將無電金屬鍍覆浴施用於具有所述催化劑的所述基板以便金屬鍍覆所述基板。
  2. 如申請專利範圍第1項所述的水平方法，其中所述一或多種緩衝劑選自鹼金屬氫氧化物。
  3. 如申請專利範圍第1項所述的水平方法，其中所述一或多種緩衝劑選自硝酸。
  4. 如申請專利範圍第1項所述的水平方法，其中所述離子催 化劑包括一或多種選自鈀、鉑及金的金屬離子。
  5. 如申請專利範圍第1項所述的水平方法，其中所述離子催化劑的錯合劑為雜環氮化合物。
  6. 如申請專利範圍第5項所述的水平方法，其中所述雜環氮化合物選自嘧啶衍生物、吡嗪及吡啶衍生物。
  7. 如申請專利範圍第6項所述的水平方法，其中所述吡嗪衍生物選自2,6-二甲基吡嗪、2,3-二甲基吡嗪、2,5-二甲基吡嗪、2,3,5-三甲基吡嗪、2-乙醯基吡嗪、胺基吡嗪、乙基吡嗪、甲氧基吡嗪、3,4-二甲基吡嗪及2-(2'-羥乙基)吡嗪。
  8. 如申請專利範圍第6項所述的水平方法，其中所述嘧啶衍生物選自尿嘧啶、巴比妥酸、乳清酸、胸腺嘧啶、2-胺基嘧啶、6-羥基-2,4-二甲基嘧啶、6-甲基尿嘧啶、2-羥基嘧啶、4,6-二氯嘧啶、2,4-二甲氧基嘧啶、2-胺基-4,6-二甲基嘧啶、2-羥基-4,6-二甲基嘧啶及6-甲基異胞嘧啶。
  9. 如申請專利範圍第6項所述的水平方法，其中所述吡啶衍生物選自4-二甲胺基吡啶、4-胺基吡啶、2-胺基吡啶、4-(甲胺基)吡啶、2-(甲胺基)吡啶、2-胺基-4,6-二甲基吡啶、2-二甲胺基-4,6-二甲基吡啶、4-二乙胺基吡啶、2-(吡啶-3-基)-乙酸、2-胺基-3-(吡啶-3-基)-丙酸、2-胺基-3-(吡啶-2-基)-丙酸、3-(吡啶-3-基)-丙烯酸、3-(4-甲基吡啶-2-基)丙烯酸及3-(吡啶-3-基)-丙烯醯胺。
  10. 如申請專利範圍第1項所述的水平方法，其中所述水性酸性預浸組合物的pH值小於7。
  11. 如申請專利範圍第1項所述的水平方法，其中所述基板包括多個通孔、通道或其組合。
TW106103743A 2016-02-29 2017-02-03 具有離子催化劑的基板的無電金屬鍍覆的水平方法 TWI606138B (zh)

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