201012970 六、發明說明： 【發明所屬之技術領域】 本發明係關於一種以抑制晶絲之發生爲目的之銅或銅 合金材料用蝕刻液、鑛敷前處理方法、及電子零件用構件 之形成方法。 本申請案係在曰本國中以2008年8月8日所申請之 日本專利申請編號2 008-205 85 1作爲基礎而主張優先權者 φ ，藉由參照此申請案，引用於本申請案。 【先前技術】 錫及錫合金（錫-銅（Sn-Cu)、錫-銀（Sn-Ag)、錫_ 鉍（Sn-Bi )等）鏟敷皮膜係因焊接潤濕性優異，故被廣 泛利用於電子零件等。但，從其錫及錫合金鍍敷皮膜係易 產生所謂晶絲之數+41»~數mm之鬚狀的結晶已爲人所知， 此晶絲產生自錫及錫合金鍍敷皮膜時，係在電氣、電子基 板中引起電路或端子之短路，明顯降低製品之性能或信賴 性。 此處，說明有關晶絲之產生機構。於銅及銅合金材料 上實施錫及錫合金鎪敷理之試料中，係隨時間變化於銅及 銅合金材料與錫及錫合金鍍敷皮膜之界面形成銅-錫金屬 間化合物層。此金屬間化合物層係若銅之擴散朝向錫鍍敷 皮膜的表面而朝一方向進行，集中於錫鍍敷皮膜的粒界， 故不均一地形成於其界面。繼而，如此做法而不均一地形 成之金屬間化合物層係沿著錫及錫合金鍍敷皮膜的粒界而 -5 - 201012970 成長，同時並於錫及錫合金鍍敷皮膜產生應力。認爲晶絲 係爲於此錫及錫合金鍍敷皮膜上所產生之應力緩和所形成 的結晶，亦即晶絲係使其應力產生成驅動力者。 爲抑制如此之晶絲的發生，至今可使用如以下之對策 (例如參照非專利文獻1 )。 例如，已提出於錫及錫合金鍍敷皮膜的基底形成鎳鍍 敷之技術。此技術係藉由使所形成之鎳鍍敷作爲材料之銅 與錫及錫合金鍍敷皮膜之金屬間化合物形成之阻隔，而抑 制晶絲之產生。 又，其他之方法係已提出使錫及錫合金鍍敷皮膜之膜 厚增厚至10〜2 0 μιη以上之技術。此技術係增厚鍍敷皮膜之 膜厚，藉由金屬間化合物層之形成所產生之內部應力的影 響抑制至鍍敷表層及很難，而抑制晶絲之產生者。 又，於錫及錫合金鍍敷處理後，實施熱處理或回焊處 理之技術已被提出（例如參照專利文獻1或2)。此等之 技術係藉由對鍍敷皮膜實施熱處理或回焊處理，俾緩和錫 及錫合金鍍敷皮膜之殘留應力，同時並於銅或銅合金材料 與鍍敷皮膜之界面形成均一之金屬間化合物層，而發揮抑 制銅更進一步對錫及錫合金鍍敷皮膜中擴散之效果。繼而 ，其結果，所謂抑制晶絲之產生者。 非專利文獻 1 三菱電機技報，1979年，vol.53, No. 1 1 專利文獻1 特開2005-307240號公報 專利文獻2 特開2006-161146號公報 -6- 201012970 【發明內容】 〔發明之揭示〕 〔發明欲解決之課題〕 然而，形成鎳鍍敷皮膜作爲上述之基底之技術，或增 厚錫及錫合金鍍敷皮膜之膜厚的技術中，係其晶絲抑制之 效果不充分，依必需之特性有無法鎳鍍敷之零件時，或， Φ 有無法增厚膜厚之零件時係不能適用。 又，對錫及錫合金鍍敷後實施熱處理或回焊處理的技 術時，係藉其熱處理或回焊處理於錫及錫合金鍍敷皮膜上 形成氧化皮膜，產生焊接潤濕性降低等之錫及錫合金鍍敷 皮膜的劣化。又，回焊處理時，所熔融之錫及錫合金鍍敷 皮膜會流動，而於膜厚產生參差不齊。進一步，進行此等 之熱處理或回焊處理時，係必須鍍敷處理後準備新的設備 而進行處理，造成設備成本或處理時間的增加。 籲 進一步，藉由形成Sn-Cu、Sn-Ag、Sn-Bi等之錫合金 鍍敷皮膜，相較於形成錫鍍敷皮膜時，晶絲之抑制效果係 提高’但要管理皮膜中之合金比率或鍍敷液之合金比率乃 非常困難，故有品質不安定之問題。 又進一步，較以往，目的在於提昇錫及錫合金鍍敷皮 膜與材料之密著性的提高，於鏟敷處理之前步驟實施蝕刻 處理’一般，常使用以硫酸與過氧化氫水作爲主成分之藥 液作爲銅、銅合金材料的蝕刻液。但，以其硫酸與過氧化 氫水作爲主成分之蝕刻液，係主要以銅及銅合金材料之表 201012970 面的氧化皮膜或加工變質層的除去作爲目的而被使用者， 即使對於銅及銅合金材料之表面而使用，亦只有形成平坦 且平滑的形狀。其結果，銅·錫金屬間化合物層局部地產 生於銅及銅合金材料與錫及錫合金鍍敷皮膜之界面，於鍍 敷皮膜產生應力，無法抑制晶絲之產生。 如此地’伴隨錫及錫合金鍍敷皮膜之形成而產生的晶 絲之抑制，係至今已嘗試各種的對策，但發揮充分效果的 技術尙未被開發。因此，強烈期望開發無損錫及錫合金鍍敷 皮膜之性能，且有效地抑制晶絲之產生的晶絲抑制方法。 本發明係有鑑於此等之習知技術之問題點以及要求而 成者’目的在於提供一種未降低錫及錫合金鍍敷皮膜的性 能’可有效地抑制發生於錫及錫合金鍍敷皮膜上之晶絲， 可防止有關連接性等之信賴性的降低之銅及銅合金材料用 蝕刻液、鍍敷前處理方法、以及電子零件用構件之形成方 法。 〔用以解決課題之手段〕 本發明人等爲解決上述課題，專心硏究之結果，發現 在錫及錫合金鍍敷處理的鍍敷前表面處理步驟中，使用以 第二銅離子源、鹵素離子源、有機酸作爲主成分之銅或銅 合金材料用蝕刻液而進行使銅及銅合金材料之表面粗化之 錫及錫合金鍍敷前處理，形成表面粗度大且微細之凹凸形 狀’可有效地抑制從錫及錫合金鍍敷皮膜產生之晶絲。 亦即’本發明之銅或銅合金材料用蝕刻液，係用以抑 -8 - 201012970 制產生於錫及錫合金鍍敷皮膜上之晶絲，可使用於銅或銅 合金材料之表面的蝕刻液，且以第二銅離子源、鹵素離子 源、與有機酸作爲主成分。 又’本發明之鍍敷前處理方法，係用以抑制產生於錫 及錫合金鍍敷皮膜上之晶絲的銅或銅合金材料表面的鍍敷 前處理方法，其特徵在於：使用以第二銅離子源、鹵素離 子源、與有機酸作爲主成分之銅或銅合金材料用蝕刻液， Φ 使上述銅或銅合金材料之表面進行蝕刻處理而粗化。 又，本發明之電子零件用構件之形成方法，係具有如 下步驟：使用以第二銅離子源、鹵素離子源、有機酸作爲 主成分之銅或銅合金材料用蝕刻液而進行蝕刻之蝕刻處理 步驟；及，對於在上述蝕刻處理步驟被粗化之銅或銅合金 材料使其形成錫及錫合金鑛敷皮膜之鍍敷處理步驟。 〔用以實施發明之最佳形態〕 φ 以下’詳細說明有關本實施形態，即用以抑制產生於 錫及錫合金鍍敷皮膜上之晶絲的銅或銅合金用蝕刻液、以 及使用其蝕刻液的鍍敷前處理方法。 本發明之銅及銅合金材料用蝕刻液係目的在於抑制伴 隨錫及錫合金鍍敷皮膜的形成而產生之晶絲，可使用於鍍 敷處理前之蝕刻處理的蝕刻液。對於電子零件用構件之導 線架等的銅及銅合金材料，實施電解脫脂處理或酸洗處理 等之一般特定的表面處理後，使用此蝕刻液而蝕刻處理銅 或銅合金材料表面，形成表面粗度大且微細凹凸。繼而， -9 - 201012970 其後’藉由實施錫及錫合金鍍敷處理而形成鍍敷皮膜，形 成電子零件用構件。 此處，本實施形態之銅及銅合金材料係可舉例如至少 其表面以銅或銅合金材料所形成者，或，如導線架等全體 以銅或銅合金所形成者。又，至少其表面以銅或銅合金所 形成者係亦包含於絕緣樹脂表面層合銅（銅合金）者。 首先’說明有關本實施形態，即於鍍敷前蝕刻表面處 理所使用之銅或銅合金材料用蝕刻液。此蝕刻液係以第二 銅離子源、鹵素離子源、與有機酸作爲主成分。 第二銅離子源係可使用氯化銅（II )、溴化銅（Π ) 、氫氧化銅（II)、或醋酸酮（II)、犠酸酮（II)等之 有機酸的銅鹽等，此等之第二銅離子源係可1種單獨使用 ，或，亦可以任意之比率倂用2種以上。 此第一銅離子源之含量爲2~50g/L’宜爲5~25g/L。 此第二銅離子源之含量未達2g/L時，蝕刻速度會降低， 又，多於5 Og/L時係看不到晶絲抑制的效果之提昇。 鹵素離子源係氯離子、溴離子等之離子源，可使用例 如在鹽酸、氯化鈉、氯化鉀、氯化鈣、氯化銨、溴化鉀、 溴化氫酸、氯化銅、氯化鋅、氯化鐵、溴化鐵、溴化錫、 溴化銅等之溶液中可使鹵素離子解離之化合物。此等之鹵 素離子源係可1種單獨使用，或亦可以任意之比率倂用2 種以上。又，例如氯化銅（II )係可使用來作爲具有鹵素 離子源、與上述之第二銅離子源的兩者之作用者。 此鹵素離子源之含量爲5~200g/L’宜爲10〜150g/L。 201012970 鹵素離子源之含量未達5 g/L時，蝕刻速度會降低，又， 多於200g/L時係看不到晶絲抑制的效果之提昇。 有機酸係可舉例如蟻酸、醋酸、丙酸、醋酸、吉草酸 、己酸、硬脂酸等之飽和脂肪族單羧酸、草酸、丙二酸、 琥珀酸、戊二酸、己二酸、癸二酸等之飽和脂肪族二羧酸 、丙烯酸、丙醇酸、巴豆酸、油酸、甲基丙烯酸等之不飽 和脂肪族單羧酸、馬來酸、富馬酸等之不飽和脂肪族二羧 φ 酸、安息香酸、酞酸、桂皮酸等之碳環羧酸、噻吩羧酸、 菸鹼酸等之雜環羧酸、甘醇酸、乳酸、白氨酸、蘋果酸、 酒石酸、葡萄糖酸、檸檬酸等之脂肪族羥酸、水揚酸、沒 食子酸等之芳香族羥酸。此等之有機酸係可1種單獨使用 ，或，亦可以任意之比率倂用2種以上。 有機酸之含量係5~3 00 g/L，宜爲10〜200 g/L。有機 酸之含量未達5 g/L時係蝕刻速度會降低，又，多於300 g/L時，看不出晶絲抑制效果之進一步提昇，而不經濟。 φ 如此，本實施形態之銅及銅合金材料用蝕刻液係以第 二銅離子源、鹵素離子源、有機酸作爲主成分，使用此蝕 刻液而作爲錫及錫合金鍍敷處理之前處理而對於銅或銅合 金表面實施蝕處理。藉此，相較於自以往所使用之蝕刻液 ，使形成於銅或銅合金材料之凹凸形狀（表面粗度）增大 ，且可微細地形成，可有效地抑制晶絲之產生。 亦即，使用至今一般的蝕刻液而於蝕刻處理之錫及錫 合金鍍敷皮膜中，沿著其鍍敷皮膜之粒界而局部地形成 銅-錫金屬間化合物層。對此，使用上述之本實施形態之 -11 - 201012970 蝕刻液而實施蝕刻處理之錫及錫合金鍍敷皮膜中，係藉此 蝕刻處理’於銅或銅合金材料上形成表面粗度大且微細之 凹凸形狀，金屬間化合物層可於界面全面約均一地形成。 藉此，鍍敷皮膜內之應力被界面全體分散，未局部地集中 ，其結果，可抑制晶絲之產生。 又，本實施形態之蝕刻液中係進一步含有聚胺化合物 、及聚乙烯基化合物之中的任何一種以上。具體上聚胺化 合物係可使用例如聚亞乙基亞胺、聚烷撐基聚胺等。又， 聚乙烯基化合物係可使用聚乙烯基吡咯烷酮、聚乙烯基醇 等。又，此等之聚胺化合物、及聚乙烯基化合物係可1種 單獨使用，或亦可以任意之比率倂用2種以上。 此等之聚胺化合物、及聚乙烯基化合物之含量係 0.0001 〜10 g/L，宜爲 0.0005 〜5 g/L。含量未達 0.000 1 g/L 時係無法得到因添加所產生之晶絲抑制效果，而多於1 0 g/L時，係不僅未看到因添加所產生之晶絲抑制效果之提 昇，蝕刻速度會降低。 如此地，藉由以第二銅離子源、鹵素離子源、有機酸 作爲主成分之蝕刻液中進一步含有聚胺化合物、及聚乙烯 基化合物之中的任何一種以上，而可對於銅或銅合金材料 ，可形成表面粗度更大且微細凹凸形狀。繼而，藉此，可 防止應力局部集中，可更有效地抑制晶絲之產生。 亦即，認爲藉由含有聚胺化合物或聚乙烯基化合物， 俾此等之化合物於銅或銅合金材料之表面不連續地吸附而 製作出孔蝕狀態者。繼而，推測在聚胺化合物或聚乙烯基 -12- 201012970 化合物吸附之部位與不吸附的部位，蝕刻量產生差，其成 爲凹凸而表現者。藉此，於銅或銅合金材料之表面，可形 成表面粗度更大且微細之凹凸。 未蝕刻處理時或以習知之蝕刻液處理時係如上述般， 銅朝錫鍍敷皮膜之表面而朝一方向擴散，同時集中於錫鍍 敷皮膜之粒界，故於銅或銅合金材料與錫鍍敷皮膜之界面 形成不均一的金屬間化合物層。繼而，藉由形成此不均一 Φ 的金屬間化合物層，於錫鍍敷皮膜之內部產生應力之結果 ，產生晶絲。 但，如本實施形態，含有聚胺化合物或聚乙烯基化合 物，可形成表面粗度更大且微細之凹凸，銅或銅合金材料 與錫鍍敷皮膜之接觸面積增加，又，銅之擴散方向不會成 爲一方向而可隨機進行。若銅或銅合金材料與錫鎪敷皮膜 之接觸面積增加，銅之擴散的驅動力會分散，而可抑制於 錫鍍敷皮膜之粒界的擴散集中，換言之，減少於粒界之供 φ 給量。又，銅之擴散並非一方向，而爲隨機，可形成更平 滑之均一的金屬間化合物層。其結果，推測於錫鍍敷皮膜 之內部很難產生應力，可抑制晶絲之產生。 本實施形態之蝕刻液中係進一步亦可含有第二鐵離子 源、鋅離子源、及鎳離子源之中的任何一種以上。 具體上，第二鐵離子源係可使用例如氯化鐵（III)、 溴化鐵（III )、碘化鐵（III)、硫酸鐵（III)、硝酸鐵 (III) '醋酸鐵（III)、檸檬酸鐵（III)銨等。又，鋅 離子源係可使用氯化鋅（II )、溴化鋅（II )、碘化鋅（ -13- 201012970 π)、硫酸鋅（II)、硝酸鋅（II)、醋酸鋅（II)、蟻酸 鋅（II)、草酸鋅（II)等。又，鎳離子源係可使用氯化 鎳（Π)、溴化鎳（11)、碘化鎳（II)、硫酸鎳（II)、 硝酸鎳（II )、醋酸鎳（II )、蟻酸鎳（Π )、磺胺酸鎳 (II)、草酸鎳（Π)等。 此等之第二鐵離子源、鋅離子源、及鎳離子源係可1 種單獨使用，或亦可以任意之比率倂用2種以上。又，此 等化合物之含量係0.00005〜0.005g/L，宜爲 0.0001〜0.002 g/L。含量未達〇.〇〇〇〇5g/L時係無法得到因添加所產生之 效果，又，多於0.005 g/L時係看不到效果之提昇。 如此做法，藉由以第二銅離子源、鹵素離子源、有機 酸作爲主成分之蝕刻液中進一步含有第二鐵離子源、鋅離 子源、及鎳離子源之中的任何一種以上，可抑制於鍍敷液 中之銅離子濃度的變動所產生之蝕刻速度的降低。又，可 進行有效率之蝕刻處理，可更有效地抑制晶絲之產生。 又，本實施形態之蝕刻劑係可進一步含有各種之添加 劑。例如，可實施抑制pH之變動而安定之飩刻處理，可 含有公知之pH安定化劑。又，添加劑係不限於此，而亦 可含有其他各種之添加劑。 藉由使用如此之本實施形態的蝕刻液而實施蝕刻液， 於導線架等之銅及銅合金材料的表面，可形成表面粗度大 且微細之凹凸形狀（表面粗度）。繼而，藉此，於銅或銅 合金材料與錫及錫合金鍍敷皮膜之間所形成之銅-錫金屬 間化合物層略均一地形成於界面全體，可防止應力局部集 -14- 201012970 中，而可有效地抑制用以緩和局部性應力集中所產生之晶 絲。 其次，說明有關使用上述蝕刻液之蝕刻處理方法。在 本實施形態中係對於銅或銅合金材料實施錫及錫合金鍍敷 處理之前，使用上述之蝕刻液作爲鍍敷前處理，欲實施粗 化銅或銅合金材料之表面的蝕刻處理。 亦即，對於銅或銅合金材料，進行公知之脫脂處理、 0 酸洗處理等之特定的清洗處理之後，使用上述之銅或銅合 金材料用蝕刻液，而實施作爲錫及錫合金鍍敷前處理的蝕 刻處理，使表面粗度大且微細之凹凸形狀形成於銅或銅合 金材料之表面。其後，對於藉蝕刻處理而粗化表面之銅或 銅合金材料，實施錫及錫合金鍍敷處理。 此蝕刻處理係可使用公知之方法而進行，例如使銅或 銅合金材料浸漬於上述之蝕刻液，或使其蝕刻液藉噴塗方 式接觸，俾進行蝕刻處理。又，可通電之銅或銅合金材料 φ 的情形係亦可以電解處理進行電解蝕刻。 蝕刻處理之處理時間並無特別限定，但例如以1~3 00 秒，較佳係以5~200秒處理。 又，蝕刻液之溫度條件並無特別限定，但例如1 0〜80 °C，宜爲 25〜50°C。 藉此蝕刻處理，而於銅或銅合金材料之表面形成表面 粗度大且微細之凹凸形狀。具體上，宜於銅或銅合金材料 之表面形成Ra値爲0.2 μιη以上之凹凸。又，本發明中之 平均粗度Ra係依JIS Β 060 1 - 1 994所定義之「算術平均粗 -15- 201012970 度」同樣者，具體上係從粗曲線朝其平均線之方向取得一 定之基準長度，合計從此取得之部分的平均線至粗曲線之 偏差的絕對値，進行平均來求取。 如此，在本實施形態中係就錫及錫合金鍍敷前處理而 言，使用上述之蝕刻液而於銅及銅合金材料之表面形成 Ra値0.2 μπι以上之大小且微細之凹凸形狀。藉此，藉其 後之鍍敷處理所形成之錫鍍敷皮膜與銅或銅合金材料之界 面所產生的金屬間化合物層，略均一地形成於其界面全體 ，可抑制應力之局部性集中。其結果，可抑制受應力集中 的發生所形成之晶絲。 又，在作爲錫及錫合金鍍敷前處理之蝕刻處理中，於 銅或銅合金材料之表面形成表面粗度大且微細之凹凸形狀 而抑制晶絲的產生，故受其後之鍍敷處理所形成之錫及錫 合金鍍敷皮膜的焊接潤濕性、或銅或銅合金材料與錫及錫 合金鍍敷皮膜之密著性不受影響。如此地，不降低錫及錫 合金鍍敷皮膜的性能，而可有效地抑制晶絲之產生。 如此做法，使用上述之蝕刻液而實施鑛敷前處理之蝕 刻處理，若於表面形成表面粗度大且微細之凹凸形狀，其 次，對其銅或銅合金材料表面實施錫及錫合金鍍敷處理。 此錫及錫合金鍍敷處理係可適用公知之鍍敷方法、條件， 並無特別限定。 錫及錫合金鍍敷處理條件並無特別限定，但例如鍍敷 液之溫度爲15〜55 °C，鍍敷時間係宜依所希望之鍍敷膜厚 而變化。 -16- 201012970 在本實施形態中，如上述般，於銅或銅合金材料之表 面使用以第二銅離子源、鹵素離子源、有機酸作爲主成分 之蝕刻液’進行鍍敷前處理之蝕刻處理，於銅或銅合金材 料之表面形成凹凸形狀。繼而，其後，藉錫及錫合金鍍敷 處理而形成銅鍍敷皮膜，以形成電子零件用構件。如此做法 所形成之電子零件用構件係無成爲短路等原因之晶絲的產生 ’又，成爲維持焊接潤濕性等之鍍敷皮膜的性能之狀態。 Φ 以上’如詳細地說明般，本實施形態之蝕刻液係以第 二銅離子源、鹵素離子源、有機酸作爲主成分，使用此蝕 刻液而作爲錫及錫合金鍍敷處理之前處理而對銅或銅合金 表面實施蝕刻處理。藉此蝕刻處理，可使形成於銅或銅合 金材料之凹凸形狀（表面粗度）形成大且微細，可更有效 地抑制晶絲之產生。 亦即，以此蝕刻處理所形成之表面粗度大且微細之凹 凸形狀’以使產生於銅材料與錫及錫合金鏟敷皮膜之界面 φ 的金屬間化合物層略均一地形成於界面全體，可抑制錫鍍 敷皮膜內之應力局部地集中。其結果，可抑制用以使發生 於錫及錫合金鍍敷皮膜之應力緩和所產生之晶絲。 又，如習知般，未對鍍敷皮膜實施熱處理或回焊處理 以抑制晶絲之產生，鍍敷前處理而使用上述之蝕刻液的蝕 刻處理，俾抑制晶絲之產生，故可防止因熱處理或回焊處 理之實施所產生之焊接潤濕性降低等的錫及錫合金鎪敷皮 膜之劣化，並可維持電子零件用構件之性能。繼而，如此 地，爲不使焊接潤濕性劣化，即使如於導線架上形成錫或 -17- 201012970 錫合金鍍敷皮膜之於基體上之被焊接合部形成錫或錫合金 鍍敷皮膜時，亦可有效地適用。 進一步，只於錫及錫合金鍍敷處理之前處理步驟進行蝕 刻處理’可有效地抑制晶絲，故不須增加處理步驟數或增設 特別之設備’可容易且有效地抑制晶絲之產生，同時並可 形成無連接不良等之信賴性提昇的良好電子零件用構件。 又，本發明係不限定於上述之實施形態，在不超出發 明之要旨的範圍的設計變更等亦包含於本發明中。又，上 述之本實施形態的蝕刻液所含有的各種化合物係顯示可適 用之一例者，不限定於上述所列舉者。 【實施方式】 實施例 以下，說明有關本發明之實施例。又，使用本發明之 銅或銅合金用的蝕刻液、以及使用其蝕刻液之蝕刻處理方 法，係不限定於下述之實施例。 (實施例1~8 ) 就實施例而言，對於銅合金材料（C194)導線架（表 面積：0.245 dm2)，使用由下述表1所示之實施例1~8的 組成所構成之鈾刻液而以浸漬方法蝕刻處理之後，使用下 述所示之組成所構成之錫鍍敷浴而實施錫鏟敷處理作爲評 估試料。 實施處理之評估試料係在保持於30°C〜60%RH之恆溫 -18- 201012970 槽內進行保管，經過4000小時後，藉掃描電子顯微鏡（ SEM)，觀察所形成之錫鍍敷皮膜上的晶絲。 又，在評估試驗中，對於蝕刻處理後之表面粗度（Ra )及凹凸平均間隔（Sm )亦藉雷射顯微鏡進行測定。測定 方法係使用超深渡形狀測定顯微鏡（股份公司Keyence製 VK- 8850 )，鈾刻處理後之銅合金材料之每一試料測定3 點，測定平均値。又，在本實施例中所測定之凹凸平均間 φ 隔（Sm)係藉JIS B 0601- 19 94所規定之「凹凸之平均 間隔」，具體上，從粗曲線，朝其平均線之方向僅取得一 定之基準長度，求出對應於一個之山峰及相鄰其之1個山 谷之平均線的長度之和，表示平均値者。若Sm很小，判 斷凹凸之眼很細小。 <處理步驟> 電解脫脂（2分）-> 水洗（15秒）χ3次—酸洗（20 φ 秒）—水洗（1 5秒）X3次―蝕刻（浸漬處理）—水洗（ 1 5秒）χ3次—酸洗（20秒）—錫鍍敷（下述條件）—水 洗（15秒）χ3次―中和—水洗（15秒）χ3次—離子交換 水洗—乾燥 <錫鍍敷浴之組成> 甲烷磺酸錫（II) : 90 g/L ( SI1 爲 5 0g/L)[Technical Field] The present invention relates to an etching solution for a copper or copper alloy material, a pre-mineral treatment method, and a method for forming an electronic component member for the purpose of suppressing the occurrence of a crystal filament . The present application claims priority on the basis of Japanese Patent Application No. 2 008-205 85, filed on Aug. 8, 2008, which is incorporated herein by reference. [Prior Art] Tin and tin alloys (Sn-Cu, Sn-Ag, Sn-Bi, etc.) are excellent in wettability due to soldering. Widely used in electronic parts and so on. However, it is known from the tin and tin alloy plating film that a crystal of a so-called crystal filament number of +41»~mm is known. When the crystal filament is produced from a tin and tin alloy plating film, It causes short circuit of circuit or terminal in electrical and electronic substrates, which significantly reduces the performance or reliability of the product. Here, the mechanism for generating the filament is explained. In the samples of tin and tin alloy enamel applied to copper and copper alloy materials, a copper-tin intermetallic compound layer was formed at the interface between the copper and copper alloy materials and the tin and tin alloy plating film over time. In the intermetallic compound layer, if the diffusion of copper proceeds toward the surface of the tin plating film in one direction and concentrates on the grain boundary of the tin plating film, it is unevenly formed at the interface. Then, the unevenly formed intermetallic compound layer grows along the grain boundary of the tin and tin alloy plating film -5 - 201012970, and stress is generated on the tin and tin alloy plating film. It is considered that the crystal wire is a crystal formed by the relaxation of the stress generated on the tin and tin alloy plating film, that is, the crystal wire is used to cause the stress to be a driving force. In order to suppress the occurrence of such a crystal filament, the following countermeasures can be used (see, for example, Non-Patent Document 1). For example, it has been proposed to form a nickel plating technique on a substrate of a tin and tin alloy plating film. This technique suppresses the generation of crystal filaments by forming a barrier between the formed nickel plating material and the intermetallic compound of the tin and tin alloy plating film. Further, other methods have been proposed to thicken the film thickness of the tin and tin alloy plating film to 10 to 20 μm or more. This technique thickens the film thickness of the plating film, suppresses the influence of the internal stress generated by the formation of the intermetallic compound layer to the plating surface layer, and is difficult to suppress the generation of the crystal wire. Further, after the tin and tin alloy plating treatment, a technique of performing heat treatment or reflow processing has been proposed (for example, refer to Patent Document 1 or 2). These techniques reduce the residual stress of the tin and tin alloy plating film by heat treatment or reflow treatment of the plating film, and form a uniform metal between the interface of the copper or copper alloy material and the plating film. The compound layer exerts an effect of suppressing the diffusion of copper into the tin and tin alloy plating film. Then, as a result, the producer of the crystal filament is suppressed. Non-Patent Document 1 MITSUBISHI TECHNOLOGIES, 1979, vol. 53, No. 1 1 Patent Document 1 JP-A-2005-307240 (Patent Document 2) JP-A-2006-161146A-6-201012970 [Invention] DISCLOSURE OF THE INVENTION [Problem to be Solved by the Invention] However, in the technique of forming a nickel plating film as the above-mentioned substrate or thickening the film thickness of the tin and tin alloy plating film, the effect of suppressing the crystal wire is insufficient. If there are parts that cannot be nickel-plated according to the necessary characteristics, or Φ, parts that cannot thicken the film thickness are not applicable. In addition, when a technique of performing heat treatment or reflow treatment after tin and tin alloy plating is performed, an oxide film is formed on the tin and tin alloy plating film by heat treatment or reflow treatment, and tin having a reduced weld wettability is generated. And deterioration of the tin alloy plating film. Further, during the reflow process, the molten tin and the tin alloy plating film flow, and the film thickness is uneven. Further, in the case of performing such heat treatment or reflow processing, it is necessary to prepare a new apparatus after the plating treatment, thereby causing an increase in equipment cost or processing time. Further, by forming a tin alloy plating film of Sn-Cu, Sn-Ag, Sn-Bi or the like, the suppression effect of the crystal wire is improved as compared with the case of forming a tin plating film, but the alloy in the film is managed. The ratio or the alloy ratio of the plating solution is very difficult, so there is a problem of unsatisfactory quality. Further, in order to improve the adhesion between the tin and tin alloy plating film and the material, the etching process is performed before the shovel treatment. In general, sulfuric acid and hydrogen peroxide water are often used as main components. The chemical solution is used as an etching solution for copper and copper alloy materials. However, the etching liquid containing sulfuric acid and hydrogen peroxide as a main component is mainly used for the purpose of removing the oxide film or the processed metamorphic layer on the surface of the surface of the copper and copper alloy material 201012970, even for copper and copper. The surface of the alloy material is used only to form a flat and smooth shape. As a result, the copper-tin intermetallic compound layer is locally produced at the interface between the copper and copper alloy material and the tin and tin alloy plating film, and stress is generated in the plating film, and the generation of the crystal filament cannot be suppressed. As a result of the suppression of the crystal generated by the formation of the tin and the tin alloy plating film, various measures have been tried so far, but the technique for exhibiting sufficient effects has not been developed. Therefore, it is strongly desired to develop a method for suppressing the suppression of the properties of tin and tin alloy plating films and effectively suppressing the generation of crystal wires. The present invention has been made in view of the problems of the prior art and the requirement that the purpose of the invention is to provide a coating that does not reduce the tin and tin alloy plating film, which is effective in suppressing the occurrence of tin and tin alloy plating films. The crystal wire is an etching liquid for copper and copper alloy materials, a pre-plating treatment method, and a method for forming an electronic component member, which are capable of preventing reduction in reliability such as connectivity. [Means for Solving the Problem] In order to solve the above problems, the inventors of the present invention have found that the second copper ion source and the halogen are used in the surface treatment step before the plating of the tin and tin alloy plating treatment. A copper or copper alloy material having an ion source or an organic acid as a main component is subjected to pre-treatment of tin and tin alloys for roughening the surface of copper and a copper alloy material with an etching solution to form a surface having a large surface roughness and a fine uneven shape. The crystal filaments generated from the tin and tin alloy plating film can be effectively suppressed. That is, the etching solution for the copper or copper alloy material of the present invention is used for the etching of the surface of the tin or tin alloy plating film by the -8 - 201012970, and can be used for etching the surface of the copper or copper alloy material. The liquid is a second copper ion source, a halogen ion source, and an organic acid as a main component. Further, the pre-plating treatment method of the present invention is a pre-plating treatment method for suppressing the surface of a copper or copper alloy material which is produced on a tin and tin alloy plating film, and is characterized in that: A copper ion source, a halogen ion source, an etching solution for a copper or copper alloy material having a main component as an organic acid, and Φ are subjected to an etching treatment to roughen the surface of the copper or copper alloy material. Further, the method for forming a member for an electronic component according to the present invention has the step of etching using an etching solution using a copper or copper alloy material having a second copper ion source, a halogen ion source, and an organic acid as a main component. And a plating treatment step of forming a tin and tin alloy mineral coating on the copper or copper alloy material roughened in the above etching treatment step. [Best Mode for Carrying Out the Invention] φ Hereinafter, the etching solution for copper or copper alloy for suppressing the crystal filaments generated on the tin and tin alloy plating film, and etching using the same will be described in detail. Pre-plating treatment of liquid. The etching solution for copper and copper alloy materials of the present invention is intended to suppress the formation of a crystal filament accompanying the formation of a tin and tin alloy plating film, and to provide an etching solution for etching treatment before the plating treatment. The copper and copper alloy materials such as lead frames for electronic component members are subjected to general specific surface treatment such as electrolytic degreasing treatment or pickling treatment, and then the etching solution is used to etch the surface of the copper or copper alloy material to form a rough surface. Large and fine bumps. Then, -9 - 201012970 thereafter, a plating film is formed by performing tin and tin alloy plating treatment to form a member for an electronic component. Here, the copper and copper alloy material of the present embodiment may be, for example, a copper or copper alloy material formed on the surface thereof, or a copper or copper alloy such as a lead frame. Further, at least the surface formed of copper or a copper alloy is also included in the surface of the insulating resin to laminate copper (copper alloy). First, the etching liquid for copper or copper alloy material used for etching the surface treatment before plating will be described. This etching liquid is mainly composed of a second copper ion source, a halogen ion source, and an organic acid. The second copper ion source may be a copper salt of an organic acid such as copper (II) chloride, copper (b) bromide, copper (II) hydroxide, or ketone acetate (II) or decanoate (II). These second copper ion sources may be used singly or in combination of two or more kinds in any ratio. The content of the first copper ion source is preferably 2 to 50 g/L' of 5 to 25 g/L. When the content of the second copper ion source is less than 2 g/L, the etching rate is lowered, and when it is more than 5 Og/L, the effect of suppressing the crystal filament is not observed. The source of the halogen ion is an ion source such as chloride ion or bromide ion, and for example, hydrochloric acid, sodium chloride, potassium chloride, calcium chloride, ammonium chloride, potassium bromide, hydrogen bromide, copper chloride or chlorine can be used. A compound which can dissociate halogen ions in a solution of zinc, iron chloride, iron bromide, tin bromide or copper bromide. These halogen ion sources may be used singly or in combination of two or more kinds in any ratio. Further, for example, copper (II) chloride can be used as a source having both a halogen ion source and the above-described second copper ion source. The content of the halogen ion source is 5 to 200 g/L', preferably 10 to 150 g/L. 201012970 When the content of the halogen ion source is less than 5 g/L, the etching speed will decrease, and when it is more than 200 g/L, the effect of suppressing the crystal filament will not be improved. Examples of the organic acid include saturated aliphatic monocarboxylic acids such as formic acid, acetic acid, propionic acid, acetic acid, oxalic acid, caproic acid, and stearic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, and adipic acid. An unsaturated aliphatic monocarboxylic acid such as sebacic acid, such as saturated aliphatic dicarboxylic acid, acrylic acid, propionic acid, crotonic acid, oleic acid or methacrylic acid, unsaturated aliphatic monocarboxylic acid, maleic acid or fumaric acid. Heterocyclic carboxylic acid, glycolic acid, lactic acid, leucine, malic acid, tartaric acid, glucose, such as carboxylic acid, benzoic acid, citric acid, cinnamic acid, etc., carbocyclic carboxylic acid, thiophenecarboxylic acid, nicotinic acid, etc. An aromatic hydroxy acid such as aliphatic hydroxy acid, salicylic acid or gallic acid such as acid or citric acid. These organic acids may be used singly or in combination of two or more kinds in any ratio. The content of the organic acid is 5 to 300 g/L, preferably 10 to 200 g/L. When the content of the organic acid is less than 5 g/L, the etching rate is lowered. Further, when it is more than 300 g/L, the effect of suppressing the crystal filament is not further improved, which is uneconomical. φ As described above, in the etching solution for copper and copper alloy materials of the present embodiment, the second copper ion source, the halogen ion source, and the organic acid are used as the main components, and the etching liquid is used as the tin and tin alloy plating treatment. The surface of the copper or copper alloy is etched. As a result, the uneven shape (surface roughness) formed in the copper or copper alloy material is increased and formed finely compared to the etching liquid used in the past, and the generation of the crystal filament can be effectively suppressed. That is, a copper-tin intermetallic compound layer is locally formed along the grain boundary of the plating film by etching the tin and tin alloy plating film using the conventional etching liquid. On the other hand, in the tin and tin alloy plating film which is subjected to the etching treatment using the above-described -11 - 201012970 etching solution of the present embodiment, the etching treatment is performed on the copper or copper alloy material to have a large surface roughness and fineness. The uneven shape and the intermetallic compound layer can be formed approximately uniformly in the entire interface. Thereby, the stress in the plating film is dispersed by the entire interface, and is not locally concentrated, and as a result, the generation of the crystal filament can be suppressed. Further, the etching solution of the present embodiment further contains at least one of a polyamine compound and a polyvinyl compound. Specifically, for example, polyethyleneimine, polyalkylenepolyamine or the like can be used as the polyamine compound. Further, as the polyvinyl compound, polyvinylpyrrolidone, polyvinyl alcohol or the like can be used. Further, these polyamine compounds and polyvinyl compounds may be used singly or in combination of two or more kinds in any ratio. The content of the polyamine compound and the polyvinyl compound is 0.0001 to 10 g/L, preferably 0.0005 to 5 g/L. When the content is less than 0.000 1 g/L, the effect of suppressing the filament generated by the addition cannot be obtained, and when it is more than 10 g/L, the improvement of the inhibition effect of the crystal by the addition is not observed, and etching is performed. The speed will decrease. In this way, the etching solution containing the second copper ion source, the halogen ion source, and the organic acid as a main component further contains at least one of a polyamine compound and a polyvinyl compound, and can be used for copper or a copper alloy. The material can form a surface having a larger thickness and a fine uneven shape. Then, by this, local concentration of stress can be prevented, and generation of crystal filaments can be more effectively suppressed. That is, it is considered that a compound having a pitting state is formed by discontinuously adsorbing a compound such as a polyamine compound or a polyvinyl compound on the surface of a copper or copper alloy material. Then, it is presumed that the amount of etching is poor in the portion where the polyamine compound or the polyvinyl -12-201012970 compound is adsorbed and the portion which is not adsorbed, and it is expressed as irregularities. Thereby, on the surface of the copper or copper alloy material, a larger and finer surface roughness can be formed. When it is not etched or treated with a conventional etching solution, as described above, copper diffuses in one direction toward the surface of the tin plating film, and concentrates on the grain boundary of the tin plating film, so that copper or copper alloy material and tin are used. The interface between the plating films forms a heterogeneous intermetallic compound layer. Then, by forming the heterogeneous Φ intermetallic compound layer, stress is generated inside the tin plating film to generate a crystal filament. However, according to the present embodiment, the polyamine compound or the polyvinyl compound is contained, and the surface roughness is larger and finer and uneven, and the contact area between the copper or copper alloy material and the tin plating film is increased, and the diffusion direction of the copper is formed. It does not become a direction and can be randomly performed. If the contact area between the copper or copper alloy material and the tin-bismuth coating increases, the driving force for diffusion of copper is dispersed, and the diffusion concentration of the grain boundary of the tin plating film can be suppressed, in other words, the supply of the grain boundary is reduced. the amount. Moreover, the diffusion of copper is not in one direction, but is random, and a smoother uniform metal intermetallic layer can be formed. As a result, it is presumed that stress is hard to be generated inside the tin plating film, and generation of the crystal wire can be suppressed. The etching solution of the present embodiment may further contain any one or more of a second iron ion source, a zinc ion source, and a nickel ion source. Specifically, the second iron ion source may be, for example, iron (III) chloride, iron (III) bromide, iron (III) iodide, iron (III) sulfate, iron (III) nitrate, iron (III) acetate. , iron (III) citrate and the like. Further, zinc ion source may be zinc (II) chloride, zinc (II) bromide, zinc iodide (-13-201012970 π), zinc (II) sulfate, zinc (II) nitrate, zinc (II) acetate. , zinc formate (II), zinc (II) oxalate, and the like. Further, the nickel ion source may be nickel chloride (ruthenium), nickel bromide (11), nickel (II) iodide, nickel (II) sulfate, nickel (II) nitrate, nickel (II) acetate, and nickel formate ( Π ), nickel sulfonate (II), nickel oxalate (Π), and the like. These second iron ion source, zinc ion source, and nickel ion source may be used singly or in combination of two or more kinds in any ratio. Further, the content of these compounds is 0.00005 to 0.005 g/L, preferably 0.0001 to 0.002 g/L. When the content is less than 〇.〇〇〇〇5g/L, the effect due to the addition cannot be obtained, and when it is more than 0.005 g/L, the effect is not improved. In this way, the etching solution containing the second copper ion source, the halogen ion source, and the organic acid as a main component further contains any one of the second iron ion source, the zinc ion source, and the nickel ion source, thereby suppressing A decrease in the etching rate due to a change in the concentration of copper ions in the plating solution. Further, an efficient etching treatment can be performed, and the generation of the crystal filament can be more effectively suppressed. Further, the etchant of the present embodiment may further contain various additives. For example, it is possible to carry out an etching treatment which suppresses the fluctuation of pH and is stable, and may contain a known pH stabilizer. Further, the additive is not limited thereto, and may contain other various additives. By using the etching liquid of the present embodiment, the etching liquid is applied to form a surface having a large surface roughness and a fine uneven shape (surface roughness) on the surface of the copper or copper alloy material such as a lead frame. Then, the copper-tin intermetallic compound layer formed between the copper or copper alloy material and the tin and tin alloy plating film is slightly uniformly formed on the entire interface, and the stress local assembly can be prevented from -14 to 201012970. The crystal filaments generated by the local stress concentration can be effectively suppressed. Next, an etching treatment method using the above etching liquid will be described. In the present embodiment, before the tin or tin alloy plating treatment is applied to the copper or copper alloy material, the etching liquid described above is used as the pre-plating treatment, and the etching treatment of the surface of the roughened copper or copper alloy material is performed. In other words, the copper or copper alloy material is subjected to a specific cleaning treatment such as a known degreasing treatment or a zero pickling treatment, and then the copper or copper alloy material is used as an etching solution before the plating is performed as a tin and tin alloy. The etching treatment of the treatment causes the surface roughness to be large and the fine concavo-convex shape to be formed on the surface of the copper or copper alloy material. Thereafter, the copper or copper alloy material which has been roughened by the etching treatment is subjected to tin and tin alloy plating treatment. This etching treatment can be carried out by a known method. For example, a copper or copper alloy material is immersed in the above-mentioned etching liquid, or the etching liquid is brought into contact with the etching solution, and the etching treatment is performed. Further, in the case of a copper or copper alloy material φ which can be energized, electrolytic etching can also be performed by electrolytic treatment. The processing time of the etching treatment is not particularly limited, but is, for example, 1 to 300 seconds, preferably 5 to 200 seconds. Further, the temperature condition of the etching liquid is not particularly limited, but is, for example, 10 to 80 ° C, preferably 25 to 50 ° C. By this etching treatment, a surface having a large surface roughness and a fine uneven shape is formed on the surface of the copper or copper alloy material. Specifically, it is preferable to form irregularities having a Ra 値 of 0.2 μm or more on the surface of the copper or copper alloy material. Further, the average roughness Ra in the present invention is the same as the "arithmetic average coarseness - 15 - 201012970 degrees" defined in JIS 060 060 1 - 1 994, and specifically takes a certain direction from the thick curve toward the average line thereof. The reference length is obtained by averaging the total enthalpy of the deviation from the average line to the coarse curve of the portion obtained therefrom. As described above, in the present embodiment, in the pre-plating treatment of tin and tin alloy, the above-described etching liquid is used to form a fine uneven shape of Ra 値 0.2 μm or more on the surface of the copper and copper alloy material. Thereby, the intermetallic compound layer formed by the interface between the tin plating film formed by the subsequent plating treatment and the copper or copper alloy material is slightly uniformly formed on the entire interface thereof, and the local concentration of stress can be suppressed. As a result, the crystal filament formed by the occurrence of stress concentration can be suppressed. Further, in the etching treatment for the pre-plating treatment of tin and tin alloy, a surface having a large surface roughness and a fine concavo-convex shape is formed on the surface of the copper or copper alloy material to suppress the generation of the crystal filament, so that the subsequent plating treatment is performed. The weld wettability of the formed tin and tin alloy plating film or the adhesion of the copper or copper alloy material to the tin and tin alloy plating film is not affected. Thus, the performance of the tin and tin alloy plating film is not lowered, and the generation of the crystal wire can be effectively suppressed. In this way, the etching treatment of the pre-mine treatment is performed using the etching liquid described above, and if the surface has a large surface roughness and a fine concavo-convex shape, the surface of the copper or copper alloy material is subjected to tin and tin alloy plating treatment. . This tin and tin alloy plating treatment can be applied to a known plating method and conditions, and is not particularly limited. The tin and tin alloy plating treatment conditions are not particularly limited. For example, the temperature of the plating solution is 15 to 55 ° C, and the plating time is preferably changed depending on the desired plating film thickness. In the present embodiment, as described above, the etching of the pre-plating treatment is performed on the surface of the copper or copper alloy material using an etching liquid having a second copper ion source, a halogen ion source, and an organic acid as a main component. The treatment forms a concave-convex shape on the surface of the copper or copper alloy material. Then, a copper plating film is formed by tin and tin alloy plating treatment to form a member for an electronic component. In this case, the member for the electronic component is formed without the occurrence of a filament which is caused by a short circuit or the like, and is in a state of maintaining the performance of the plating film such as solder wettability. Φ or more, as described in detail, the etching liquid of the present embodiment is mainly composed of a second copper ion source, a halogen ion source, and an organic acid, and is treated as a tin and tin alloy plating treatment using the etching solution. The copper or copper alloy surface is subjected to an etching treatment. By this etching treatment, the uneven shape (surface roughness) formed in the copper or copper alloy material can be made large and fine, and the generation of the crystal filament can be more effectively suppressed. That is, the surface roughness formed by the etching treatment is large and the fine concavo-convex shape is formed so that the intermetallic compound layer generated at the interface φ between the copper material and the tin and tin alloy scraping film is uniformly formed on the entire interface. The stress concentration in the tin plating film can be suppressed from being locally concentrated. As a result, the crystal filament generated by the relaxation of the stress occurring in the tin and tin alloy plating film can be suppressed. Further, as is conventionally, the plating film is not subjected to heat treatment or reflow treatment to suppress the generation of the crystal filaments, and the etching treatment using the etching liquid described above is performed before the plating treatment, thereby suppressing the generation of the crystal filaments, thereby preventing the occurrence of the crystal filaments. The deterioration of the solder wettability caused by the heat treatment or the reflow treatment is deteriorated by the tin and tin alloy coating film, and the performance of the member for electronic parts can be maintained. Then, in order to prevent the weld wettability from deteriorating, even if tin or a -17-201012970 tin alloy plating film is formed on the lead frame to form a tin or tin alloy plating film on the bonded portion of the substrate It can also be effectively applied. Further, the etching process can be effectively performed only before the tin and tin alloy plating treatment process, so that the crystal filament can be effectively suppressed, so that the number of processing steps or the addition of a special device can be easily and effectively suppressed, and at the same time, the generation of the crystal filament can be easily and effectively suppressed. It is also possible to form a good electronic component for the reliability improvement without connection failure. Further, the present invention is not limited to the above-described embodiments, and design changes and the like that do not deviate from the gist of the invention are also included in the present invention. Further, the various compounds contained in the etching liquid of the present embodiment described above are not limited to the above-mentioned ones. [Embodiment] Embodiments Hereinafter, embodiments of the present invention will be described. Further, the etching liquid for copper or copper alloy of the present invention and the etching treatment method using the etching liquid thereof are not limited to the following examples. (Examples 1 to 8) For the examples, for the copper alloy material (C194) lead frame (surface area: 0.245 dm2), uranium engraving consisting of the compositions of Examples 1 to 8 shown in Table 1 below was used. After the liquid was etched by the immersion method, a tin-plating treatment was carried out using a tin plating bath having the composition shown below as an evaluation sample. The evaluation sample for the treatment was stored in a constant temperature of -18-201012970 kept at 30 ° C to 60% RH. After 4000 hours, the scanning electron microscope (SEM) was used to observe the formed tin plating film. Crystal wire. Further, in the evaluation test, the surface roughness (Ra) and the average unevenness interval (Sm) after the etching treatment were also measured by a laser microscope. For the measurement method, an ultra-deep shape measuring microscope (VK-8850, manufactured by Keyence Corporation) was used, and each sample of the copper alloy material after the uranium engraving treatment was measured at 3 points, and the average enthalpy was measured. Further, in the present embodiment, the unevenness average φ interval (Sm) is the "average interval of the unevenness" defined by JIS B 0601-1994, specifically, from the thick curve to the direction of the average line thereof. A predetermined reference length is obtained, and the sum of the lengths of the average lines corresponding to one mountain and one of the adjacent valleys is obtained, and the average is displayed. If the Sm is small, the eye that determines the bump is very small. <Processing step> Electrolytic degreasing (2 points)-> Water washing (15 seconds) χ 3 times - pickling (20 φ seconds) - water washing (15 seconds) X3 times - etching (immersion treatment) - washing (1 5 Second) χ 3 times - pickling (20 seconds) - tin plating (the following conditions) - water washing (15 seconds) χ 3 times - neutralization - water washing (15 seconds) χ 3 times - ion exchange washing - drying & < tin plating Composition of bath> Tin (II) methane sulfonate : 90 g/L (SI 1 is 50 g/L)
70%甲烷磺酸：135g/L 界面活性劑：聚氧乙烯壬基苯基醚（EO加成莫耳數9 -19- 20101297070% methanesulfonic acid: 135g/L surfactant: polyoxyethylene nonylphenyl ether (EO addition mole number 9 -19- 201012970
):6g/L <錫鍍敷處理條件> 陰極電流密度：l〇A /dm2 鍍敷時間：3 5秒 液溫：4 5 °C 鍍敷膜厚：2·5μπι (比較例1 ) 又，就比較例1而言，對於與在實施例所使用者同樣 的銅合金材料（C194)導線架（表面積：0.24 5 dm2)，於 錫鍍敷處理前不進行蝕刻處理，使用與實施例同樣之上述 錫鍍敷浴而進行錫鍍敷處理。 繼而，與實施例同樣做法，使已實施錫鍍敷處理之試 料於保持在30°C〜60%RH之恆溫槽內進行保管，經過4000 小時後，藉掃描電子顯微鏡（SEM )，觀察所形成之錫鍍 Q 敷皮膜上的晶絲。 (比較例2~8 ) 就比較例2~8而言，對於銅合金材料（C194 )導線架 (表面積：0.245 dm2 )，使用由下述表2所示之比較例 2〜8的組成所構成之蝕刻液而以與實施例同樣之浸漬方法 進行蝕刻處理之後，使用與上述同樣之組成所構成之錫鍍 敷浴而實施錫鍍敷處理作爲評估試料。 -20- 201012970 繼而’與實施例同樣做法，使已實施處理之評估試料 於保持在30°C〜60%RH之恆溫槽內進行保管，經過4000 小時後’藉掃描電子顯微鏡（SEM )，觀察所形成之錫鍍 敷皮膜上的晶絲。又，對於蝕刻處理後之表面粒度（Ra ) 及凹凸平均間隔（Sm )亦使用超深渡形狀測定顯微鏡（股 份公司 Keyence製 VK- 88 5 0 )，蝕刻處理後之銅或銅合 金材料之每一試料測定3點，測定平均値。又，有關此表 φ 面粗度（Ra )及凹凸平均間隔（Sm )係亦測定有關錫鍍 敷處理前之比較例1中的導線架。 (測定結果） 在下述之表1及表2中表示實施例及比較例之測定結 果。又，在表1及表2中晶絲評估結果之欄記載之「〇」 、「△」、「X」係意指以下者。 〇：晶絲之產生零 φ △:可觀察到晶絲，但其長度未達1 〇μιη X :可觀察到晶絲，且其長度爲1 0 μ m以上 又，在圖1中，在實施例1及實施例3之處理中，顯 示對於導線架實施蝕刻處理而形成凹凸形狀時之表面狀態 的SEM像（圖1A:實施例1、圖1B:實施例3)，進一 步於圖2中，在比較例2及比較例3之處理中，顯示對於 導線架實施鈾刻處理而形成凹凸形狀時之表面狀態的SEM 像（圖2A :比較例2、圖2B :比較例3 )。 (實施例1~8) -21 - 201012970 〔表1〕 實 施 例 藥品名及組成 Ιϊ 錫平均 膜厚 晶絲評 估結果 溫度 CC) 處理時間 (秒） 蝕刻量 (mg) 表面粗度 Ra(^) 凹凸形狀之平 均間隔Sm(pm) 1 氯化銅(II) 30 醋酸 30 氯化鈉 30 離子交換水其餘 45 80 41.9 0.22 2.98 2.8 Δ 2 氯化銅(II) 20 氯化第二鐵(III) 0.005 醋酸 30 氯化納 30 離子交換水其餘 45 80 43.3 0.24 2.88 2.9 Δ 3 氯化銅(II) 90 蟻酸鈉 50 鹽酸 20 聚亞乙基亞胺(分子 ,s 量 300) 離子交換水其餘 35 50 27.5 0.39 2.36 2.7 〇 4 醋酸銅(Π) 70 酒石麵 100 氯化鈉 45 氫氧化鈉 15 聚亞乙基亞胺(分子η nnn$ 量 1200) 離子交換水其餘 55 20 39.5 0.43 2.40 2.6 〇 5 溴化銅(Π) 90 甘醇麵 20 溴化鈉 45 氫氧化鈉 5 聚乙烯基吡咯烷酮 K-30(分子量4⑻00) 離子交換水其餘 35 80 36.5 0.27 2.54 2.7 〇 6 蟻酸銅(II) 35 蟻酸 35 氯化鉀 30 氫氧化鈉 25 聚乙烯基吡咯烷酮 j 2 K-90(分子量 360000) 離子交換水其餘 40 100 41.2 0.35 2.46 2.4 〇 7 溴化銅(II) 55 檸檬瞧 1〇〇 氯化鈉 45 聚乙烯醇1400(聚合 度約1400) 離子交換水其餘 35 120 46.5 0.43 2.75 2.7 〇 8 溴化銅(II) 20 溴化鎳 0.0005 檸檬麵 1〇〇 氯化鈉 45 聚乙烯醇1400(聚合 度約1400) 離子交換水其餘 35 120 45.0 0.40 2.72 2.8 〇 (比較例1~8 ) -22- 201012970 〔表2〕): 6 g / L < tin plating treatment conditions > Cathodic current density: l 〇 A / dm 2 plating time: 3 5 seconds liquid temperature: 4 5 ° C plating film thickness: 2 · 5 μπι (Comparative Example 1) Further, in Comparative Example 1, the lead frame (surface area: 0.24 5 dm 2 ) of the copper alloy material (C194) similar to the user of the example was not subjected to etching treatment before the tin plating treatment, and was used and examples. The tin plating bath was similarly applied to the tin plating bath. Then, in the same manner as in the examples, the sample subjected to the tin plating treatment was stored in a thermostatic chamber maintained at 30 ° C to 60% RH, and after 4000 hours, it was observed by a scanning electron microscope (SEM). The tin on the Q coated Q film. (Comparative Examples 2 to 8) In Comparative Examples 2 to 8, the copper alloy material (C194) lead frame (surface area: 0.245 dm2) was composed of the compositions of Comparative Examples 2 to 8 shown in Table 2 below. After the etching liquid was etched in the same manner as in the examples, a tin plating bath composed of the same composition as described above was used to carry out a tin plating treatment as an evaluation sample. -20- 201012970 Then, in the same way as in the example, the evaluation sample that has been processed is kept in a thermostatic chamber maintained at 30 ° C to 60% RH, and after 4000 hours, it is observed by scanning electron microscopy (SEM). The crystal filament on the formed tin plating film. Further, for the surface particle size (Ra) and the average unevenness interval (Sm) after the etching treatment, an ultra-deep shape measuring microscope (VK-88 5 0 manufactured by the company Keyence) was used, and each of the copper or copper alloy materials after the etching treatment was used. One sample was measured at 3 points, and the average enthalpy was measured. Further, regarding the surface roughness (Ra) and the unevenness interval (Sm) of the table, the lead frame in Comparative Example 1 before the tin plating treatment was also measured. (Measurement Results) The measurement results of the examples and comparative examples are shown in Tables 1 and 2 below. Further, "〇", "△", and "X" described in the column of the results of the evaluation of the crystal wires in Tables 1 and 2 mean the following. 〇: The crystal filament is produced by zero φ △: the crystal filament can be observed, but its length is less than 1 〇μιη X : the crystal filament can be observed, and its length is 10 μm or more. In Fig. 1, in the implementation In the processes of the first embodiment and the third embodiment, an SEM image of the surface state when the lead frame is subjected to the etching treatment to form the uneven shape is shown (FIG. 1A: Example 1, FIG. 1B: Example 3), and further, in FIG. 2, In the processes of Comparative Example 2 and Comparative Example 3, an SEM image of the surface state when the lead frame was subjected to uranium engraving to form an uneven shape was shown (FIG. 2A: Comparative Example 2, FIG. 2B: Comparative Example 3). (Examples 1 to 8) -21 - 201012970 [Table 1] Example Drug name and composition 锡 Tin average film thickness crystal wire evaluation result temperature CC) Treatment time (seconds) Etching amount (mg) Surface roughness Ra (^) Average spacing of concave and convex shapes Sm(pm) 1 Copper (II) chloride 30 Acetic acid 30 Sodium chloride 30 Ion exchange water remaining 45 80 41.9 0.22 2.98 2.8 Δ 2 Copper chloride (II) 20 Chlorinated second iron (III) 0.005 acetic acid 30 sodium chloride 30 ion exchange water remaining 45 80 43.3 0.24 2.88 2.9 Δ 3 copper chloride (II) 90 sodium formate 50 hydrochloric acid 20 polyethyleneimine (molecular, s amount 300) ion exchange water remaining 35 50 27.5 0.39 2.36 2.7 〇4 Copper acetate (Π) 70 tartar 100 Sodium chloride 45 Sodium hydroxide 15 Polyethyleneimine (molecular η nnn$ 1200) Ion exchange water remaining 55 20 39.5 0.43 2.40 2.6 〇5 Copper bromide (Π) 90 Glycol surface 20 Sodium bromide 45 Sodium hydroxide 5 Polyvinylpyrrolidone K-30 (molecular weight 4 (8) 00) Ion exchange water remaining 35 80 36.5 0.27 2.54 2.7 〇6 Antacid copper (II) 35 Formic acid 35 Potassium chloride 30 sodium hydroxide 25 polyvinylpyrrolidone j 2 K-90 (molecular weight 360,000) ion exchange Water remaining 40 100 41.2 0.35 2.46 2.4 〇7 Copper (II) bromide 55 lemon 瞧 1 〇〇 sodium chloride 45 polyvinyl alcohol 1400 (degree of polymerization about 1400) ion exchange water remaining 35 120 46.5 0.43 2.75 2.7 〇 8 bromination Copper (II) 20 Nickel bromide 0.0005 Lemon noodles 1 〇〇 Sodium chloride 45 Polyvinyl alcohol 1400 (degree of polymerization about 1400) Ion exchange water remaining 35 120 45.0 0.40 2.72 2.8 〇 (Comparative examples 1~8) -22- 201012970 〔Table 2〕
比 較 例 藥品名及組成 (g/L) 蝕刻 錫平均 膜厚 (μιη) 晶絲評 估結果 溫度 CC) 處理時間 (秒） 蝕刻量 (mg) 表面粗度 Ra((im) 凹凸形狀之平 均間隔Sm(nm) 1 無蝕刻處理 - - - 0.08 3.85 2.5 X 2 過硫酸鈉 200 硫酸 15 離子交換水其餘 30 40 87.0 0.37 4.30 2.5 X 3 過氧化氫水(35%) 50 硫酸 150 離子交換水其餘 40 120 85.5 0.22 4.55 2.5 X 4 過氧化氫水(35%) 50 硫酸 150 離子交換水其餘 40 60 45.3 0.16 3.96 2.4 X 5 過氧化氫水(35%) 50 硫酸 1〇〇 1H-四唑 0.2 鹽酸 0.01 離子交換水其餘 30 80 79.1 0.35 4.15 2.9 X 6 過氧化氫水(35%) 50 硫酸 1〇〇 聚亞乙基亞胺(分子 nnm 量 600) 離子交換水其餘 40 120 85.0 0.23 4.25 2.7 X 7 醋酸銅(II) 30 犠酸鈉 200 離子交換水其餘 35 100 43.1 0.28 3.60 2.4 X 8 氯化銅(II) 30 氯化鈉 35 離子交換水其餘 35 100 34.5 0.22 3.75 2.6 XComparative example drug name and composition (g/L) Etching tin average film thickness (μιη) Crystal wire evaluation result temperature CC) Processing time (seconds) Etching amount (mg) Surface roughness Ra ((im) Average interval of uneven shape Sm (nm) 1 No etching treatment - - - 0.08 3.85 2.5 X 2 Sodium persulfate 200 Sulfuric acid 15 Ion exchange water remaining 30 40 87.0 0.37 4.30 2.5 X 3 Hydrogen peroxide water (35%) 50 Sulfuric acid 150 Ion exchange water remaining 40 120 85.5 0.22 4.55 2.5 X 4 Hydrogen peroxide water (35%) 50 Sulfuric acid 150 Ion exchange water remaining 40 60 45.3 0.16 3.96 2.4 X 5 Hydrogen peroxide water (35%) 50 Sulfuric acid 1〇〇1H-tetrazole 0.2 Hydrochloric acid 0.01 ion Exchange water remaining 30 80 79.1 0.35 4.15 2.9 X 6 Hydrogen peroxide water (35%) 50 Sulfuric acid 1 〇〇 Polyethyleneimine (molecular nnm 600) Ion exchange water remaining 40 120 85.0 0.23 4.25 2.7 X 7 Copper acetate (II) 30 sodium citrate 200 ion exchange water remaining 35 100 43.1 0.28 3.60 2.4 X 8 copper chloride (II) 30 sodium chloride 35 ion exchange water remaining 35 100 34.5 0.22 3.75 2.6 X
從表1之實施例的結果可知，藉由含有第二銅離子源 — 之氯化銅（Π)、有機酸之醋酸，與鹵素離子源之氯化鈉 的鈾刻液而進行蝕刻處理，其後進行錫鍍敷處理之實施例 1中，係雖稍可確認出晶絲之產生，但僅可稍確認出其長 度爲1 Ομηι以下之晶絲，確認出可抑制晶絲之產生。可知 此係從蝕刻處理之導線架的表面Ra値變粗至0.22 μιη，認 爲藉由於其表面形成凹凸形狀，而使銅-錫金屬間化合物 層略均一地形成於界面全體，可抑制鍍敷皮膜上之應力局 部集中。 又，在實施例2中，藉由進一步含有作爲第二鐵離子 -23- 201012970 源之氯化第二鐵（III)，即使在以使第二銅離子之氯化銅 (II )的含量爲20g/L之情形，亦與實施例1同樣地可於 導線架表面形成凹凸形狀，可抑制晶絲之產生。 進一步，在以第二銅離子源、有機酸、與鹵素離子源 作爲主成分的蝕刻液中，進一步含有各種之聚胺化合物、 或聚乙烯化合物的實施例3〜8中，係晶絲之產生未完全被 確認而可完全地防止晶絲之產生。認爲此事係從此等之實 施例3~8的導線架中之表面粗度Ra値成爲0.27~0.43μπι 亦可判斷，相較於實施例1及2，更增大表面粗度，可使 微細之凹凸形狀形成於導線架之表面，而使金屬間化合物 層略均一地形成於界面全體，而可抑制應力局部集中。 另外，對於此等之實施例的結果，若硏究有關表2所 示之比較例，就錫鍍敷處理之前步驟而言在未蝕刻處理導 線架之比較例1中，可確認出許多具有1 〇μιη以上之長度 的晶絲發生。認爲此係從導線架之表面的粗度Ra値爲 0.0 8 μπι亦可瞭解，藉由未進行蝕刻處理，於導線架與錫 鍍敷皮膜之接觸面未形成凹凸形狀，而其結果，局部地形 成金屬間化合物層，且鍍敷皮膜之應力未被分散。 又，就鍍敷前處理步驟而言，即使在對於導線架實施 蝕刻處理之比較例2〜8中，亦確認出具有1 Ομιη以上之長 度的晶絲發生。此等之比較例中，在比較例2、3、5~8中 係如表2分別所示般，蝕刻處理後之導線架表面的粗度 Ra値成爲0·22~0.37μπι，表面粗度不變大，但與實施例 1〜8之結果所示的表面粗度之差係稍微。但，如上述般， -24- 201012970 在實施例1〜8中不產生具有ΙΟμιη以上之長度的晶絲，但 在此等之比較例2、3、5~8中產生具有ΙΟμιη以上之長度 的晶絲。此事係可有效地抑制晶絲之產生者，暗示不僅依 存於以蝕刻處理所產生之表面粗度大小，亦依存於其形狀 之凹凸形狀。 此處，若硏究顯示實施例之結果的表1、與顯示比較 例之結果的表2中之蝕刻處理後的凹凸形狀之平均間隔 Sm ( μιη )，在實施例1〜8中藉蝕刻處理而形成於導線架 表面之凹凸形狀的平均間隔係Sm値爲2.36μπι〜2.98μιη， 尤其在特別含有各種之聚胺化合物、或聚乙烯基化合物之 實施例3~8中，係Sm値爲2.36~2.75μιη。如此地，可知 在實施例1〜8中可使表面粗度大且微細凹凸形狀形成於導 線架表面。 另外，在比較例中，在已實施蝕刻處理之比較例2〜8 的全部中，形成於導線架表面之凹凸形狀的平均間隔係 Sm値爲3_60μιη〜4.55μιη，相較於上述之實施例1〜8，凹凸 形狀的平均間隔Sm爲很大者。 從此蝕刻處理後之凹凸形狀的平均間隔Sm的測定結 果可知，即使表面粗度Ra値爲〇.2μιη以上之凹凸形狀， 若未形成微細之凹凸形狀，可明確地瞭解晶絲抑制效果未 被發揮。 在上述之實施例中，表面粗度大，進一步形成微細凹 凸形狀係從圖1 Α及Β所示之SEM像亦可明確地判斷。然 而，在比較例中從觀察比較例2及3中之蝕刻處理後的表 -25- 201012970 面狀態的圖2A及B顯示的SEM像可明確地瞭解’雖可判 斷形成凹凸形狀，但其形狀並非微細者。 從如此之事，可知有效地抑制晶絲之產生者係不僅依 存以蝕刻處理所產生之表面粗度大小，亦依存於其形狀之 凹凸形狀，如實施例1〜8中之蝕刻處理般’藉由形成表面 粗度大且微細凹凸形狀，可有效地抑制晶絲之產生。 又，若從蝕刻液之組成的觀點亦加上評估，在以比較 例2之過氧化鈉與硫酸作爲主成分之蝕刻液、或以比較例 3、5、6之過氧化氫水與硫酸作爲主成分之蝕刻液中，表 面粗度Ra成爲0.22〜0.37μιη，雖可形成凹凸形狀，但如上 述般，從凹凸形狀的平均間隔Sm値或圖2判斷，無法形 成微細之凹凸形狀。 繼而，進一步在比較例2、3、5、6中係雖可形成Ra 値爲 0.22〜0.37μηι 的表面粗度，但蝕刻量多達 7 9.1〜8 7. Omg，另外，以由與比較例3同樣的組成所構成 之蝕刻液減少蝕刻量至45.3mg而處理之比較例4中，表 面粗度Ra値爲0·16μιη。從此事，與實施例1〜8比較，可 知若未增大蝕刻量，無法形成Ra値爲0.22〜0.37μιη之表 面粗度。對此，在實施例1〜8中之蝕刻處理中，就50mg 以下之蝕刻量可形成大的表面粗度之凹凸形狀，同時，如 上述般並可形成微細的凹凸形狀。 在蝕刻處理中，增大蝕刻量時，改變構件之大小，進 一步產生電氣特性等之性能劣化。若亦鑑於如此之點，在 實施例1〜8中’不以很少之蝕刻量產生電氣特性等之劣化 -26- 201012970 ，可形成表面粗度大且微細的凹凸形狀。 又，在實施例1〜8中使用作爲蝕刻液之主成分的第二 銅離子源、有機酸、與鹵素離子源之中不含有鹵素離子源 的蝕刻液而進行處理之比較例7、與使用未含有有機酸之 鈾刻液而處理之比較例8中，如上述般，具有很大之表面 粗度的凹凸形狀係可形成，但無法形成微細的凹凸形狀， 而無晶絲抑制效果。從此結果，可知藉由使用以第二銅離 φ 子源、有機酸、與鹵素離子源作爲主成分之蝕刻液而處理 ，可使表面粗度大且微細的凹凸形狀形成於導線架等之表 面，其結果，可有效地抑制晶絲。 從以上之實施例及比較例之結果，可知就錫鍍敷處理 之前處理而言，使形成鏟敷皮膜之導線架等的銅及銅合金 材料之表面藉由以第二銅離子源、有機酸、與鹵素離子源 作爲主成分之蝕刻液而進行蝕刻處理，於其表面形成表面 粗度大且微細的凹凸形狀，俾可有效地抑制晶絲。 0 〔產業上之利用可能性〕 若依上述之本發明，在錫及錫合金鍍敷處理之前處理 中，使用以第二銅離子源、鹵素離子源、與有機酸作爲主 成分之蝕刻液，可使銅或銅合金材料之表面粗化而形成表 面粗度大且微細的凹凸形狀，故可防止於錫及錫合金之鍍 敷皮膜局部性產生應力，可有效地抑制晶絲之產生。 又，在錫及錫合金鍍敷處理之前處理步驟中，藉蝕刻 處理以形成凹凸形狀’故不產生鍍敷皮膜之焊接潤濕性降 低等之性能的降低，即使對於鍍敷皮膜實施熱處理或回焊 -27- 201012970 處理，亦可抑制晶絲之產生。進一步，不須增加處理步驟 數或增設特別之設備。 [圖式簡單說明】 圖1A及圖1B係在實施例 1及實施例 3之處理中， 對於導線架而實施蝕刻處理以形成凹凸形狀時之表面狀態 的SEM像。 圖2A及圖2B係在比較例2及比較例3之處理中’ 對於導線架而實施蝕刻處理以形成凹凸形狀時之表面狀態 的SEM像。From the results of the examples in Table 1, it is known that the etching treatment is carried out by uranium engraving of sodium chloride containing a second source of copper ions, acetic acid of an organic acid, and sodium chloride of a halogen ion source. In Example 1 after the tin plating treatment, although the generation of the crystal filaments was slightly confirmed, only the crystal filaments having a length of 1 Ομηι or less were slightly confirmed, and it was confirmed that the generation of the crystal filaments was suppressed. It can be seen that this is from the surface Ra of the lead frame of the etching process to 0.22 μm, and it is considered that the copper-tin intermetallic compound layer is formed uniformly on the entire interface by the uneven shape on the surface thereof, and plating can be suppressed. The stress on the membrane is locally concentrated. Further, in Example 2, by further containing the second iron (III) chloride as the source of the second iron ion-23-201012970, even if the content of the copper (II) chloride of the second copper ion is In the case of 20 g/L, in the same manner as in the first embodiment, irregularities can be formed on the surface of the lead frame, and generation of the crystal wires can be suppressed. Further, in the etching liquid containing the second copper ion source, the organic acid, and the halogen ion source as a main component, in Examples 3 to 8 which further contain various polyamine compounds or polyethylene compounds, the generation of the crystal filaments The formation of the filaments is completely prevented without being fully confirmed. It is considered that the surface roughness Ra 中 in the lead frames of the third to eighth embodiments is 0.27 to 0.43 μπι, and it is judged that the surface roughness is increased as compared with the first and second embodiments. The fine concavo-convex shape is formed on the surface of the lead frame, and the intermetallic compound layer is formed slightly uniformly on the entire interface, and local concentration of stress can be suppressed. Further, with respect to the results of the examples, if the comparative examples shown in Table 2 were examined, in the first example of the tin plating treatment, in Comparative Example 1 in which the lead frame was not etched, it was confirmed that many had 1 The filaments of the length above 〇μιη occur. It is considered that the roughness Ra 値 of the surface of the lead frame is 0.0 8 μπι, and it is understood that the contact surface between the lead frame and the tin plating film is not formed into a concave-convex shape by the etching treatment, and as a result, the result is partially The intermetallic compound layer is formed in the ground, and the stress of the plating film is not dispersed. Further, in the pre-plating treatment step, even in Comparative Examples 2 to 8 in which the lead frame was subjected to the etching treatment, it was confirmed that the filament having a length of 1 Ο μm or more occurred. In the comparative examples, in Comparative Examples 2, 3, and 5 to 8, as shown in Table 2, the roughness Ra of the surface of the lead frame after the etching treatment was 0·22 to 0.37 μm, and the surface roughness was obtained. It did not become large, but the difference in surface roughness shown by the results of Examples 1 to 8 was slightly. However, as described above, -24-201012970 does not produce a crystal filament having a length of ΙΟμηη or more in Examples 1 to 8, but in Comparative Examples 2, 3, and 5 to 8, a length of ΙΟμιη or more is produced. Crystal wire. This is effective in suppressing the generation of the crystal filaments, suggesting that it depends not only on the surface roughness caused by the etching treatment but also on the uneven shape of the shape. Here, the average interval Sm (μιη) of the uneven shape after the etching treatment in Table 1 showing the results of the examples and the results of the comparative examples are shown, and etching treatment is performed in Examples 1 to 8. The average interval Sm 凹凸 of the uneven shape formed on the surface of the lead frame is 2.36 μm to 2.98 μm, especially in Examples 3 to 8 in which various polyamine compounds or polyvinyl compounds are particularly contained, the Sm値 is 2.36. ~2.75μιη. As described above, in Examples 1 to 8, it was found that the surface roughness was large and the fine uneven shape was formed on the surface of the wire frame. Further, in the comparative example, in all of Comparative Examples 2 to 8 in which the etching treatment was performed, the average interval Sm 凹凸 of the uneven shape formed on the surface of the lead frame was 3 to 60 μm to 4.55 μm, compared to Example 1 described above. ～8, the average interval Sm of the uneven shape is large. As a result of measuring the average interval Sm of the uneven shape after the etching treatment, it is understood that even if the surface roughness Ra 値 is not less than 2 μm, if the fine uneven shape is not formed, it is possible to clearly understand that the effect of suppressing the crystal filament is not exhibited. . In the above-described embodiment, the surface roughness is large, and the formation of the fine concave convex shape is also clearly determined from the SEM images shown in Figs. 1 and Β. However, in the comparative example, it can be clearly understood from the observation of the SEM images shown in FIGS. 2A and 2B of the surface of Tables 25-201012970 after the etching treatment in Comparative Examples 2 and 3, although the shape of the uneven shape can be judged, but the shape thereof is determined. Not a subtle one. From such a thing, it is understood that the person who effectively suppresses the generation of the crystal filament not only depends on the surface roughness generated by the etching treatment but also depends on the uneven shape of the shape, as in the etching treatment in Examples 1 to 8 The formation of the surface is coarse and the fine concavo-convex shape is formed, and the generation of the crystal filament can be effectively suppressed. Further, from the viewpoint of the composition of the etching liquid, the etching liquid containing sodium peroxide and sulfuric acid as the main component of Comparative Example 2 or the hydrogen peroxide water and sulfuric acid of Comparative Examples 3, 5, and 6 were used as the evaluation. In the etching liquid of the main component, the surface roughness Ra is 0.22 to 0.37 μm, and the uneven shape can be formed. However, as described above, the fine uneven shape cannot be formed from the average interval Sm 凹凸 of the uneven shape or FIG. 2 . Further, in Comparative Examples 2, 3, 5, and 6, the surface roughness of Ra 値 was 0.22 to 0.37 μηι, but the etching amount was as high as 7 9.1 to 8 7. Omg, and the comparison example In the comparative example 4 in which the etching liquid consisting of the same composition reduced the etching amount to 45.3 mg, the surface roughness Ra値 was 0·16 μm. From this point of view, as compared with Examples 1 to 8, it was found that the surface roughness of Ra from 0.22 to 0.37 μm could not be formed without increasing the amount of etching. On the other hand, in the etching treatment in the first to eighth embodiments, the etching amount of 50 mg or less can form a large unevenness of the surface roughness, and as described above, a fine uneven shape can be formed. In the etching process, when the etching amount is increased, the size of the member is changed to further deteriorate the performance of electrical characteristics and the like. In view of the above, in the first to eighth embodiments, the deterioration of electrical characteristics or the like is not caused by a small amount of etching, -26-201012970, and a rough surface having a large surface roughness and fineness can be formed. Further, in Examples 1 to 8, Comparative Example 7 and use of a second copper ion source, an organic acid, and an etching liquid containing no halogen ion source among the halogen ion sources were used as the main component of the etching solution. In Comparative Example 8 which was treated without the uranium enrichment of the organic acid, as described above, the uneven shape having a large surface roughness can be formed, but the fine uneven shape cannot be formed, and the effect of suppressing the filament is not obtained. As a result, it has been found that the surface of the lead frame or the like can be formed on the surface of the lead frame or the like by using an etching liquid having a second copper ion source, an organic acid, and a halogen ion source as a main component. As a result, the crystal filament can be effectively suppressed. From the results of the above examples and comparative examples, it is understood that the surface of the copper and copper alloy material such as the lead frame forming the scribing film is treated by the second copper ion source or the organic acid in the treatment before the tin plating treatment. The etching treatment is performed with an etching solution containing a halogen ion source as a main component, and a surface having a large surface roughness and a fine uneven shape is formed on the surface thereof, whereby the crystal filament can be effectively suppressed. [Industrial Applicability] According to the above invention, in the treatment before the tin and tin alloy plating treatment, an etching solution using a second copper ion source, a halogen ion source, and an organic acid as a main component is used. The surface of the copper or copper alloy material can be roughened to form a large surface roughness and a fine uneven shape. Therefore, local stress can be prevented from being locally applied to the plating film of tin and tin alloy, and the generation of the crystal filament can be effectively suppressed. Further, in the processing step before the tin and tin alloy plating treatment, the etching treatment is performed to form the uneven shape, so that the deterioration of the solder wettability of the plating film or the like is not caused, even if the plating film is subjected to heat treatment or back. Welding -27- 201012970 treatment can also inhibit the generation of crystal filaments. Further, there is no need to increase the number of processing steps or add special equipment. BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1A and FIG. 1B are SEM images of a surface state in which an etching process is performed on a lead frame to form a concavo-convex shape in the processes of the first embodiment and the third embodiment. 2A and 2B are SEM images of the surface state when the lead frame is subjected to an etching treatment to form a concavo-convex shape in the processes of Comparative Example 2 and Comparative Example 3.
-28--28-