200905011 九、發明說明 【發明所屬之技術領域】 本發明係關於鋁或鋁合金之表面處理方法，尤其於晶 圓上藉由電鍍形成UMB(金屬墊層）或凸塊時之鋁或鋁合金 之表面處理方法。 【先前技術】 傳統上，作爲於矽圓上形成UMB或凸塊之方法，可 使用於晶圓上所圖型化之鋁薄膜電極，施以鋅取代處理， 形成鋅被膜後，由無電解電鍍形成凸塊之方法，取代上述 鋅取代處理，施以鈀處理後，由無電解鍍鎳形成凸塊之方 法，或以鎳直接取代鋁薄膜電極之表面後，由自己觸媒型 無電解鍍鎳形成凸塊之方法等。 另外，由如此方法形成無電解鍍鎳被膜之UMB或凸 塊，爲改善電氣特性，尤其降低電阻，於無電解鍍鎳被膜 上，再施以無電解鍍銅。此時，因無電解鍍鎳被膜無觸媒 性，不能直接無電解鍍銅於無電解鍍鎳被膜上，所以傳統 上施以用以賦予觸媒性於無電解鍍鎳被膜之銅取代處理。 然而，此銅取代處理容易侵蝕無電解鍍鎳被膜，該結 果係底層（鋁或鋁合金）攻擊（侵蝕），而有銅取代處理形成 之無電解鍍銅被膜之密合性變低之問題。 【發明內容】 發明之揭示 -5- 200905011 本發明係有鑑於上述情況所實施者，提供於鋁或鋁合 金上形成無電解鍍鎳被膜，進而於此無電解鍍鎳被膜上形 成無電解鍍銅被膜，處理鋁或鋁合金之表面時，不過度侵 蝕無電解鍍鎳被膜，賦予良好的觸媒性，形成無電解鍍銅 被膜，可賦予無電解鍍銅被膜之高密合性之鋁或鋁合金之 表面處理方法爲目的。 本發明者爲達成上述目的，努力檢討的結果係發現於 鋁或鋁合金上形成無電解鍍鎳被膜，進而於此無電解鍍鎳 被膜上形成無電解鍍銅被膜，處理鋁或鋁合金之表面時， 於無電解鍍鎳被膜之表面，藉由取代電鍍或無電解電鍍， 形成Ag、Au、Pd、Pt、Rh或此等合金之中間電鍍被膜， 藉由形成無電解鍍銅被膜，可賦予良好的觸媒性之無電解 鍍銅被膜，另外，所得之無電解鍍銅被膜亦具有高密合性 者，而完成本發明。 因此，本發明係提供下述鋁或鋁合金之表面處理方法 (1): 至少於表面上具有鋁或鋁合金之被處理物之上述鋁或 鋁合金上形成無電解鍍鎳被膜，進而於該無電解鍍鎳被膜 上形成無電解鍍銅被膜之鋁或鋁合金之表面處理方法， 包含 除去上述被處理物之上述鋁或鋁合金表層上所形成之 鋁氧化被膜，於上述鋁或鋁合金上形成無電解鍍鎳被膜之 -6 - 200905011 鍍鎳步驟， 於上述無電解鍍鎳被膜之表面，藉由取代電鍍或無電 解電鍍，形成 Ag、Au、Pd、Pt、Rh或此等合金之中間電 鍍被膜之中間電鍍步驟，及 於上述中間電鍍被膜之表面，形成無電解鍍銅被膜之 鍍銅步驟 爲特徵之鋁或鋁合金之表面處理方法。 (2): 上述鍍鎳步驟係包含浸漬上述被處理物於含有可取代 鋁之金屬之鋁氧化被膜用除去液，除去上述鋁氧化被膜， 並形成上述除去液中所含可取代鋁之金屬之取代金屬靥；^ 步驟， 以具有氧化作用之酸性液除去該取代金屬層之步驟， 及 除去上述取代金屬層所露出之鋁或鋁合金上，形成無 電解鍍鎳被膜之步驟爲特徵之（1)記載之表面處理方法。 (3) : 上述鋁氧化被膜用除去液係含有可取代鋁之金屬的_ 、及酸而成爲特徵之（2)記載之表面處理方法。 (4) : 上述鋁氧化被膜用除去液係含有可取代鋁之金屬的鹽 200905011 或氧化物 '及該金屬離子之可溶化劑、及鹼而成，pH爲 10〜13.5爲特徵之（2)記載之表面處理方法。 (5)： 上述鋁氧化被膜用除去液係更含有界面活性劑而成爲 特徵之（3)或（4)記載之表面處理方法。 依據本發明’於鋁或鋁合金上形成無電解鍍鎳被膜， 進而於此無電解鍍鎳被膜上形成無電解鍍銅被膜，處理鋁 或鋁合金之表面時，可賦予良好的觸媒性，形成無電解鍍 銅被膜，所得之無電解鍍銅被膜，爲具有高密合性者。 用以實施發明之最佳形態 以下係更詳細地說明本發明。 本發明之表面處理方法係至少於表面上具有鋁或鋁合 金之被處理物之上述鋁或鋁合金上形成無電解鍍鎳被膜， 進而於該無電解鍍鎳被膜上形成無電解鍍銅被膜之鋁或鋁 合金之表面處理方法， 包含除去上述被處理物之上述鋁或鋁合金表層上所形 成之鋁氧化被膜，於上述鋁或鋁合金上形成無電解鍍鎳被 膜之鍍鎳步驟， 於上述無電解鍍鎳被膜之表面，藉由取代電鍍或無電 解電鍍，形成Ag、Au、Pd、Pt、Rh或此等合金之中間電 鍍被膜之中間電鍍步驟，及 於上述中間電鑛被膜之表面，形成無電解鍍銅被膜之 -8- 200905011 鍍銅步驟者。以下係說明關於上述各步驟。 [鍍鎳步驟] 本發明中’除去被處理物之鋁或鋁合金表層上所形成 之銘氧化被膜’於鋁或鋁合金上形成無電解鍍鎳被膜，除 去銘氧化被膜’可使用傳統已知方法，除去鋁氧化被膜， 於露出之銘或鋁合金上，形成無電解鍍鎳被膜。 达匕時’浸漬被處理物於含有可取代鋁之金屬之鋁氧化 被膜用除去液’除去鋁氧化被膜，並形成除去液中所含可 取代銘之金屬之取代金屬層，以具有氧化作用之酸性液除 去此取代金屬層’亦可於除去取代金屬層所露出之鋁或鋁 合金上，形成無電解鍍鎳被膜。 作爲此銘氧化被膜用除去液，可適合使用含有可取代 隹呂之金屬的鹽、及酸、及含有界面活性劑尤佳而成者（酸 性除去液）、或可取代鋁之金屬的鹽或氧化物、及該金屬 離子之可溶化劑、及鹼 '及含有界面活性劑尤佳而成，pH 爲1 〇〜1 3 · 5者（鹼性除去液）。 (酸性除去液） 作S酸性除去液所含之構成金屬鹽之金屬，只要可取 代銘之金屬即可，並無特別的限制，但以比鋁之離子化傾 向小之金屬爲宜’可舉例如鋅、鐵、鈷、鎳、錫、鉛、銅 、水銀、銀、鉛、金、鈀等，作爲上述金屬鹽，可舉例如 此金屬之硝酸鹽或硫酸鹽等之水溶性鹽。尤其，就除去液 -9 - 200905011 之安定性或對鋁或鋁合金素材攻擊性少等之理由，以硫酸 鹽爲宜。此等係可單獨1種或倂用2種以上。其中，因銀 、鎳、銅於其他部位析出之虞少，所以適宜，尤其，銅、 銀之離子化傾向比銘小許多，所以更容易進行取代反應， 可縮短蝕刻處理時間，所以適宜。 作爲酸性除去液所使用之金屬鹽濃度，雖非特別限制 者，作爲金屬量，通常爲lppm以上，以l〇ppm以上爲宜 ，上限通常爲10,000ppm以下，以5,000ppm以下爲宜。 金屬鹽的濃度過小時，不能與底層之鋁充分地進行取代， 發生必須進行金屬鹽補給。另一方面，濃度過大時，錯或 鋁合金係於晶圓上所圖型化之電極時，侵鈾鋁或鋁合金底 層以外之構件，或超出於鋁或鋁合金底層以外之構件而析 出。 作爲酸性除去液所含酸，雖非特別限定者，但必須爲 溶解氧化膜的酸，可舉例如硫酸、磷酸、鹽酸、氫氟酸等 ’此等係可單獨1種或倂用2種以上。其中，就除去液之 安定性、或對鋁或鋁合金素材攻擊性少等之觀點上，以硫 酸爲宜。 酸於除去液中之濃度，雖非特別限制者，但通常爲 l〇g/L以上，以5g/L以上爲宜，上限通常爲5〇Og/L以下 ’以300g/L以下爲宜。酸的濃度過小時，不能溶解氧化 膜而無效果，另一方面，濃度過大時，侵蝕鋁或鋁合金底 層以外之構件。 -10- 200905011 (鹼性除去液） 作爲鹼性除去液所含之構成金屬鹽或金屬氧化物之金 屬’只要可取代鋁之金屬即可，並無特別的限制，但以比 銘之離子化傾向小之金屬爲宜，可舉例如錳、鋅、鐵、鈷 、鎳、錫、鉛、銅、水銀、銀、鉑、金、鈀等，作爲上述 # ®鹽’可舉例如如此金屬之硝酸鹽或硫酸鹽等之水溶性 鹽。其中，以錳、鋅與底層之鋁之還原電位差小爲宜。 作爲鹼性除去液所使用之金屬鹽或金屬氧化物之濃度 ’雖非特別限制者，作爲金屬量，通常爲lPpm(mg/L)以 上’以 10ppm(mg/L)以上爲宜，上限通常爲 10,000ppm (mg/L)以下，以5,000ppm(mg/L)以下爲宜。金屬鹽或金屬 氧化物的濃度過小時，不能與底層之鋁充分地進行取代， 發生必須進行金屬鹽或金屬氧化物補給。另一方面，濃度 過大時’於鋁或鋁合金係晶圓上所圖型化之電極時，侵蝕 鋁或鋁合金底層以外之構件，或超出於鋁或鋁合金底層以 外之構件而析出。 作爲鹼性除去液所含金屬離子之可溶化劑，雖非特別 限定者’但可使用通常的配位劑、螯合劑。具體上，可使 用如乙醇酸、乳酸、蘋果酸、酒石酸、檸檬酸、葡糖酸、 庚葡糖酸等之羥基羧酸及該鹽、甘油、胺基二羧酸、氮川 三乙酸、EDTA(乙二胺四乙酸）、羥乙基伸乙基二胺三乙酸 、二伸乙基三胺五乙酸、聚胺基聚羧酸等之胺基羧酸及該 鹽、HEDP(羥基亞乙基二磷酸）、胺基三甲基磺酸、伸乙基 二胺四甲基磺酸等之亞磷酸系螯合劑及該鹽、伸乙基二胺 -11 - 200905011 、二伸乙基三胺、三伸乙基四胺等之胺系螯合劑等。 作爲鹼性除去液所使用之可溶化劑之濃度，雖非特別 限定者，但相對於所使用之金屬鹽，可溶化劑之總濃度爲 0.5〜10(莫耳比），以〇.8〜5(莫耳比）爲宜。 作爲鹼性除去液所含的鹼，雖非特別限定者，但必須 爲溶解氧化膜的鹼，可舉例如LiOH、NaOH、KOH等之鹼 金屬或氫氧化三甲基銨（TMAH)銨、膽鹼等之四級銨之氫 氧化物等。另外，鹼之添加量係使除去液之p Η爲規定範 圍的量’亦即’使ρ Η爲1 0〜1 3 · 5，以1 1〜1 3爲宜的量。 pH若未滿10時，溶解速度有明顯降低之虞，pH若超過 1 3 . 5時，溶解速度過快而不能控制。 上述氧化被膜除去液中，對於酸性除去液及鹼性除去 液中任一種’就賦予水沾濕性之觀點，以含界面活性劑爲 宜。作爲所使用之界面活性劑，雖非特別限定者，但可舉 例如聚乙二醇、聚環氧乙烷·聚環氧丙烷嵌塊共聚型活性 劑之非離子型界面活性劑、其他之陰離子型、陽離子型界 面活性劑，就均勻處理性之觀點，其中以非離子型、陰離 子型爲宜。此等係可單獨1種或倂用2種以上。 例如使用聚乙二醇作爲界面活性劑，該分子量雖非特 別限定者，但通常爲1 0 0以上，以2 0 0以上爲宜，上限通 常爲20, 〇〇〇以下，以6,000以下爲宜。分子量若過大時， 溶解性變差’另一方面，分子量若過小時，不能賦予水沾 濕性。另外’作爲聚乙二醇’可使用市售物。 另外’作爲界面活性劑之除去液中之濃度，雖非特別 -12- 200905011 限定者’通常爲lppm(mg/L)以上，以10ppm(mg/L)以上爲 且’上限通常爲 5,000ppm(mg/L)以下，以 2,000ppm (mg/L)以下爲宜。界面活性劑於除去液中之濃度若過小時 ’所得之水沾濕性效果低，另一方面，濃度若過大時，於 銘或銘合金以外之構件上析出取代金屬。 另外，上述氧化被膜用除去液係酸性除去液及鹼性除 去液中任一種，就操作安全性之觀點，以調製爲水溶液爲 宜，但亦可使用其他溶劑，例如甲醇、乙醇、IPA(異丙醇 )等，或與水之混合溶劑。另外，此等溶劑係可單獨1種 或倂用2種以上。 浸漬具有鋁或鋁合金之被處理物於除去液時之浸漬條 件，雖非特別限定者，但有鑑於應除去鋁氧化被膜之厚度 等而可適當設定，但通常爲1分鐘以上，以2分鐘以上爲 宜，上限通常爲20分鐘以下’以15分鐘以下爲宜。浸清 時間過短時，未進行取代，氧化被膜不能充分除去，另一 方面，浸漬時間若過長時，自取代金屬層之小孔侵入除去 液，有溶出鋁或鋁合金之虞。 另外’作爲浸漬時之溫度’雖非特別限定者，但通常 爲20°C以上’以25 °C以上爲宜，上限通常爲l〇〇t：以下， 以9 5 °C以下尤佳。浸漬溫度若過低時，不能溶解氧化被膜 ’另一方面’浸漬溫度若過高時’侵入鋁或鋁合金以外之 構件。另外’浸漬時，就均勻處理之觀點，以進行液攪样 或被處理物搖動爲宜。 使用上述氧化被膜除去液時，除去鋁氧化被膜，並且 -13- 200905011 形成可取代銘之金屬之取代金屬層，此取代金屬層係可由 具有氧化作用之酸性液除去’於除去取代金屬層之鋁或鋁 合金上，直接或進行鋅取代處理或絶處理後，進行電鍍。 以具有氧化;作用之酸性液除去取代金屬層時，就緩和 底層之鋁或鋁合金之反應性之觀點，可使用氧化作用之酸 性液。此時’作爲具有氧化作用之酸性液係以使用於硝酸 等之具有氧化作用的酸或該水溶液、硫酸、鹽酸等之不具 有氧化作用的酸或該水溶液中，添加1種或2種以上之氧 化劑’例如過氧化氫、過硫酸鈉、過硫酸銨、過硫酸鉀等 者爲宜。此時’酸係具有溶解取代金屬之作用，氧化劑係 具有緩和對鋁或鋁合金底層反應性之作用。另外，氧化劑 中’由氫及氧所形成，就還原時成爲水之觀點，以過氧化 氫爲宜’另外’就具有安定性，容易操作之觀點，以過硫 酸鈉、過硫酸鉀爲宜。 在此，使用硝酸作爲酸（及氧化劑）時，溶解液（水溶液 )中之硝酸量，通常爲200ml/L以上，以3 00ml/L以上爲 宜，上限通常爲l，000ml/L以下，以70〇ml/L以下爲宜。 硝酸量若過少時，氧化力低，反應不停止。另外，所謂 l，0 00ml/L之硝酸係指總量爲硝酸。 另外，使用氧化劑時，溶解液中之氧化劑量，通常爲 50g/L以上’以75g/L以上爲宜，上限通常爲500g/L以下 ，以3 00g/L以下爲宜。氧化劑量若過少時，氧化力低， 反應不停止，另一方面，若過多時，經濟性差。另外’如 此與氧化劑共同使用之鹽酸、硫酸等酸的濃度，通常爲 -14- 200905011 l〇g/L以上’以l5g/L以上爲宜，上限通常爲500g/L以下 ’以3 00g/L以下爲宜。酸的濃度若過小時，發生難以溶 解取代金屬層，另一方面，濃度若過大時，有侵蝕鋁或銘 合金以外之構件之虞。另外，在此使用的酸係以非氧化性 者爲宜’但亦可爲硝酸等之氧化性酸，另外，亦可混合氧 化性酸及非氧化性酸使用。 於此溶解處理，作爲處理時間，並無特別限制，例如 可以5〜3 0 0秒進行溶解處理，作爲溶解處理溫度，例如 可採用1 0〜4〇t之條件。另外，溶解處理中，電鑛被處理 物係可靜止，或可搖動，亦可進行液攪拌。 除去鋁氧化被膜，露出的鋁或鋁合金上，形成無電解 鍍鎳被膜。此無電解鍍鎳係可使用已知之無電解鍍鎳浴， 可舉例如含有硫酸鎳、有機酸（琥珀酸、蘋果酸、檸檬酸 等）、次亞磷酸鈉等之無電解鍍鎳浴，亦可使用市售之電 鍍浴。 形成無電解鍍鎳被膜之膜厚通常爲1〜20 μηι程度，配 合形成電鍍被膜的膜厚，選定電鍍溫度及電鍍時間，通常 電鍍溫度爲50〜95 °C，電鍍時間爲5〜120分鐘。 另外，無電解鍍鎳係可直接施於鋁或鋁合金表面，另 外，亦可由辞取代處理、鈀處理等，對鋁或鋁合金表面進 行活化處理後，進行無電解鍍鎳處理。作爲如此活性化處 理，尤其鋅取代處理，其中藉由施以鹼鋅取代處理，於鋁 或鋁合金表面，形成鋅被膜，就提升電鍍被膜之密合性上 之觀點係適合的。 -15- 200905011 在此，作爲鋅取代處理’具體上係指使用含鋅鹽之溶 液’進行取代析出鋅之處理者。鹼鋅取代處理時，使用鹼 性之鋅酸溶液者’另外，作爲酸性鋅取代處理時，使用含 酸性鋅鹽之溶液’進行取代析出鋅之處理者，此等係可以 已知方法進行。另外’作爲鈀處理，使用含鈀鹽之溶液， 進行取代析出鈀之處理者，可以已知方法進行。 [中間電鍍步驟] 本發明中以上述鍍鎳步驟形成之無電解鑛鎳被膜之表 面上，藉由取代電鍍或無電解電鍍，形成Ag、Au、Pd、 Pt、Rh或此等合金之中間電鍍被膜。此取代電鍍或無電解 電鍍係可使用含有Ag、Au、Pd、Pt或Rh之已知取代電 鍍浴或無電解電鍍浴，可舉例如含有金屬（Ag、Au、Pd、 Pt、Rh)鹽、無機酸（硫酸、鹽酸等）、有機酸（琥珀酸、蘋 果酸、檸檬酸等）等之取代電鍍浴、含有金屬（Ag、Au、Pd 、Pt、Rh)鹽、配位劑（有機酸、EDTA等）、還原劑（甲酸、 次亞磷酸鈉、聯氨等）等之無電解電鍍浴，亦可使用市售 之電鍍浴。 形成中間電鍍被膜之膜厚通常爲0.005〜Ι.Ομιη，以 0.01〜0.5 μιη程度爲宜，配合形成電鍍被膜之膜厚，選定 電鍍溫度及電鍍時間，通常電鍍溫度係30〜80 °C，電鍍時 間爲10秒〜10分鐘。形成此人§、八11、？(1、？1、尺11或此 等合金之中間電鍍被膜，藉由後述的鍍銅步驟，形成無電 解鍍銅被膜，可賦予良好觸媒性，形成無電解鍍銅被膜。 -16- 200905011 [鍍銅步驟] 本發明中，於上述中間電鍍步驟形成之中間 表面，形成無電解鍍銅被膜。對此無電解鍍銅係 知之無電解鍍銅浴，可舉例如含有硫酸銅、配ί: 酸、EDTA等）、甲醛水等之無電解鍍銅浴，亦可 之電鍍浴。 形成的無電解鍍銅被膜之膜厚通常爲0.05 -度’配合形成電鍍被膜的膜厚，選定電鍍溫度及 ’通常電鍍溫度係2 0〜7 5 °C，電鍍時間爲5分鐘 〇 本發明對象之至少於表面上具有鋁或鋁合金 物，可爲被處理物整體爲鋁或鋁合金所形成，亦 或鋁合金被覆於非鋁材質（例如矽、F R A (印刷基 ))之全部或部份表面者。另外，作爲該鋁或鋁合 ’並無特別限定，對於例如坯料材、壓延材、鑄 膜等’可良好適用。另外，於非鋁材質表面形成 金之被膜時’作爲此被膜之形成方法，雖無特別 但作爲該形成方法’例如真空蒸著法、濺鍍法、 法等之氣相電鍍法係適合的。 作爲此被膜厚度’就使確實殘留鋁或鋁合金 點上，通常爲0.5 μηι以上，以1 μιη以上爲宜。另 度上限雖無特別限定’但通常爲1〇〇μιη以下。 另外’作爲上述被膜成份，只要爲鋁或鋁合 並非特別的限定者，對於例如Al-Si(Si含有率爲 電鍍被膜 可使用已 S劑（酒石 使用市售 -1 0 μ m 程 電鍍時間 :〜6小時 之被處理 可爲以鋁 板之基材 金之形態 造材、被 鋁或鋁合 限定者， 離子電鍍 底層之觀 外，該厚 金即可， 0.5 〜1 .0 -17- 200905011 重量％)、Al-Cu(Cu含有率爲〇·5〜1.0重量％)等之合金被 膜，亦可適用。 【實施方式】 實施例 以下係表示實施例及比較例’由本發明具體地說明， 但本發明並非侷限於下述實施例者。 [實施例1] 作爲電鍍被處理物，使用由濺鍍法被覆銘層厚度爲 5 μιη之矽板，對此鋁層，依序施以如表1所示處理。關於 所得電鍍被膜之特性，評估結果如表2所示。 表1 處理 藥液 條件 (1) 清潔劑/表面洗淨 Epitas MCL-1 6 * 5 0°C 5分鐘 (2) 除去氧化被膜 下述氧化被膜除 5 〇°c 1分鐘 (3) 除去黑粉 50% HN〇3 2 0°C 3 〇秒鐘 (4) 第一鋅酸鹽處理 Epitas MCT-1 7* 2 〇〇c 1 〇秒鐘 (5) 除去鋅酸被膜 1 5 0% HN〇3 20°C 60秒鐘 (6) 第二鋅酸鹽處理 Epitas MCT-1 7 * 2 0°C 3 〇秒鏟 (7) 無電解鍍鎳 Epitas NPR-18* 膜厚3_ (8) 取代電鍍（亞硫酸金） Epitas TDS-20* 膜厚 〇 . 0 4 n m (9) 氺 · 無電解鍍銅 U itrf 丫 雄 H/W△七 /Λ — Epitas PSP-20* 膜厚8 :上村工業股份有限公司 氧化被膜除去液：含作爲金屬鹽之2g/L之硫酸鋅 -18- 200905011 作爲可溶化劑之l〇g/L之EDTA_2Na、作爲界面活性劑之 lg/L之 PEG(聚乙二醇）-1〇〇〇、作爲鹼之NaOH，調整成 PH12.4之水溶液 [實施例2] 除了以（8)之取代鑛金（亞硫酸金）作爲取代鍍金（氰化 金）（藥液：Epitas TDL-20(上村工業股份有限公司製），條 件：膜厚爲〇.〇5 μιη)以外，與實施例1同樣地施以處理。 關於所得之電鍍被膜之特性，評估結果如表2所示。 [實施例3] 除了以（8)之取代鍍金（亞硫酸金）作爲無電解鍍Pd(藥 液：Epitas TFP_3〇(上村工業股份有限公司製），條件：膜 厚爲0.06 μιη)以外，與實施例1同樣地施以處理。關於所 得之電鍍被膜之特性，評估結果如表2所示。 [比較例1] 除了未實施（8)之取代鍍金（亞硫酸金）以外，與實施例 1同樣地施以處理。關於所得之電鍍被膜之特性，評估結 果如表2所示。 [比較例2] 除了以（8)之取代鍍金（亞硫酸金）作爲銅取代處理（藥 液：硫酸銅爲〇.5g/L硫酸（62_5%)1 Og/L，條件：20°C 30 -19- 200905011 秒鐘）以外’與實施例1同樣地施以處理。關於所得之電 鍍被膜之特性，評估結果如表2所示。200905011 IX. INSTRUCTIONS OF THE INVENTION [Technical Field] The present invention relates to a surface treatment method for aluminum or aluminum alloy, particularly aluminum or aluminum alloy when a UMB (metal underlayer) or a bump is formed by electroplating on a wafer. Surface treatment method. [Prior Art] Conventionally, as a method of forming a UMB or a bump on a circle, an aluminum film electrode for patterning on a wafer can be subjected to zinc substitution treatment to form a zinc film, and electroless plating is performed. a method of forming a bump, instead of the above zinc substitution treatment, after the palladium treatment, forming a bump by electroless nickel plating, or directly replacing the surface of the aluminum thin film electrode with nickel, the self-electrolytic nickel plating by the self-catalyst type A method of forming a bump or the like. Further, UMB or bumps of the electroless nickel-plated film are formed by such a method, and in order to improve electrical characteristics, particularly to lower the electric resistance, electroless copper plating is applied to the electroless nickel plating film. At this time, since the electroless nickel plating film has no catalytic property and cannot be directly electrolessly plated on the electroless nickel plating film, a copper substitution treatment for imparting a catalytic property to the electroless nickel plating film is conventionally applied. However, this copper substitution treatment easily erodes the electroless nickel plating film, and the result is attack (erosion) by the underlayer (aluminum or aluminum alloy), and the adhesion of the electroless copper plating film formed by the copper substitution treatment becomes low. SUMMARY OF THE INVENTION The present invention has been made in view of the above circumstances, and provides an electroless nickel plating film formed on aluminum or an aluminum alloy, and further forms an electroless copper plating on the electroless nickel plating film. When the surface of aluminum or aluminum alloy is treated with a film, the electroless nickel plating film is not excessively eroded, and good catalytic properties are imparted to form an electroless copper plating film, and aluminum or aluminum alloy which can impart high adhesion to the electroless copper plating film can be provided. The surface treatment method is for the purpose. In order to achieve the above object, the inventors of the present invention have found that an electroless nickel plating film is formed on aluminum or an aluminum alloy, and an electroless copper plating film is formed on the electroless nickel plating film to treat the surface of the aluminum or aluminum alloy. When an electroless copper plating film is formed by forming an electroless copper plating film on the surface of the electroless nickel plating film by substitution plating or electroless plating, Ag, Au, Pd, Pt, Rh or an alloy thereof is formed. The electrocatalytic copper plating film having good catalytic properties and the resulting electroless copper plating film have high adhesion, and the present invention has been completed. Therefore, the present invention provides a surface treatment method (1) for aluminum or aluminum alloy described below: forming an electroless nickel plating film on at least the above aluminum or aluminum alloy having a treated object of aluminum or aluminum alloy on the surface, and further a surface treatment method for forming an aluminum or aluminum alloy of an electroless copper plating film on an electroless nickel plating film, comprising: forming an aluminum oxide film formed on a surface layer of the aluminum or aluminum alloy on which the object to be treated is removed, on the aluminum or aluminum alloy Forming an electroless nickel plating film -6 - 200905011 nickel plating step, forming Ag, Au, Pd, Pt, Rh or the middle of the alloy on the surface of the above electroless nickel plating film by substitution plating or electroless plating The intermediate plating step of the plating film, and the surface treatment method of the aluminum or aluminum alloy characterized by the copper plating step of the electroless copper plating film on the surface of the intermediate plating film. (2) The nickel plating step includes removing the aluminum oxide film by immersing the object to be treated in an aluminum oxide film containing a metal which can replace aluminum, and forming a metal which can replace aluminum in the removal liquid. Substituting the metal ruthenium; ^ step, the step of removing the substituted metal layer by an acidic liquid having oxidation, and removing the aluminum or aluminum alloy exposed by the substituted metal layer to form an electroless nickel plating film (1) ) The surface treatment method described. (3) The surface treatment method according to (2), characterized in that the removal liquid for the aluminum oxide film contains a metal which can replace the metal of aluminum and an acid. (4): The aluminum oxide film removal liquid contains a salt of a metal which can replace aluminum, 200905011, an oxide, a solubilizing agent of the metal ion, and a base, and is characterized by a pH of 10 to 13.5. The surface treatment method described. (5): The surface treatment method described in (3) or (4), wherein the aluminum oxide film removal liquid system further contains a surfactant. According to the invention, an electroless nickel plating film is formed on aluminum or an aluminum alloy, and an electroless copper plating film is formed on the electroless nickel plating film, and when the surface of the aluminum or aluminum alloy is treated, good catalytic properties can be imparted. The electroless copper plating film is formed, and the obtained electroless copper plating film is a film having high adhesion. BEST MODE FOR CARRYING OUT THE INVENTION The present invention will be described in more detail below. The surface treatment method of the present invention forms an electroless nickel plating film on at least the aluminum or aluminum alloy having a treated object of aluminum or aluminum alloy on the surface, and further forms an electroless copper plating film on the electroless nickel plating film. a surface treatment method for aluminum or aluminum alloy, comprising: an aluminum oxide film formed on the surface layer of the aluminum or aluminum alloy on which the object to be treated is removed, and a nickel plating step of forming an electroless nickel plating film on the aluminum or aluminum alloy, An intermediate plating step of forming an intermediate plating film of Ag, Au, Pd, Pt, Rh or the alloy by electroless plating or electroless plating on the surface of the electroless nickel plating film, and on the surface of the intermediate electric ore film, Forming an electroless copper plating film -8- 200905011 Copper plating step. The following is a description of each of the above steps. [Nickel plating step] In the present invention, the "oxidized film formed on the surface of the aluminum or aluminum alloy from which the object to be treated is removed" forms an electroless nickel-plated film on aluminum or an aluminum alloy, and the oxide film is removed. In the method, the aluminum oxide film is removed, and an electroless nickel plating film is formed on the exposed metal or aluminum alloy. When the ruthenium is impregnated, the aluminum oxide film is removed from the aluminum oxide film containing the metal which can replace the aluminum, and the substituted metal layer containing the metal which is substituted in the removal liquid is formed to have an oxidation effect. The removal of the substituted metal layer by the acidic liquid may also form an electroless nickel-plated film on the aluminum or aluminum alloy exposed by the replacement metal layer. As the removal liquid for the oxide film, a salt containing a metal which can replace the ruthenium, an acid, a salt-containing compound (acid-removing solution), or a metal which can replace the metal of aluminum or The oxide, the solubilizing agent for the metal ion, the base, and the surfactant are particularly preferable, and the pH is 1 〇 1 to 3 · 5 (alkaline removing liquid). (Acid removal liquid) The metal constituting the metal salt contained in the S acid removal liquid is not particularly limited as long as it can replace the metal of the name, but it is preferable to use a metal having a smaller ionization tendency than aluminum. For example, zinc, iron, cobalt, nickel, tin, lead, copper, mercury, silver, lead, gold, palladium, etc., as the above metal salt, a water-soluble salt such as a nitrate or a sulfate of the metal can be exemplified. In particular, sulfate is preferred for the purpose of removing the stability of the liquid -9 - 200905011 or the less aggressiveness of the aluminum or aluminum alloy material. These may be used alone or in combination of two or more. Among them, silver, nickel, and copper are less likely to precipitate in other parts, and therefore, the ionization tendency of copper and silver is much smaller than that of the first one. Therefore, it is easier to carry out the substitution reaction and shorten the etching treatment time. The metal salt concentration to be used as the acid removal liquid is not particularly limited, and the amount of the metal is usually 1 ppm or more, preferably 1 〇 ppm or more, and the upper limit is usually 10,000 ppm or less, and preferably 5,000 ppm or less. When the concentration of the metal salt is too small, it cannot be sufficiently substituted with the aluminum of the underlying layer, and metal salt replenishment must occur. On the other hand, when the concentration is too large, the aluminum alloy is attached to the electrode patterned on the wafer, and the member other than the uranium aluminum or aluminum alloy underlayer or the member other than the aluminum or aluminum alloy underlayer is precipitated. The acid contained in the acid removal liquid is not particularly limited, but it is preferably an acid which dissolves the oxide film, and examples thereof include sulfuric acid, phosphoric acid, hydrochloric acid, hydrofluoric acid, etc., and the like may be used alone or in combination of two or more. . Among them, sulfuric acid is preferred from the viewpoints of the stability of the removal liquid or the less aggressiveness to aluminum or aluminum alloy material. The concentration of the acid in the removal liquid is not particularly limited, but is usually l〇g/L or more, preferably 5 g/L or more, and the upper limit is usually 5 〇Og/L or less ‘300 g/L or less. When the concentration of the acid is too small, the oxide film cannot be dissolved and the effect is not obtained. On the other hand, when the concentration is too large, the member other than the aluminum or aluminum alloy underlayer is eroded. -10-200905011 (Alkaline removal liquid) The metal constituting the metal salt or the metal oxide contained in the alkaline removal liquid is not particularly limited as long as it can replace the metal of aluminum, but ionization is carried out by The metal tends to be small, and examples thereof include manganese, zinc, iron, cobalt, nickel, tin, lead, copper, mercury, silver, platinum, gold, palladium, etc., and the above-mentioned #® salt can be, for example, a metal nitrate. a water-soluble salt such as a salt or a sulfate. Among them, the reduction potential difference between manganese, zinc and aluminum of the bottom layer is preferably small. The concentration of the metal salt or the metal oxide used as the alkaline removal liquid is not particularly limited, and the metal amount is usually 1 Ppm (mg/L) or more and is preferably 10 ppm (mg/L) or more, and the upper limit is usually It is preferably 10,000 ppm (mg/L) or less and 5,000 ppm (mg/L) or less. When the concentration of the metal salt or the metal oxide is too small, it cannot be sufficiently substituted with the aluminum of the underlayer, and it is necessary to supply the metal salt or the metal oxide. On the other hand, when the concentration is too large, the electrode patterned on the aluminum or aluminum alloy wafer erodes the member other than the aluminum or aluminum alloy underlayer, or precipitates beyond the aluminum or aluminum alloy underlayer. The solubilizing agent for the metal ion contained in the alkaline removing liquid is not particularly limited, but a usual complexing agent or a chelating agent can be used. Specifically, a hydroxycarboxylic acid such as glycolic acid, lactic acid, malic acid, tartaric acid, citric acid, gluconic acid, heptanogluconic acid or the like and the salt, glycerin, aminodicarboxylic acid, nitrogen triacetic acid, EDTA can be used. (Ethylenediaminetetraacetic acid), hydroxyethyl-ethylidene diamine triacetic acid, di-ethyltriamine pentaacetic acid, polyaminopolycarboxylic acid, and the like, and the salt, HEDP (hydroxyethylidene II) a phosphorous acid-based chelating agent such as phosphoric acid), aminotrimethylsulfonic acid, ethyldiaminetetramethylsulfonic acid, etc., and the salt, ethyldiamine-11 - 200905011, diethylidene triamine, three An amine-based chelating agent such as ethyltetramine is stretched. The concentration of the solubilizing agent used as the alkaline removing liquid is not particularly limited, but the total concentration of the solubilizing agent is 0.5 to 10 (mole ratio) with respect to the metal salt to be used, and 〇.8~ 5 (Morbi) is appropriate. The alkali contained in the alkaline removal liquid is not particularly limited, but it is preferably an alkali which dissolves the oxide film, and examples thereof include alkali metals such as LiOH, NaOH, and KOH, or ammonium trimethylammonium hydroxide (TMAH). a hydroxide of a quaternary ammonium such as a base or the like. Further, the amount of the base added is such that the amount of p Η of the removal liquid is a predetermined range, i.e., ρ Η is 1 0 to 1 3 · 5 , and preferably 1 1 to 1 3 . If the pH is less than 10, the dissolution rate is significantly lowered. If the pH exceeds 13.5%, the dissolution rate is too fast to be controlled. In the above-mentioned oxide film-removing liquid, it is preferable to contain a surfactant in view of imparting water wettability to any of the acid-removing liquid and the alkaline-removing liquid. The surfactant to be used is not particularly limited, and examples thereof include a nonionic surfactant of polyethylene glycol, a polyethylene oxide/polypropylene oxide block copolymerization type active agent, and other anions. The type of the cationic surfactant is preferably a nonionic or anionic type from the viewpoint of uniform handling. These may be used alone or in combination of two or more. For example, polyethylene glycol is used as the surfactant, and the molecular weight is not particularly limited, but is usually 100 or more, preferably 200 or more, and the upper limit is usually 20 or less, and preferably 6,000 or less. . When the molecular weight is too large, the solubility is deteriorated. On the other hand, if the molecular weight is too small, water wettability cannot be imparted. Further, a commercially available product can be used as the polyethylene glycol. Further, the concentration in the removal liquid as the surfactant is not particularly limited to -12-200905011, and is usually 1 ppm (mg/L) or more, 10 ppm (mg/L) or more, and the upper limit is usually 5,000 ppm ( Below mg/L), it is preferably 2,000 ppm (mg/L) or less. When the concentration of the surfactant in the removal liquid is too small, the water wetting effect obtained is low. On the other hand, if the concentration is too large, a substitution metal is precipitated on a member other than the alloy of Ming or Ming. Further, in the above-mentioned oxide film removal liquid-based acid removal liquid and alkaline removal liquid, it is preferable to prepare an aqueous solution from the viewpoint of handling safety, but other solvents such as methanol, ethanol, and IPA may be used. Propanol), etc., or a mixed solvent with water. Further, these solvents may be used alone or in combination of two or more. The immersion conditions in the case of immersing the object to be treated having aluminum or an aluminum alloy in the removal liquid are not particularly limited, but may be appropriately set in consideration of the thickness of the aluminum oxide film to be removed, etc., but usually 1 minute or longer and 2 minutes. The above is suitable, and the upper limit is usually 20 minutes or less '15 minutes or less is suitable. When the immersion time is too short, the oxidized film is not sufficiently removed. On the other hand, when the immersion time is too long, the removal liquid is infiltrated from the pores of the substituted metal layer, and aluminum or aluminum alloy is eluted. Further, the "temperature at the time of immersion" is not particularly limited, but is usually 20 ° C or higher and preferably 25 ° C or higher, and the upper limit is usually l〇〇t: or less, and preferably 95 ° C or less. When the immersion temperature is too low, the oxide film cannot be dissolved. On the other hand, when the immersion temperature is too high, the member other than aluminum or aluminum alloy is invaded. Further, in the case of "dipping", it is preferred to carry out liquid stirring or shaking of the object to be treated. When the above oxide film removing liquid is used, the aluminum oxide film is removed, and -13-200905011 forms a substitute metal layer which can replace the metal, and the substituted metal layer can be removed by the acidic liquid having oxidation effect. On the aluminum alloy, electroplating is carried out directly or after zinc substitution treatment or treatment. When the substituted metal layer is removed by an acidic liquid having an oxidizing action, the acidity of the oxidizing effect can be used from the viewpoint of alleviating the reactivity of the aluminum or aluminum alloy of the underlayer. In this case, as the acidic liquid having an oxidizing action, an acid having an oxidizing action such as nitric acid or an acid having no oxidizing effect such as the aqueous solution, sulfuric acid or hydrochloric acid or the aqueous solution may be added in one or two or more kinds. An oxidizing agent such as hydrogen peroxide, sodium persulfate, ammonium persulfate or potassium persulfate is preferred. At this time, the acid system has a function of dissolving the substituted metal, and the oxidizing agent has a function of alleviating the reactivity with the aluminum or aluminum alloy underlayer. Further, in the oxidizing agent, 'hydrogen and oxygen are formed, and hydrogen peroxide is preferred in terms of water, and hydrogen peroxide is preferred. In addition, it is preferable to use sodium persulfate or potassium persulfate from the viewpoint of stability. Here, when nitric acid is used as the acid (and oxidizing agent), the amount of nitric acid in the solution (aqueous solution) is usually 200 ml/L or more, preferably 300 ml/L or more, and the upper limit is usually 1,500 ml/L or less. 70 〇 ml / L or less is appropriate. If the amount of nitric acid is too small, the oxidizing power is low and the reaction does not stop. Further, the so-called nitric acid of 1,00 ml/L means that the total amount is nitric acid. Further, when an oxidizing agent is used, the amount of the oxidizing agent in the solution is usually 50 g/L or more, preferably 75 g/L or more, and the upper limit is usually 500 g/L or less, preferably 300 MPa/L or less. When the amount of the oxidizing agent is too small, the oxidizing power is low, and the reaction does not stop. On the other hand, if the amount is too large, the economy is poor. In addition, the concentration of the acid such as hydrochloric acid or sulfuric acid used together with the oxidizing agent is usually -14 to 200905011 l〇g/L or more 'more preferably 15g/L or more, and the upper limit is usually 500g/L or less' to 300g/L. The following is appropriate. If the concentration of the acid is too small, it is difficult to dissolve the substituted metal layer. On the other hand, if the concentration is too large, there is a tendency to erode aluminum or a member other than the alloy. Further, the acid to be used herein is preferably non-oxidizing, but may be an oxidizing acid such as nitric acid, or may be used by mixing an oxidizing acid and a non-oxidizing acid. The dissolution treatment is not particularly limited as the treatment time. For example, the dissolution treatment may be carried out in 5 to 300 seconds, and as the dissolution treatment temperature, for example, a condition of 10 to 4 Torr may be employed. Further, in the dissolution treatment, the electric ore treatment may be stationary, or may be shaken, or may be stirred by liquid. The aluminum oxide film is removed, and the exposed aluminum or aluminum alloy forms an electroless nickel plating film. As the electroless nickel plating, a known electroless nickel plating bath can be used, and for example, an electroless nickel plating bath containing nickel sulfate, an organic acid (succinic acid, malic acid, citric acid, etc.) or sodium hypophosphite can also be used. A commercially available electroplating bath can be used. The film thickness of the electroless nickel plating film is usually about 1 to 20 μm, and the film thickness of the plating film is combined, and the plating temperature and the plating time are selected. Usually, the plating temperature is 50 to 95 ° C, and the plating time is 5 to 120 minutes. Further, the electroless nickel plating may be applied directly to the surface of the aluminum or aluminum alloy, or may be subjected to an electroless nickel plating treatment by subjecting the surface of the aluminum or aluminum alloy to activation treatment by a substitution treatment or a palladium treatment. As such an activation treatment, in particular, a zinc substitution treatment in which a zinc coating is formed on the surface of aluminum or an aluminum alloy by applying an alkali zinc substitution treatment is preferable from the viewpoint of improving the adhesion of the plating film. -15- 200905011 Here, as the zinc substitution treatment 'specifically, it means a process of substituting zinc by using a solution containing a zinc salt. In the case of the alkali zinc substitution treatment, a basic zinc acid solution is used. In addition, when the acid zinc substitution treatment is used, the treatment of zinc precipitation is carried out using a solution containing an acidic zinc salt, and these can be carried out by a known method. Further, as a treatment for palladium, a solution obtained by substituting palladium using a solution containing a palladium salt can be carried out by a known method. [Intermediate Plating Step] In the present invention, Ag, Au, Pd, Pt, Rh or intermediate plating of these alloys is formed on the surface of the electroless nickel film formed by the above nickel plating step by substitution plating or electroless plating. Membrane. For the substitution plating or electroless plating, a known substitution plating bath or an electroless plating bath containing Ag, Au, Pd, Pt or Rh may be used, and for example, a metal (Ag, Au, Pd, Pt, Rh) salt may be contained. a substitutional plating bath of an inorganic acid (sulfuric acid, hydrochloric acid, etc.), an organic acid (succinic acid, malic acid, citric acid, etc.), a metal (Ag, Au, Pd, Pt, Rh) salt, a complexing agent (organic acid, An electroless plating bath such as EDTA or the like, a reducing agent (formic acid, sodium hypophosphite, hydrazine, etc.) may be used, and a commercially available electroplating bath may also be used. The film thickness of the intermediate plating film is usually 0.005 to Ι.Ομιη, preferably 0.01 to 0.5 μηη, and the film thickness of the plating film is matched, and the plating temperature and the plating time are selected. Usually, the plating temperature is 30 to 80 ° C, and plating is performed. The time is 10 seconds to 10 minutes. Form this person §, eight 11,? (1, ?1, ruler 11, or an intermediate plating film of these alloys, an electroless copper plating film is formed by a copper plating step to be described later, and an excellent electrocatalytic property can be imparted to form an electroless copper plating film. -16- 200905011 [Plating Step] In the present invention, an electroless copper plating film is formed on the intermediate surface formed by the intermediate plating step. The electroless copper plating bath known from electroless copper plating may, for example, contain copper sulfate. An electroless copper plating bath such as acid, EDTA, etc., or formaldehyde water, or an electroplating bath. The film thickness of the formed electroless copper plating film is usually 0.05-degrees to match the film thickness of the plating film, and the plating temperature and the 'normal plating temperature are 20 to 7 5 ° C, and the plating time is 5 minutes. At least the surface has aluminum or aluminum alloy, which may be formed by aluminum or aluminum alloy as a whole, or aluminum alloy coated with all or part of non-aluminum material (such as enamel, FRA (printing base)). Surface. Further, the aluminum or aluminum alloy is not particularly limited, and can be suitably applied to, for example, a green material, a rolled material, a cast film or the like. Further, when a gold film is formed on the surface of a non-aluminum material, the method for forming the film is not particularly preferable, but a vapor phase plating method such as a vacuum evaporation method, a sputtering method, or the like is suitable as the formation method. The thickness of the film is such that the aluminum or aluminum alloy is surely left, and is usually 0.5 μη or more, preferably 1 μm or more. The upper limit is not particularly limited, but is usually 1 〇〇 μηη or less. In addition, as the above-mentioned film component, as long as aluminum or aluminum is not particularly limited, for example, Al-Si (Si content is a plating film, and an S agent can be used (a commercially available -10 μm process plating time for tartar) : ~6 hours of processing can be made in the form of aluminum sheet metal, limited by aluminum or aluminum, the surface of the ion plating, the thick gold can be, 0.5 ~1 .0 -17- 200905011 An alloy film such as a weight %) or an Al-Cu (Cu content: 5% to 1.0% by weight) may be applied. [Embodiment] Examples Hereinafter, examples and comparative examples will be specifically described. However, the present invention is not limited to the following embodiments. [Example 1] As a plating material, a ruthenium plate having a thickness of 5 μm was deposited by sputtering, and the aluminum layer was sequentially applied as a table. The treatment shown in Fig. 1. Regarding the characteristics of the obtained plating film, the evaluation results are shown in Table 2. Table 1 Treatment liquid conditions (1) Detergent/surface cleaning Epitas MCL-1 6 * 5 0 ° C 5 minutes (2) Remove the oxide film and remove the oxide film by 5 〇 °c for 1 minute (3) to remove black 50% HN〇3 2 0°C 3 〇 seconds (4) First zincate treatment Epitas MCT-1 7* 2 〇〇c 1 〇 seconds (5) Removal of zinc acid film 1 5 0% HN〇3 20 ° C 60 seconds (6) Second zincate treatment Epitas MCT-1 7 * 2 0 ° C 3 〇 shovel (7) Electroless nickel plating Epitas NPR-18* film thickness 3_ (8) instead of plating ( Gold sulfite) Epitas TDS-20* Film thickness 〇. 0 4 nm (9) 氺· Electroless copper plating U itrf 丫雄 H/W△七/Λ — Epitas PSP-20* Film thickness 8 : Shangcun Industrial Co., Ltd. Oxidation film removal solution of the company: zinc sulfate containing 2 g/L as a metal salt-18-200905011 EDTA_2Na as a solubilizing agent, lg/L as a surfactant, PEG (polyethylene glycol) -1〇〇〇, as a base NaOH, adjusted to an aqueous solution of PH 12.4 [Example 2] In addition to (8) substituted gold (gold sulfite) as a substitution gold plating (gold cyanide) (medicine: Epitas TDL-20 (manufactured by Uemura Industrial Co., Ltd.), except that the film thickness was 〇.〇5 μιη), was treated in the same manner as in Example 1. The evaluation results of the obtained plating film are shown in Table 2. [Embodiment 3 In the same manner as in the first embodiment except that gold plating (gold sulfite) was replaced by (8) electroless plating Pd (chemical liquid: Epitas TFP_3 (manufactured by Uemura Kogyo Co., Ltd.), condition: film thickness: 0.06 μm) The ground is treated. Regarding the characteristics of the obtained plating film, the evaluation results are shown in Table 2. [Comparative Example 1] Treatment was carried out in the same manner as in Example 1 except that the substitution gold plating (gold sulfite) of (8) was not carried out. Regarding the characteristics of the obtained plating film, the evaluation results are shown in Table 2. [Comparative Example 2] A gold substitution treatment (gold sulfite) was used as a copper substitution treatment (chemical solution: copper sulfate was 〇. 5 g/L sulfuric acid (62 5%) 1 Og/L, Condition: 20 ° C 30 -19-200905011 Other than the second, the treatment was carried out in the same manner as in the first embodiment. The evaluation results of the obtained electroless plating film are shown in Table 2.
評估 實施例 比較例 1 2 3 1 2 無電解鍍銅之外觀 良好 良好 良好 不佳 良好 _ 密合性 良好 良好 良好 • 不佳 對底層之侵飩 te » \N 姐 j\\\ te - 有 •無電解鍍銅被膜之外觀：由目測及實體顯微鏡觀察 ’無未附著及不均勻爲良好’以未附著及不均勻爲不佳。 •密合性：矽板連著電鍍被膜折斷，電鍍被膜未剝離 而斷裂者爲良好，Ni/Cu間剝離者爲不佳。 •對底層之侵蝕：無對底層之侵蝕者爲「無」’侵蝕底 層者爲「有」。 -20-Evaluation Example Comparative Example 1 2 3 1 2 The appearance of electroless copper plating is good, good, good, good, good, good, good, good, good, good, good, poor, inferior to the bottom layer, te » \N sister j\\\ te - yes Appearance of electroless copper plating film: It was observed by visual inspection and a stereoscopic microscope that "no unattachment and unevenness were good", and it was not preferable to have no adhesion and unevenness. • Adhesiveness: The enamel plate is broken by the plating film, and the plating film is not peeled off, and the fracture is good, and the Ni/Cu peeling is not good. • Erosion of the bottom layer: “No” for those who are not eroded by the bottom layer. -20-