200416308 ⑴ 玖、發明說明 【發明所屬之技術領域】 本發明係關於鎳電鍍處理時，以高電鏟良率即可延長 使用壽命，此結果致使減少陽極材料之交換次數，除有助 於電鍍裝置之工廠自動化（FA化）外，可達低成本化之鎳 合金陽極材料。 【先前技術】 例如近年製造半導體裝置等，必須形成高純度鎳薄膜 ，或形成此高純度鎳薄膜，使用具有99.99質量。/。以上之 高純度鎳爲陽極材料，利用電鍍法進行。 另方面，自近年電鍍裝置之工廠自動化及形成高純度 鎳薄膜之低成本化面而言，其現況爲經常要求高純度鎳陽 極材料提升電鍍良率，即進一歩延長使用壽命，詳言之係 提升每1個高純度鎳陽極材料之高純度鎳薄膜之形成比例 【發明內容】 〔發明之揭示〕 在此本發明者們自上述觀點，著眼於該鎳電鍍用之高 純度鎳陽極材料，以期提升電鍍良率進行硏究之結果，淸 楚 (a)—般於鎳電鑛處理，用以自電解液中之高純度鎳 陽極材料洗脫定量之鎳，於該陽極材料經常以一定之電流 -5- (2) (2)200416308 ，例如流通2A/ dm2以控制負荷電壓，隨之該負荷電壓 自該電極材料洗脫之鎳變化因應表面性狀而上升者，例如 1 .3V之初期負荷電壓（電鍍開始5分鐘後之電壓）以上升至 2.5 V之時點爲電極材料之使用壽命； (b) 另方面，自該陽極材料洗脫之鎳，以樹枝狀進行 ，最後該陽極材料呈海綿狀，例如約2.5 V之負荷電壓顯 示電極材料之海綿狀態樣者，此時點爲使用壽命，在此若 持續電鍍，負荷電壓急速上升，引起陰極電鍍面之加水分 解，因此加水分解產生之氫與氧中，尤其是氫捲入鎳電鍍 薄膜內，因存在小孔顯著傷及薄膜特性之理由者； (c) 於質量％，若將由矽：30〜3 00ppm、鋁：30〜 3〇Oppm殘餘鎳及必存雜質所成之鎳合金作爲鎳電鍍之陽 極材料，自鎳電鍍處理中該陽極材料之鎳洗脫形態細微化 ，即鎳電鍍初期之樹枝狀洗脫形態及同最後期之海綿狀洗 脫形態之細微化，藉此明顯控制陽極材料之負荷電壓上升 ，相對地可歷經長時間之電鍍處理，提升電鍍良率，相對 地增加每電極材料之電鍍處理量。 此發明係根據上述硏究結果者。 本發明顯示高電鑛良率之鎳電鍍用之鎳合金陽極材料 其一*態樣’其特徵爲質量％，係由Ϊ夕：3〇〜300ppm、銘： 30〜3 00ppm殘餘鎳及必存雜質所成者。 再者本發明顯示高電鍍良率之鎳電鍍用之鎳合金陽極 材料另一態樣，其特徵爲於具有9 9.9 9質量％以上純度之 高純度鎳以矽及鋁爲合金成分， - 6- (3) (3)200416308 以分別含矽：30〜3 00ppm， 銘：30 〜300ppm， 之比例所成之鎳合金所構成者。 又，構成此本發明鎳合金陽極材料之鎳合金，如上述 以含矽及鋁共存之狀態電鍍處理中之電極材料之洗脫態樣 明顯細微化，且抑制電鍍電壓之上升，有助於使用壽命長 期化之作用，隨之僅含矽或鋁時，或該兩成分其一之含有 量低於30ppm時，無法達到該作用所期之效果，反之若 矽及鋁其一之含有量若超過3 00 ppm，爲抑制自陽極材料 表面對鎳電解液中之洗脫，此成爲電鍍電壓上升之原因， 相對地因縮短使用壽命，即使電鍍良率降低，將其含有羹 分别定爲矽：30〜300ppm、鋁：30〜300ppm。 【實施方式】 接著，以實施例具體說明本發明鎳合金陽極材料。 用電熱式熔解坩鍋，真空熔解於表1所示純度之高純 度鎳’此以鎳矽合金及鎳鋁合金之形式，分別以3 〇〜 300ppm之範圍內添加所定量之砂及銘使其含有以鑄成高 純度鎮合金，鑄造直徑·· 100mm X長度·· 120mm之錠， 於此以1 l〇〇°C之溫度熱鍛壓作成寬度：lWmm X厚度： 23mm之板材後，再施以冷壓延作成寬度·· 125mm X 厚度 :1 0 m m之冷延板，再於此以4 5 0〜7 5 0 °C範圍內之溫度維 持1小時之條件施以再晶化熱處理，作成分別如表〗所示 之平均晶體粒徑，接著自此切出長度·· 100mm X寬度： -7- (4) (4)200416308 5 0mm χ厚度：10mm之尺寸，最後用面削加工作成厚度 :7.5mm，分別製造如表1所示矽及鋁含有量之本發明鎳 合金陽極材料（以下稱爲本發明陽極材料〜〗4。 以比較之目的，如同表1所示至少鎳及鋁中一者之含 有量係本發明之範圍以外之同一條件分別製造比較鎳合金 陽極材料（以下稱爲比較陽極材料）。 - 再用以調查純度之影響，用市售99.9%鎳及99.99%鎳 ， 之l〇mm厚板，同樣分別製造習知鎳合金陽極材料（以下 鲁 稱爲習知陽極材料）1〜2。 接著，對於此結果所得本發明陽極材料1〜1 4、比較 陽極材料1〜6、及習知陽極材料1〜2，於脫脂及酸浸處 理之狀態，裝入附攪拌葉片之電鍍槽，以 陰極材料：無氧銅， 電解液：含氯化鎳：5g/l、氨基磺酸鎳：3 5 0g/l、硼 酸；40g/l、表面活性劑 0.06g/l、pH : 4.0 之氨基磺酸溶液， % 電解液之溫度：5 5 °C， 電流密度：2 A/dm2， 之條件於該陰極材料表面進行鎳電鍍之電鍍測試，測 定電鍍中之顯示電壓上升至2.5V(2.5V之顯示電壓係 於陰極材料表面加水分解產生之電壓）之電鎳時間。 (5) (5)200416308 表1 種類别 高純度鎳之純 度(質量％) 石夕含有量 (ppm) 鋁含有量 (ppm) 平均晶體粒徑 電鍍時間 (小時） 本 1 99.996 40.7 148.5 23.4 69.3 發 2 99.995 70.1 187.2 21.3 71.4 明 3 99.994 149.1 150.2 15.6 75.2 陽 4 99.993 201.3 148.9 23.7 74.7 極 5 99.995 250.8 151.4 24.0 72.1 材 6 99.992 296.9 150.6 30.7 64.4 料 7 99.996 148.8 40.2 32.2 63.0 8 99.994 150.5 101.3 20.2 70.2 9 99.996 147.9 150.4 80.6 64.1 10 99.992 150.3 200.8 28.9 67.0 11 99.995 146.7 251.8 42.6 66.8 12 99.992 150.3 298.7 50.3 63.7 13 99.994 31.2 60.3 25.4 66.2 14 99.995 72.1 32.0 33.6 64.9 比 1 99.992 21.7* 148.0 26.5 59.4 較 2 99.987 346.2* 149.3 30.3 58.8 陽 3 99.996 25.5* 21.5* 22.3 59.1 極 4 99,993 149.0 20.4* 31.6 57.2 材 5 99.985 150.1 350.6* 27.8 58.4 料 6 99.981 348.5* 351.9* 26.9 55.3 習 1 99.97 0.1 0.1 25.6 53.2 知 陽 極 材 料 2 99.99 0.1 0.2 28.8 56.1 (表中之*係表示本發明範圍以外之含有量） (6) (6)200416308 〔產業上利用性〕 自表1示結果，淸楚矽及鋁之含有量皆爲30〜 300ppm之本發明陽極材料}〜“，不依賴平均粒徑，皆 顯示長之電鍍時間，此於鎳電鍍處理時，其意爲顯示陽極 材料之局電鎳良率，對此如比較陽極材料1〜6所示至少 含砂及絕中其一之含有量若爲此發明之範圍外，相對地電 鍍時間短，很難提升陽極材料之電鍍良率。又，如習知陽 極材料1〜2所示，幾乎不含矽、鋁但相對地電鍍時間亦 短，淸楚很難提升陽極材料之電鍍良率。 如上所述，本發明鎳合金陽極材料，於鎳電鍍處理時 ，高電鍍良率即可延長使用壽命，此結果以致減少陽極材 料之交換次數，除有助於電鍍裝置之工廠自動化外，可達 低成本化等帶來工業上有利之效果。 -10-200416308 ⑴ 玖, description of the invention [Technical field to which the invention belongs] The present invention relates to a nickel plating process, which can prolong the service life with a high power shovel yield. This results in reducing the number of anode material exchanges, in addition to helping the plating device In addition to factory automation (FA), low-cost nickel alloy anode materials can be achieved. [Prior art] For example, in the manufacture of semiconductor devices in recent years, it is necessary to form a high-purity nickel thin film, or to form this high-purity nickel thin film, which has a quality of 99.99. /. The above high-purity nickel is used as an anode material, and is performed by a plating method. On the other hand, in terms of the factory automation of electroplating equipment and the low cost of forming high-purity nickel films in recent years, the current situation is that high-purity nickel anode materials are often required to improve the plating yield, that is, to extend the service life. Increase the formation ratio of high-purity nickel thin film for each high-purity nickel anode material [Content of the Invention] [Disclosure of the Invention] Here, the inventors focus on the high-purity nickel anode material for nickel plating from the above point of view, with a view to The results of research on improving the yield of electroplating are as follows: (a) —generally treated with nickel ore, used to elute a certain amount of nickel from the high-purity nickel anode material in the electrolyte. The anode material is often supplied with a certain current. -5- (2) (2) 200416308, for example, 2A / dm2 is circulated to control the load voltage, and the nickel that elutes from the electrode material of the load voltage increases with the surface properties, such as the initial load voltage of 1.3V (Voltage after 5 minutes from the start of electroplating) The service life of the electrode material is taken at the point when it rises to 2.5 V; (b) On the other hand, the nickel eluted from the anode material is carried out in a dendritic shape. The electrode material is sponge-like. For example, a load voltage of about 2.5 V indicates the sponge state of the electrode material. At this point, the service life is used. If continuous plating is performed, the load voltage rises rapidly, causing the water on the cathode plating surface to decompose. Among the generated hydrogen and oxygen, especially hydrogen is engulfed in the nickel-plated film, there are reasons for the small holes to significantly damage the film characteristics; (c) In mass%, if silicon: 30 ~ 300 ppm, aluminum: 30 ~ A nickel alloy formed by 300 ppm residual nickel and necessary impurities is used as the anode material for nickel plating. The nickel elution form of the anode material during the nickel plating process is refined, that is, the dendritic elution form at the initial stage of nickel plating and the same as the final The finer sponge-like elution morphology can be used to significantly control the increase in load voltage of the anode material. Relatively, it can undergo a long period of electroplating treatment, improve the plating yield, and relatively increase the amount of electroplating treatment per electrode material. This invention is based on the above research results. The present invention shows a nickel alloy anode material for nickel electroplating with high power ore yield. It is characterized by mass%. It is composed of 30 to 300 ppm of residual nickel and 30 to 300 ppm of residual nickel and must be stored. Made of impurities. Furthermore, the present invention shows another aspect of a nickel alloy anode material for nickel plating with high plating yield, which is characterized in that high-purity nickel having a purity of 99.9% by mass or more uses silicon and aluminum as alloy components,-6- (3) (3) 200416308 A nickel alloy made of silicon containing: 30 ~ 300 ppm, inscription: 30 ~ 300ppm, respectively. In addition, the nickel alloy constituting the nickel alloy anode material of the present invention significantly reduces the elution state of the electrode material in the electroplating treatment in the state in which silicon and aluminum are coexistent, and suppresses the increase in plating voltage, which is helpful for use. The effect of prolonged life, when it contains only silicon or aluminum, or the content of one of the two components is less than 30ppm, the effect expected by the effect cannot be achieved, otherwise if the content of one of the silicon and aluminum exceeds 3 00 ppm. In order to suppress the elution of the nickel electrolyte from the surface of the anode material, this is the reason for the increase in plating voltage. Relatively, the service life is shortened. Even if the plating yield is reduced, the content of plutonium is determined as silicon: 30 ~ 300ppm, aluminum: 30 ~ 300ppm. [Embodiment] Next, the nickel alloy anode material of the present invention will be specifically described with examples. Using an electrothermal melting crucible, vacuum-melt the high-purity nickel with the purity shown in Table 1. In the form of nickel-silicon alloy and nickel-aluminum alloy, add the specified amount of sand and inscription to the range of 30 ~ 300ppm, respectively. Contains ingots with high purity cast alloys, casting diameters ... 100mm X length ... 120mm, which are hot-forged at a temperature of 1100 ° C to produce a width: 1Wmm X thickness: 23mm. Cold-rolled to make a width of 125mm X Thickness: cold-rolled sheet of 10 mm, and then recrystallize heat treatment at a temperature in the range of 450 ~ 750 ° C for 1 hour. The average crystal grain size shown in the table, and then cut out length 100mm X width: -7- (4) (4) 200416308 5 0mm χ thickness: the size of 10mm, and finally use the surface shaving to add thickness: 7.5 mm, the nickel alloy anode materials of the present invention (hereinafter referred to as the anode materials of the present invention ~) as shown in Table 1 were manufactured separately as shown in Table 1. For comparison purposes, as shown in Table 1, at least one of nickel and aluminum The content is under the same conditions outside the scope of the present invention. Anode materials (hereinafter referred to as comparative anode materials).-To investigate the effect of purity, commercially available 99.9% nickel and 99.99% nickel, 10mm thick plates, were also used to manufacture conventional nickel alloy anode materials (hereinafter Lu (Referred to as conventional anode materials) 1 to 2. Next, the anode materials 1 to 1 of the present invention obtained according to this result, comparative anode materials 1 to 6, and conventional anode materials 1 to 2 are in a state of degreasing and acid leaching. Into a plating tank with stirring blades, with cathode material: oxygen-free copper, electrolyte: containing nickel chloride: 5g / l, nickel sulfamate: 350g / l, boric acid; 40g / l, surfactant 0.06g / l, sulfamic acid solution of pH: 4.0,% electrolyte temperature: 5 5 ° C, current density: 2 A / dm2, the conditions of the cathode material were subjected to a nickel plating plating test to determine the plating process The display voltage rises to 2.5V (the display voltage of 2.5V is the voltage generated by the decomposition of water on the surface of the cathode). (5) (5) 200416308 Table 1 Purity (mass%) of high-purity nickel Evening content (ppm) Aluminum content (ppm) Average crystal grain size Plating time (Hours) Ben 1 99.996 40.7 148.5 23.4 69.3 Issue 2 99.995 70.1 187.2 21.3 71.4 Ming 3 99.994 149.1 150.2 15.6 75.2 Sun 4 99.993 201.3 148.9 23.7 74.7 Poles 5 99.995 250.8 151.4 24.0 72.1 Materials 6 99.992 296.9 150.6 30.7 64.4 Materials 7 99.996 148.8 40.2 32.2 63.0 8 99.994 150.5 101.3 20.2 70.2 9 99.996 147.9 150.4 80.6 64.1 10 99.992 150.3 200.8 28.9 67.0 11 99.995 146.7 251.8 42.6 66.8 12 99.992 150.3 298.7 50.3 63.7 13 99.994 31.2 60.3 25.4 66.2 14 99.995 72.1 32.0 33.6 64.9 compared to 1 99.992 21.7 * 14 26.5 59.4 compared to 2 99.987 346.2 * 149.3 30.3 58.8 positive 3 99.996 25.5 * 21.5 * 22.3 59.1 pole 4 99,993 149.0 20.4 * 31.6 57.2 material 5 99.985 150.1 350.6 * 27.8 58.4 material 6 99.981 348.5 * 351.9 * 26.9 55.3 exercise 1 99.97 0.1 0.1 25.6 53.2 Known anode materials 2 99.99 0.1 0.2 28.8 56.1 (* in the table indicates the content outside the scope of the present invention) (6) (6) 200416308 [Industrial applicability] From the results shown in Table 1, The anode materials of the present invention each containing 30 to 300 ppm} ~ ", do not rely on flat The particle size shows a long plating time. When nickel plating is performed, it means to show the local nickel yield of the anode material. As shown in the comparison of anode materials 1 to 6, it contains at least one of sand and absolute one. If the content is outside the scope of the present invention, the plating time is relatively short, and it is difficult to improve the plating yield of the anode material. In addition, as shown in Xizhi anode materials 1 to 2, almost no silicon or aluminum is used, but the plating time is relatively short. It is very difficult for Chu to improve the plating yield of anode materials. As mentioned above, the nickel alloy anode material of the present invention can prolong the service life during the nickel plating process with a high plating yield. This results in reducing the number of anode material exchanges. In addition to helping the factory automation of the plating device, it can reach The cost reduction and the like bring industrially advantageous effects. -10-