TWI495767B - Iridium plating solution and method of plating using the same - Google Patents
Iridium plating solution and method of plating using the same Download PDFInfo
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Description
本發明是有關銥鍍覆液及其鍍覆方法。The present invention relates to a ruthenium plating solution and a plating method therefor.
銥係除了有很高的硬度之外，同時對於高濃度之酸或王水或是鹵素類也都顯示優異之耐蝕性的金屬。因此，其應用範圍不僅限於裝飾品，亦作為預定之金屬之硬化劑或觸媒，甚至是作為防腐蝕材及電接點等之材料而廣泛應用在工業用途。In addition to the high hardness, the lanthanum also exhibits excellent corrosion resistance for high concentrations of acid or aqua regia or halogens. Therefore, its application range is not limited to decorative materials, but also widely used in industrial applications as a hardener or catalyst for predetermined metals, and even as a material for corrosion-resistant materials and electrical contacts.
利用此銥之銥鍍覆液，已知例如將下述者當作銥化合物使用的銥鍍覆液：在陰離子成分為鹵原子之銥(III)錯鹽中，加入選自由飽和單羧酸、飽和單羧酸鹽、飽和二羧酸、飽和二羧酸鹽、飽和羥基羧酸、飽和羥基羧酸鹽、醯胺、尿素所成群組中之一種以上之化合物並加以攪拌所成者(參照專利文獻1)。For the ruthenium plating solution using the ruthenium, for example, a ruthenium plating solution which is used as a ruthenium compound is known, and a ruthenium (III) mixed salt having an anion component of a halogen atom is added to be selected from a saturated monocarboxylic acid. a compound of one or more of a group consisting of a saturated monocarboxylic acid salt, a saturated dicarboxylic acid salt, a saturated dicarboxylic acid salt, a saturated hydroxycarboxylic acid, a saturated hydroxycarboxylic acid salt, a guanamine, and a urea, and stirred (refer to Patent Document 1).
該銥鍍覆液係安定且不易分解，而有效地作為有高之電流效率與快速之鍍覆速度的具實用性的銥鍍覆液使用。The ruthenium plating solution is stable and difficult to decompose, and is effectively used as a practical ruthenium plating solution having high current efficiency and rapid plating speed.
然而，即使在如此優良之銥鍍覆液中，有關其鍍覆性狀，也有如下述之評判。例如，在作為如引導針(Lead pin)等用於電性連接的電子零件使用時(參照專利文獻2)，在銥鍍覆被膜會產生裂縫(crack)，而有發生不能充分滿足電氣特性之現象的情形。於如該引導針般之電子零件中，通常是在底層之銠上進行銥鍍覆被覆，但隨著如銠般之稀有金屬的價格高漲，而正進行檢討減少底層銠並使銥鍍覆被膜變厚而進行鍍覆處理的對應方式。如此之增厚形成銥鍍覆被膜時，就以往之銥鍍覆液而言，其裂縫的產生變成特別明顯，而產生不能滿足電氣特性的情形。However, even in such an excellent ruthenium plating solution, the plating properties are evaluated as follows. For example, when it is used as an electronic component for electrical connection such as a lead pin (see Patent Document 2), cracks may occur in the ruthenium plating film, and electrical characteristics may not be sufficiently satisfied. The situation of the phenomenon. In the electronic parts such as the guide pin, the ruthenium plating is usually performed on the bottom layer, but as the price of the rare metal such as ruthenium is high, the review is made to reduce the underlying ruthenium and the ruthenium coated film. A corresponding method of performing a plating process by thickening. When the ruthenium plating film is formed by such thickening, the occurrence of cracks in the conventional ruthenium plating solution becomes particularly remarkable, and the electrical characteristics are not satisfied.
專利文獻1：日本特開平6-316786號公報Patent Document 1: Japanese Patent Laid-Open No. Hei 6-316786
專利文獻2：日本特開平7-21867號公報Patent Document 2: Japanese Patent Laid-Open No. 7-21867
本發明是有鑑於上述情況而創研者，本發明之目的係提供一種銥鍍覆液及其鍍覆方法，可容易地形成極力抑制產生裂縫的銥鍍覆被膜。The present invention has been made in view of the above circumstances, and an object of the present invention is to provide a ruthenium plating solution and a plating method thereof, which can easily form a ruthenium plating film which suppresses cracks as much as possible.
本發明係一種銥鍍覆液，其係使用銥化合物之銥鍍覆液，該銥化合物係在陰離子成分為鹵原子的銥(III)錯鹽中加入選自由飽和單羧酸、飽和單羧酸鹽、飽和二羧酸、飽和二羧酸鹽、飽和羥基羧酸、飽和羥基羧酸鹽、醯胺、尿素所成群組中之一種以上之化合物並攪拌而得者，該銥鍍覆液之特徵為含有Fe、Co、Ni、Cu中之至少一種以上。藉由使Fe、Co、Ni、Cu之至少任一種金屬存在於鍍覆液中，即可有效地抑制在銥鍍覆被膜中之裂縫的產生。The present invention relates to a ruthenium plating solution which is a ruthenium plating solution using a ruthenium compound which is selected from a saturated monocarboxylic acid, a saturated monocarboxylic acid, and a ruthenium (III) mixed salt having an anion component of a halogen atom. a compound of one or more of a group consisting of a salt, a saturated dicarboxylic acid, a saturated dicarboxylic acid salt, a saturated hydroxycarboxylic acid, a saturated hydroxycarboxylic acid salt, a guanamine, and a urea, and stirred, the enamel plating solution It is characterized by containing at least one of Fe, Co, Ni, and Cu. By causing at least one of Fe, Co, Ni, and Cu to be present in the plating solution, it is possible to effectively suppress the occurrence of cracks in the ruthenium plating film.
本發明的銥鍍覆液中，Fe、Co、Ni、Cu之至少一種以上之含量係以0.01 g/L至10 g/L為佳。未達0.01g/L時，變得容易產生裂縫，超過10g/L時，結晶成長變得不安定。In the ruthenium plating solution of the present invention, at least one of Fe, Co, Ni, and Cu is preferably contained in an amount of from 0.01 g/L to 10 g/L. When it is less than 0.01 g/L, cracks are likely to occur, and when it exceeds 10 g/L, crystal growth becomes unstable.
該Fe、Co、Ni、Cu中之任一種金屬，較佳係以作為可溶性金屬鹽之方式含在鍍覆液中。Any one of Fe, Co, Ni, and Cu is preferably contained in the plating solution as a soluble metal salt.
本發明之銥鍍覆液中，銥係以金屬銥濃度計而含有1至200g/L為佳，更佳是10至20g/L。銥濃度少於1g/L時，電流密度之上限變小，難以供於實用，比200g/L多時，飽和後銥會變成不能溶解，同時成本變高價，而不適合實用。銥(III)錯鹽可採用六氯銥(III)酸鹽、六溴銥(III)酸鹽、六氟銥(III)酸鹽，而以六溴銥(III)酸鈉、六氯銥(III)酸鈉等為佳。In the ruthenium plating solution of the present invention, the lanthanum is preferably contained in an amount of from 1 to 200 g/L, more preferably from 10 to 20 g/L, based on the metal ruthenium concentration. When the concentration of cerium is less than 1 g/L, the upper limit of the current density becomes small, and it is difficult to supply it practically. When it is more than 200 g/L, the enthalpy becomes insoluble after being saturated, and the cost becomes high, which is not suitable for practical use. The strontium (III) salt may be a hexachloroiridium (III) acid salt, a hexabromo ruthenium (III) acid salt or a hexafluoroantimony (III) acid salt, and a sodium hexabromo ruthenium (III) hydride or a hexachloroantimony ( III) sodium or the like is preferred.
又，選自由飽和單羧酸、飽和單羧酸鹽、飽和二羧酸、飽和二羧酸鹽、飽和羥基羧酸、飽和羥基羧酸鹽、醯胺、尿素所成群組中之一種以上之化合物，係以添加0.001至1.0 mol/L為佳，更佳是添加0.01至0.2 mol/L。因此，該化合物係例如可採用乙酸、丙二酸二鈉、乙二酸等，而以丙二酸二鈉為佳。並且，將其添加量設成0.001至1.0 mol/L之原因，係因為比0.001 mol/L少時，幾乎無法顯現添加之效果，比1.0 mol/L多時，會妨礙析出之故。Further, it is selected from the group consisting of a saturated monocarboxylic acid, a saturated monocarboxylic acid salt, a saturated dicarboxylic acid, a saturated dicarboxylic acid salt, a saturated hydroxycarboxylic acid, a saturated hydroxycarboxylic acid salt, a guanamine, and a urea. The compound is preferably added in an amount of 0.001 to 1.0 mol/L, more preferably 0.01 to 0.2 mol/L. Therefore, as the compound, for example, acetic acid, disodium malonate, oxalic acid or the like can be used, and disodium malonate is preferred. Further, the reason why the amount of addition is 0.001 to 1.0 mol/L is that the effect of addition is hardly exhibited when it is less than 0.001 mol/L, and when it is more than 1.0 mol/L, precipitation is inhibited.
本發明之銥鍍覆液，因應需要，可含有用於調整pH之緩衝劑，例如：硼酸、胺基磺酸(sulfamic acid)等。The ruthenium plating solution of the present invention may contain a buffer for adjusting the pH, for example, boric acid, sulfamic acid or the like, as needed.
本發明之銥鍍覆方法，條件係設成pH為1至8、溫度為50至98℃、電流密度為0.01至3.0 A/dm2 ，而以使用pH為4至6、溫度為80至90℃、電流密度為0.1至0.8 A/dm2 之操作條件為佳。pH設為1至8之原因，係因為pH小於1時，電流密度之上限變小，變成不能實用，pH大於8時，會產生氫氧化物而生成沉澱之故。因此，溫度比50℃低時會變成極度難以析出，溫度比98℃高時，水之蒸發會變得激烈，實用上並不佳。並且，電流密度比0.1A/dm2 低時，析出速度變得極端小，電流密度比3.0 A/dm2 高時，會引起氫氣的產生，而使析出物變得不析出。The ruthenium plating method of the present invention is set to a pH of 1 to 8, a temperature of 50 to 98 ° C, a current density of 0.01 to 3.0 A/dm 2 , and a pH of 4 to 6, and a temperature of 80 to 90. ℃, current density 0.1 to 0.8 A / dm 2 of the operating conditions is preferred. The reason why the pH is set to 1 to 8 is because the upper limit of the current density becomes small when the pH is less than 1, and it becomes unpractical. When the pH is more than 8, a hydroxide is generated to cause precipitation. Therefore, when the temperature is lower than 50 ° C, it becomes extremely difficult to precipitate, and when the temperature is higher than 98 ° C, the evaporation of water becomes intense, which is not practical. Further, when the current density is lower than 0.1 A/dm 2 , the precipitation rate becomes extremely small, and when the current density is higher than 3.0 A/dm 2 , hydrogen gas is generated and precipitates are not precipitated.
依照本發明，則可形成極力抑制產生裂縫的銥鍍覆被膜。According to the present invention, it is possible to form a ruthenium plating film which suppresses the occurrence of cracks as much as possible.
以下，關於本發明之實施形態，一面參照實施例，一面說明本發明。Hereinafter, the present invention will be described with reference to the embodiments of the present invention.
在此實施例1中，係說明在銥鍍覆液中添加Fe之情形。該實施例1之液組成是如下所述。In this embodiment 1, the case where Fe is added to the ruthenium plating solution is explained. The liquid composition of this Example 1 is as follows.
六溴銥(III)酸鈉 15 g/L(換算成銥金屬)Sodium hexabromide (III) 15 g/L (converted to ruthenium metal)
硼酸 40 g/LBoric acid 40 g/L
丙二酸二鈉 0.02 mol/LDisodium malonate 0.02 mol/L
硫酸鐵7水合物 0.01 g/L(換算成鐵金屬)Iron sulfate 7 hydrate 0.01 g / L (converted to iron metal)
在實施例1中，係使用在上述六溴銥(III)酸鈉中加入作為「二羧酸鹽」的丙二酸二鈉並在熱浴(hot bath)中一面保持85℃一面以磁攪拌器(magnetic stirrer)攪拌1小時而成者，來作為銥化合物。在該銥鍍覆液中加入硫酸鐵7水合物，使鍍覆液中含有0.01 g/L之鐵。In the first embodiment, disodium malonate as a "dicarboxylate" is added to the above sodium hexabromosulfonate (III) and magnetic stirring is carried out while maintaining a temperature of 85 ° C in a hot bath. The magnetic stirrer was stirred for 1 hour to obtain a ruthenium compound. Iron sulfate 7 hydrate was added to the ruthenium plating solution to contain 0.01 g/L of iron in the plating solution.
然後，對於2cm×2cm之黃銅片測試片進行金屬打底電鍍(strike plating)處理，在1.0μm厚度之金屬鍍覆處理後，形成厚度3.0μm之銥鍍覆皮膜。鍍覆處理條件係設定pH為3.5至4、液溫度為80至85℃、電流密度為0.5 A/dm2 。Then, a 2 cm × 2 cm brass piece test piece was subjected to a metal plating treatment, and after a metal plating treatment of a thickness of 1.0 μm, a ruthenium plating film having a thickness of 3.0 μm was formed. The plating treatment conditions were such that the pH was set to 3.5 to 4, the liquid temperature was 80 to 85 ° C, and the current density was 0.5 A/dm 2 .
對於已被覆之銥鍍覆皮膜，係使用金屬顯微鏡(400倍)觀察鍍覆性狀。結果顯示在第1圖。For the coated ruthenium plating film, the plating property was observed using a metal microscope (400 times). The results are shown in Figure 1.
又，為了比較，製作由不添加Fe、Co、Ni、Cu中之任一者之空白的銥鍍覆液而形成銥鍍覆被膜者。該空白的電鍍條件係與含有Fe(鐵)之情形相同，結果顯示在第2圖。Further, for comparison, a ruthenium plating solution in which a blank of any one of Fe, Co, Ni, and Cu is not added is formed to form a ruthenium plating film. The blank plating conditions were the same as those in the case of containing Fe (iron), and the results are shown in Fig. 2.
如第2圖所示，以不含Fe之銥鍍覆液進行被覆者，確認在表面產生多數之裂縫。另一方面，如第1圖所示，含有Fe之銥鍍覆液的情形，幾乎沒有確認到裂縫。As shown in Fig. 2, when the coating was carried out with a plating solution containing no Fe, it was confirmed that a large number of cracks occurred on the surface. On the other hand, as shown in Fig. 1, in the case of the ruthenium plating solution containing Fe, almost no crack was observed.
又，使Fe之含量變化為0.005g/L、0.01 g/L、0.5 g/L、5.0 g/L、10 g/L，確認其裂縫產生的狀態時，在0.005g/L確認到有產生裂縫，但在0.01 g/L以上則未確認到產生裂縫。In addition, when the content of Fe was changed to 0.005 g/L, 0.01 g/L, 0.5 g/L, 5.0 g/L, and 10 g/L, and it was confirmed that the crack was generated, it was confirmed to be produced at 0.005 g/L. Crack, but at 0.01 g/L or more, no crack was confirmed.
在此實施例2中，係說明在銥鍍覆液中添加Co之情形。該實施例2之液組成是如下所述。In this embodiment 2, the case where Co is added to the ruthenium plating solution is explained. The liquid composition of this Example 2 is as follows.
六溴銥(III)酸鈉 15 g/L(換算成銥金屬)Sodium hexabromide (III) 15 g/L (converted to ruthenium metal)
硼酸 40 g/LBoric acid 40 g/L
檸檬酸二鈉 0.05 mol/LDisodium citrate 0.05 mol/L
硫酸鈷7水合物 0.5 g/L(換算成鈷金屬)Cobalt sulfate 7 hydrate 0.5 g / L (converted to cobalt metal)
在實施例2中，係使用在上述六溴銥(III)酸鈉中加入作為「羥基羧酸鹽」的檸檬酸二鈉並在熱浴中一面保持85℃一面以磁攪拌器攪拌1小時而成者，來作為銥化合物。在該銥鍍覆液中加入硫酸鈷，使鍍覆液中含有0.5 g/L之Co。In Example 2, disodium citrate as a "hydroxycarboxylate" was added to the above sodium hexabromosulfonate (III) and stirred by a magnetic stirrer for 1 hour while maintaining a temperature of 85 ° C in a hot bath. As a person, come as a bismuth compound. Cobalt sulfate was added to the ruthenium plating solution to contain 0.5 g/L of Co in the plating solution.
然後，對於2cm×2cm之黃銅片測試片進行金屬打底電鍍處理，在1.0μm厚度之金屬鍍覆處理後，形成厚度3.0μm之銥鍍覆皮膜。鍍覆處理條件係設定pH為3.5至4、溫度為80至85℃、電流密度為0.5 A/dm2 。Then, a 2 cm × 2 cm brass piece test piece was subjected to a metal plating treatment, and after a metal plating treatment of a thickness of 1.0 μm, a ruthenium plating film having a thickness of 3.0 μm was formed. The plating treatment conditions were such that the pH was set to 3.5 to 4, the temperature was 80 to 85 ° C, and the current density was 0.5 A/dm 2 .
對於已被覆之銥鍍覆皮膜，係使用金屬顯微鏡(400倍)觀察鍍覆性狀。結果顯示在第3圖。For the coated ruthenium plating film, the plating property was observed using a metal microscope (400 times). The results are shown in Figure 3.
如第3圖所示，含Co之銥鍍覆液之情形，幾乎沒有確認到裂縫。As shown in Fig. 3, in the case of the ruthenium plating solution containing Co, almost no crack was confirmed.
又，使Co之含量變化為0.005 g/L、0.01 g/L、0.5 g/L、5.0 g/L、10 g/L，確認其裂縫產生的狀態時，在0.005g/L確認到有產生裂縫，但在0.01 g/L以上則未確認到產生裂縫。Further, when the content of Co was changed to 0.005 g/L, 0.01 g/L, 0.5 g/L, 5.0 g/L, and 10 g/L, and it was confirmed that the state of the crack occurred, it was confirmed that it was produced at 0.005 g/L. Crack, but at 0.01 g/L or more, no crack was confirmed.
又，Co之含量設定在20.0 g/L，使用金屬顯微鏡(400倍)觀察鍍覆性狀。結果顯示在第4圖。Co之含量在20.0 g/L時，則得不到正常之析出。Further, the content of Co was set at 20.0 g/L, and the plating property was observed using a metal microscope (400 times). The results are shown in Figure 4. When the content of Co is 20.0 g/L, normal precipitation is not obtained.
在此實施例3中，係說明在銥鍍覆液中添加Ni之情形。該實施例3之液組成是如下所述。In this embodiment 3, the case where Ni is added to the ruthenium plating solution is explained. The liquid composition of this Example 3 is as follows.
六溴銥(III)酸鈉 15 g/L(換算成銥金屬)Sodium hexabromide (III) 15 g/L (converted to ruthenium metal)
硼酸 40 g/LBoric acid 40 g/L
乙二酸 0.05 mol/LOxalic acid 0.05 mol/L
硫酸鎳6水合物 0.5 g/L(換算成鎳金屬)Nickel sulfate 6 hydrate 0.5 g / L (converted to nickel metal)
在實施例3中，係使用在上述六溴銥(III)酸鈉中加入作為「二羧酸鹽」的乙二酸並在熱浴中一面保持85℃一面以磁攪拌器攪拌1小時而成者，來作為銥化合物。在該銥鍍覆液中加入硫酸鎳6水合物，使鍍覆液中含有0.5 g/L之Ni。In Example 3, oxalic acid as a "dicarboxylate" was added to the above sodium hexaborayium (III) hydride and stirred at a magnetic stirrer for 1 hour while maintaining a temperature of 85 ° C in a hot bath. As a bismuth compound. Nickel sulfate 6 hydrate was added to the ruthenium plating solution to contain 0.5 g/L of Ni in the plating solution.
然後，對於2cm×2cm之黃銅片測試片進行金屬打底電鍍處理，在1.0μm厚度之金屬鍍覆處理後，形成厚度3.0μm之銥鍍覆皮膜。鍍覆處理條件係設定pH為3.5至4、液溫度為80至85℃、電流密度為0.5 A/dm2 。Then, a 2 cm × 2 cm brass piece test piece was subjected to a metal plating treatment, and after a metal plating treatment of a thickness of 1.0 μm, a ruthenium plating film having a thickness of 3.0 μm was formed. The plating treatment conditions were such that the pH was set to 3.5 to 4, the liquid temperature was 80 to 85 ° C, and the current density was 0.5 A/dm 2 .
對於已被覆之銥鍍覆皮膜，係使用金屬顯微鏡(400倍)觀察鍍覆性狀。結果顯示在第5圖。For the coated ruthenium plating film, the plating property was observed using a metal microscope (400 times). The results are shown in Figure 5.
如第5圖所示，含Ni之銥鍍覆液之情形，幾乎沒有確認到裂縫。As shown in Fig. 5, in the case of the Ni-containing ruthenium plating solution, almost no crack was confirmed.
又，使Ni之含量變化為0.005g/L、0.01 g/L、0.5 g/L、5.0 g/L、10 g/L，確認其裂縫產生的狀態時，在0.005g/L確認到有產生裂縫，但在0.01 g/L以上則未確認到裂縫產生。In addition, when the content of Ni was changed to 0.005 g/L, 0.01 g/L, 0.5 g/L, 5.0 g/L, and 10 g/L, and it was confirmed that the state of cracks occurred, it was confirmed that it was produced at 0.005 g/L. Crack, but cracks were not confirmed above 0.01 g/L.
又，Ni之含量設定為15.0 g/L，使用金屬顯微鏡(400倍)觀察鍍覆性狀。結果顯示在第6圖。Ni之含量在15.0 g/L時則得不到正常之析出。Further, the content of Ni was set to 15.0 g/L, and the plating property was observed using a metal microscope (400 times). The results are shown in Figure 6. When the content of Ni was 15.0 g/L, normal precipitation was not obtained.
在此實施例4中，係說明在銥鍍覆液中添加Cu之情形。該實施例4之液組成是如下所述。In this embodiment 4, the case where Cu is added to the ruthenium plating solution is explained. The liquid composition of this Example 4 is as follows.
六溴銥(III)酸鈉 15 g/L(換算成銥金屬)Sodium hexabromide (III) 15 g/L (converted to ruthenium metal)
硼酸 40 g/LBoric acid 40 g/L
乙酸 0.02 mol/LAcetic acid 0.02 mol/L
硫酸銅5水合物 0.01 g/L(換算成銅金屬)Copper sulfate 5 hydrate 0.01 g / L (converted to copper metal)
在實施例4中，係使用在上述六溴銥(III)酸鈉中加入作為「單羧酸鹽」的乙酸並在熱浴中一面保持85℃一面以磁攪拌器攪拌1小時而成者，來作為銥化合物。在該銥鍍覆液中加入硫酸銅5水合物，使鍍覆液中含有0.01 g/L之Cu。In Example 4, acetic acid as a "monocarboxylate" was added to the above sodium hexaborayium (III) hydride, and the mixture was stirred by a magnetic stirrer for 1 hour while maintaining a temperature of 85 ° C in a hot bath. Come as a bismuth compound. Copper sulfate 5 hydrate was added to the ruthenium plating solution to contain 0.01 g/L of Cu in the plating solution.
然後，對於2cm×2cm之黃銅片測試片進行金屬打底電鍍處理，在1.0μm厚度之金屬鍍覆處理後，形成厚度3.0μm之銥鍍覆皮膜。鍍覆處理條件係設定pH為3.5至4、液溫度為80至85℃、電流密度為0.5A/dm2 。Then, a 2 cm × 2 cm brass piece test piece was subjected to a metal plating treatment, and after a metal plating treatment of a thickness of 1.0 μm, a ruthenium plating film having a thickness of 3.0 μm was formed. The plating treatment conditions were such that the pH was set to 3.5 to 4, the liquid temperature was 80 to 85 ° C, and the current density was 0.5 A/dm 2 .
對於已被覆之銥鍍覆皮膜，係使用金屬顯微鏡(400倍)觀察鍍覆性狀。結果顯示在第7圖。For the coated ruthenium plating film, the plating property was observed using a metal microscope (400 times). The results are shown in Figure 7.
如第7圖所示，含Cu之銥鍍覆液之情形，幾乎沒有確認到裂縫。As shown in Fig. 7, in the case of the Cu-containing ruthenium plating solution, almost no crack was confirmed.
又，使Cu之含量變化為0.005g/L、0.01 g/L、0.5 g/L、1.0 g/L，確認其裂縫產生的狀態時，在0.005g/L時確認到有裂縫產生，但在0.01 g/L以上則未確認到產生裂縫。Further, when the content of Cu was changed to 0.005 g/L, 0.01 g/L, 0.5 g/L, and 1.0 g/L, and it was confirmed that cracks were generated, cracks were observed at 0.005 g/L, but Cracks were not confirmed at 0.01 g/L or more.
在此實施例5中，係說明在銥鍍覆液中添加Co之情形。該實施例5之液組成是如下所述。In this embodiment 5, the case where Co is added to the ruthenium plating solution is explained. The liquid composition of this Example 5 is as follows.
六溴銥(III)酸鈉 5 g/L(換算成銥金屬)Sodium hexabromide (III) 5 g/L (converted to ruthenium metal)
硼酸 20 g/LBoric acid 20 g/L
丙二酸二鈉 0.10 mol/LDisodium malonate 0.10 mol/L
硫酸鈷7水合物 0.5 g/L(換算成鈷金屬)Cobalt sulfate 7 hydrate 0.5 g / L (converted to cobalt metal)
在實施例5中，係使用在上述六溴銥(III)酸鈉中加入作為「二羧酸鹽」的丙二酸二鈉並在熱浴中一面保持85℃一面以磁攪拌器攪拌1小時而成者，作為銥化合物。在該銥鍍覆液中加入硫酸鈷，使鍍覆液中含有0.5 g/L之Co。In Example 5, disodium malonate as a "dicarboxylate" was added to the above sodium hexaboronium (III) hydride and stirred by a magnetic stirrer for 1 hour while maintaining a temperature of 85 ° C in a hot bath. The original, as a bismuth compound. Cobalt sulfate was added to the ruthenium plating solution to contain 0.5 g/L of Co in the plating solution.
然後，對於2cm×2cm之黃銅片測試片進行金屬打底電鍍處理，在1.0μm厚度之金屬鍍覆處理後，形成厚度3.0μm之銥鍍覆皮膜。鍍覆處理條件係設定pH為3.5至4、液溫度為80至85℃、電流密度為0.2 A/dm2 。Then, a 2 cm × 2 cm brass piece test piece was subjected to a metal plating treatment, and after a metal plating treatment of a thickness of 1.0 μm, a ruthenium plating film having a thickness of 3.0 μm was formed. The plating treatment conditions were such that the pH was set to 3.5 to 4, the liquid temperature was 80 to 85 ° C, and the current density was 0.2 A/dm 2 .
對於已被覆之銥鍍覆皮膜，係使用金屬顯微鏡(400倍)觀察鍍覆性狀。結果顯示在第8圖。For the coated ruthenium plating film, the plating property was observed using a metal microscope (400 times). The results are shown in Figure 8.
如第8圖所示，含Co之銥鍍覆液之情形，幾乎沒有確認到裂縫。As shown in Fig. 8, in the case of the ruthenium plating solution containing Co, almost no crack was confirmed.
在此實施例6中，係說明在銥鍍覆液中添加Ni並變化鍍覆條件之情形。該實施例6之液組成是如下所述。In the sixth embodiment, the case where Ni is added to the ruthenium plating solution and the plating conditions are changed will be described. The liquid composition of this Example 6 is as follows.
六溴銥(III)酸鈉 10 g/L(換算成銥金屬)Sodium hexabromide (III) 10 g/L (converted to ruthenium metal)
硼酸 30 g/LBoric acid 30 g/L
乙二酸 0.05 mol/LOxalic acid 0.05 mol/L
硫酸鎳6水合物 0.5 g/L(換算成鎳金屬)Nickel sulfate 6 hydrate 0.5 g / L (converted to nickel metal)
在實施例6中，係使用在上述六溴銥(III)酸鈉中加入作為「二羧酸鹽」的乙二酸並在熱浴中一面保持85℃一面以磁攪拌器攪拌1小時而成者，來作為銥化合物。在該銥鍍覆液中加入硫酸鎳6水合物，使鍍覆液中含有0.5 g/L之Ni。In the sixth embodiment, oxalic acid as a "dicarboxylate" is added to the above sodium hexaborayium (III) hydride, and the mixture is stirred at a magnetic stirrer for 1 hour while maintaining a temperature of 85 ° C in a hot bath. As a bismuth compound. Nickel sulfate 6 hydrate was added to the ruthenium plating solution to contain 0.5 g/L of Ni in the plating solution.
然後，對於2cm×2cm之黃銅片測試片進行金屬打底電鍍處理，在1.0μm厚度之金屬鍍覆處理後，形成厚度3.0μm之銥鍍覆皮膜，測定析出效率。鍍覆處理條件係設定pH為2.0至8.5、液溫度為40至95℃、電流密度為0.01至2.0 A/dm2 。Then, a 2 cm × 2 cm brass piece test piece was subjected to metal plating treatment, and after a metal plating treatment of a thickness of 1.0 μm, a ruthenium plating film having a thickness of 3.0 μm was formed, and the deposition efficiency was measured. The plating treatment conditions were such that the pH was set to 2.0 to 8.5, the liquid temperature was 40 to 95 ° C, and the current density was 0.01 to 2.0 A/dm 2 .
設定液溫度為85℃、電流密度為0.5 A/dm2 ，測定變化pH時之析出效率。The set solution temperature was 85 ° C, the current density was 0.5 A/dm 2 , and the precipitation efficiency at the time of changing the pH was measured.
pH為0.5時，析出效率變成0%而沒有析出。pH為3.0時，析出效率是85%，未確認到裂縫。pH為4.0至7.0時，析出效率是95%至100%，未確認到裂縫。又，在pH為8.5時，則產生氫氧化物之沉澱。When the pH was 0.5, the precipitation efficiency became 0% without precipitation. When the pH was 3.0, the precipitation efficiency was 85%, and no crack was observed. When the pH was 4.0 to 7.0, the precipitation efficiency was 95% to 100%, and no crack was confirmed. Further, at a pH of 8.5, precipitation of hydroxide was caused.
其次，設定電流密度為0.5 A/dm2 、pH為3.5，測定變化浴溫時之析出效率。Next, the current density was set to 0.5 A/dm 2 and the pH was 3.5, and the precipitation efficiency at the time of changing the bath temperature was measured.
在浴溫40℃時，析出效率是0%時而沒有析出。在浴溫50℃時，析出效率是35%，確認到有裂縫。在浴溫60至70℃時，析出效率是40%至60%，未確認到裂縫。在浴溫80至95℃時，析出效率是90%至100%，未確認到裂縫。又，浴溫上昇到99℃時，來自電鍍浴之水之蒸發變激烈，而難以安定地進行鍍覆處理。When the bath temperature was 40 ° C, the precipitation efficiency was 0%, and no precipitation occurred. When the bath temperature was 50 ° C, the precipitation efficiency was 35%, and it was confirmed that there was a crack. At a bath temperature of 60 to 70 ° C, the precipitation efficiency was 40% to 60%, and no crack was confirmed. When the bath temperature was 80 to 95 ° C, the precipitation efficiency was 90% to 100%, and no crack was confirmed. Further, when the bath temperature was raised to 99 ° C, the evaporation of water from the plating bath became intense, and it was difficult to carry out the plating treatment stably.
其次，設定浴溫為85℃、pH為3.5，測定變化電流密度時之析出效率。Next, the bath temperature was set to 85 ° C and the pH was 3.5, and the precipitation efficiency at the time of changing the current density was measured.
在電流密度0.01 A/dm2 時，析出效率是50%，未確認到裂縫。在電流密度0.02 A/dm2 至1.0 A/dm2 時，析出效率是90%至100%，未確認到裂縫。在電流密度1.5 A/dm2 時，析出效率是60%，未確認到裂縫。在電流密度3.0 A/dm2 時，析出效率是20%，確認到有裂縫。又，在電流密度上昇到3.5 A/dm2 時，會產生氫氣，得不到正常之析出。When the current density was 0.01 A/dm 2 , the precipitation efficiency was 50%, and no crack was confirmed. At a current density of 0.02 A/dm 2 to 1.0 A/dm 2 , the precipitation efficiency was 90% to 100%, and no crack was confirmed. At a current density of 1.5 A/dm 2 , the precipitation efficiency was 60%, and no crack was confirmed. When the current density was 3.0 A/dm 2 , the precipitation efficiency was 20%, and cracks were confirmed. Further, when the current density was raised to 3.5 A/dm 2 , hydrogen gas was generated and normal precipitation was not obtained.
可容易地形成極力抑制產生裂縫的銥鍍覆被膜。It is possible to easily form a ruthenium plating film which suppresses generation of cracks as much as possible.
第1圖表示實施例1之鍍覆表面觀察照片。Fig. 1 is a view showing a photograph of a plated surface of Example 1.
第2圖表示無添加金屬之鍍覆表面觀察照片。Fig. 2 shows a photograph of the surface of the plated surface without added metal.
第3圖表示實施例2之鍍覆表面觀察照片。Fig. 3 is a view showing a photograph of a plated surface of Example 2.
第4圖表示實施例2之含Co量為20.0 g/L的鍍覆表面觀察照片。Fig. 4 is a photograph showing a plated surface of Example 2 containing a Co amount of 20.0 g/L.
第5圖表示實施例3之鍍覆表面觀察照片。Fig. 5 is a view showing a photograph of a plated surface of Example 3.
第6圖表示實施例3之含Ni量為15.0 g/L的鍍覆表面觀察照片。Fig. 6 is a view showing a photograph of a plated surface having a Ni content of 15.0 g/L of Example 3.
第7圖表示實施例4之鍍覆表面觀察照片。Fig. 7 is a view showing a photograph of a plated surface of Example 4.
第8圖表示實施例5之鍍覆表面觀察照片。Fig. 8 is a view showing a photograph of a plated surface of Example 5.
該代表圖無元件符號及其所代表之意義。The representative figure has no component symbols and the meanings it represents.
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| TW200848553A (en) * | 2007-03-08 | 2008-12-16 | Du Pont | Electroplating process |
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