1332533 % ' (1) 九、發明說明 【發明所屬之技術領域】 * 本發明係關於一種電鍍浴，特別是酸電鍍浴，包含一 陽極，一陰極和電解質。 【先前技術】 上述類型的電鍍浴爲現有技藝狀態中熟知者。此處不 φ 需另外給出文件證明。 電鍍方法，諸如銅鍍、鎳鑛、鋅鍍或錫鍍，也利用可 溶性或不溶性陽極來進行。使用可溶性陽極（也稱爲活性 陽極系統）時，在電解中陽極會溶到溶液中。不溶性陽極 — (也稱爲惰性陽極系統）在電解中不會溶到溶液中且通常 於一方面係載體材料及另一方面安裝於載體材料上的塗層 " (可稱爲活性層）所構成。於其中，常用鈦 '鈮、不銹鋼 或其他惰性金屬作爲載體材料，不過於使用此等材料的任 # 何情況中，都會在電解條件下變成鈍性。有關活性層的材 料，常使用電子傳導性材料，諸如鉑、銥或其他貴金屬， 彼等的混合氧化物或此等元素的化合物。於此，該活性層 可直接施加到載體材料的表面上或者可置於一基材上而與 載體材料相隔開。有關零材，也可以使用例如可用爲載體 材料的該等材料，諸如不銹鋼、鈦或類似者。 '通常，可以利用直流帶、脈衝電流或脈衝反向電流來 進行電鍍。 於現有技藝中，已知可將添加劑加到電鍍浴中，該等1332533 % ' (1) Description of the Invention [Technical Field of the Invention] The present invention relates to an electroplating bath, particularly an acid electroplating bath, comprising an anode, a cathode and an electrolyte. [Prior Art] Electroplating baths of the above type are well known in the state of the art. No φ here is required to provide documentation. Electroplating methods, such as copper plating, nickel ore, zinc plating or tin plating, are also carried out using a soluble or insoluble anode. When a soluble anode (also known as an active anode system) is used, the anode dissolves into the solution during electrolysis. Insoluble anodes (also known as inert anode systems) do not dissolve into solution during electrolysis and are typically coated on the one hand and on the other hand on a carrier material. Composition. Among them, titanium 'bismuth, stainless steel or other inert metal is commonly used as a carrier material, but in any case where such materials are used, it becomes blunt under electrolysis conditions. As the material of the active layer, an electron conductive material such as platinum, rhodium or other precious metal, a mixed oxide thereof or a compound of such elements is often used. Here, the active layer may be applied directly to the surface of the carrier material or may be placed on a substrate to be spaced apart from the carrier material. As the material, it is also possible to use, for example, such materials which can be used as a carrier material, such as stainless steel, titanium or the like. 'Usually, it can be plated with a DC band, pulse current or pulse reverse current. In the prior art, it is known to add an additive to an electroplating bath, such
-4- (2) (2)1332533 添加劑係作用爲例如，增亮劑、增加硬度及/或分散度。 於此，較佳者爲使用有機化合物作爲添加劑。 於電鏟操作中，於不溶性陽極上會產生氣體，諸如氧 或氯。此等氣體可能誘發電鍍浴中所含添加劑的氧化，此 可能導致此等添加劑的部份或甚至於完全分解。此種情勢 爲一種雙重缺陷。於一方面，必須連續地更換添加劑，而 於另一方面，添加劑的降解產物會引起干擾，使得有需要 經常更新或純化或再生電鍍浴，此係既不經濟又不具生態 學合理性者。 爲了解決此問題，EP 1 102 875 B1業經提出一種鹼性 電鍍浴，利用離子交換膜將陽極與陰極分開。此設計具有 使有機化合物與陽極分開之優點，此幾乎可防止添加劑氧 化。不過，此設計的缺陷在需要更多的儀器，因爲電鍍浴 需要密閉的盒子，其中陽極電解液包住陽極而陰極電解液 包住陰極。此外，需要更高的張力，此點使得該設計的經 濟效率受到質疑。不過總體而言其一項決定缺陷在於EP 1 1 02 8 75 B1提出的解決之道根本不能用於彼等情況，例如 以其所用陽極形式不能用於管件的內部塗覆。 所以，DE 102 61 493 A1提出一種不同於EP 1 102 8 75 B1的設計之陽極，其係由於一方面，一陽極基體，與 另一方面一用於陽極基體的篩網所構成，此種陽極的使用 可促成所需儀器的減少，但其對工作件，亦即陰極，僅能 以不有利之方式得到減低的層厚度分布。再者，其缺陷在 於儘管有篩網，在陽極仍可產生氣體，例如氧氣，其可能 -5- (3) 1332533 導致藥劑的氧化，此等藥劑係包含在電鍍浴者，諸如添加 劑。其結果爲，在DE 1 02 6 1 493 A1中所述配置也呈現出 _ 藥劑過高消耗之情形，此爲不經濟且也需要更多儀器者。 WO 2004/038070 A2揭示出脈衝反向電流對於從酸性 銅電鍍浴沈積銅之用途。在其中作爲範例地使用之電解質 具有在10與500毫克/升之間，通常約80毫克/升的氯離子含 量。 Φ US 2002/0036 1 44揭示用於銅沈積的帶有聚乙烯基吡 咯烷酮之銅電解液。其中所揭示的電解質包含70毫克/升 的HC1，相應於68毫克/升之氯離子含量° US 2003/085 1 33 A1揭示用於銅的電沈積之電解質， . 其可能含有20與200毫克/升之間的氯離子含量。 US 6,610,192揭示銅電解質。其中所述電解質可含1至 3〇〇克/升，較佳者150至250克/升的酸。其中也揭示HC1爲 穩定的酸。諸實施例中所述氯離子含量爲約5 0毫克/升。 Φ US 5,972，192述及用於脈衝電鑛法的含氯離子之銅電 解質。 【發明內容】 根據上述技藝狀態，本發明的目的因而爲提出一種改 良的，可克服先前所述諸缺陷之使用直流電，脈衝電流或 脈衝反向電流之電鍍浴。 該目的係因本發明提出的一種電鍍浴，特別是一種酸 電鍍浴而達成，該電鍍浴具有一陽極，一陰極和一電解質 -6- (4) 1332533 ，其中該陽極爲雙相或多相者且其中該電解質含有超過7〇 毫克/升的氯離子且進一步者5至5000毫克/升，較佳者2〇〇 - 至1200毫克/升的至少—種選自鉬、釩、鉻、鉅、鎢、給 或鈦’呈其離子形式所組成的群組中之元素。其中，所提 及的元素可用彼等的氧酸之陰離子或多陰離子，在高度酸 溶液中，或彼等的酸酐之陽離子’或多陰離子，諸如砂金 屬酸根，之形式使用。 • 令人訝異地’經發現雙相或多相陽極配合高氯離子含 量，如超過70毫克/升的氯離子，之使用可導致優異的塗 覆結果。本發明特別適合用銅電解質來實現，因爲高氯離 子含量可導致較細的銅晶體結構以及層厚度的更佳分布。 - 再者，可以施加的更高電流密度可誘導更快速的銅沈積。 本發明的實現也促成更便宜的氧化銅品質，此使得本發明 的實現特別經濟》 由鉬、釩、銷、鉬、鎢、鈴或鈦所組成的群組之元素 Φ ，呈彼等的氧酸之陰離子或多陰離子的形式，在高度酸性 溶液中，或彼等的酸酐之陽離子的形式或者雜多陰離子諸 如矽金屬酸根形式之添加，可導致結晶層與層厚度分布之 進一步改良。 本發明所得優點不是可預料到的，因爲具有活性電極 系統的電解質之氯離子含量典型地係在約80毫克/升的級 次，否則銅電極會變鈍性之故。此外，若使用活性電極系 統，更高的氯離子含量會導致降解產物的增量，此會使得 在相當短時間內就需要至少一次活性碳處理。 (5) (5)1332533 此等從現有技藝所知針對較高氯離子含量之缺陷可經 由根據本發明的實現而解決，因爲本發明使用雙相或多相 ’惰性電極系統配合高氯離子含量之故。於本發明中，電 解質含有90毫克/升至5000毫克/升，較佳者1〇〇毫克/升至 3〇〇毫克/升，更佳者120毫克/升至25 0毫克/升之氯離子。 “雙相或多相”陽極，於本發明的意義中，係指由一方 面爲陽極基體，與另一方面爲該陽極基體的篩網，所構成 之陽極。於本發明中，該陽極基體爲第一相而該篩網爲第 二相。該陽極基體本身係由一方面爲載體材料，與另一方 面的活性層所構成。於本發明中，該載體材料可爲鈦、鈮 、不銹鋼或其他惰性金屬。該活性層可爲一塗層，或可直 接施加在載體材料上。作爲活性層者，適當者爲，特別是 銥、鉑、其他貴金屬，彼等的化合物且特別是彼等的混合 氧化物。 陽極的篩網較佳地係與載體材料相隔開且係由塑膠或 金屬所構成。該篩網可爲織物或柵格或網絡。於一第一具 體實例中，該篩網爲由鈦製柵格或網絡所組成。於一第二 具體實例中，該篩網係由聚丙烯織物所形成。較佳者爲使 用兩件式篩網，其中該篩網的第一部份係由鈦製栅格或網 絡所形成，該篩網的第二部份係聚丙烯織物。於本發明中 係將聚丙烯織物放置在一方爲陽極體與另一方爲鈦製柵格 或網絡之間。具有兩件式篩網的陽極爲三相者。 雙相或多相電極系統可防止電解質被氧太高地污染及 因而藥劑的太高消耗。本發明電鍍浴因而證明爲特別經濟 -8 - (6) (6)1332533 者。 更進一步者’添加劑只被非常少量的氧破壞到小程度 ，此可顯著延遲所需的電解質純化，例如利用活性碳處理 或傳統的氧化處理。於此方面中，業經進行過的檢驗已證 明本發明電鍍浴的操作時間比現有技藝已知的電鑛浴增加 3 0 0%° 本發明進一步提供一種電鍍方法，其中係使用呈現出 上述諸特性的電鍍浴。其中，該沈積較佳者係利用直流電 進行的。藉此’可以得到特別細的晶體結構，其可導致改 進的沈積層物理性質。其中，本發明電鍍浴可用於水平與 垂直兩種裝置之中。 取代直流電者，本發明電鍍浴也適合用於利用脈衝電 鍍來塗敷金屬。 依氯離子含量而定，可得到不同的層厚度分布，其總 體而言比現有技藝所知的層厚度分布更爲佳。例如，如下 所述，依氯離子含量且在其他程序參數不變之下，在一印 刷板上，具有不同直徑的10個孔洞之平均層厚度爲： (鑽孔中心至表面的關係） 75毫克/升的氯離子促成72%層厚度分布（分散） 1〇〇毫克/升的氯離子促成89%層厚度分布（分散） 125毫克/升的氯離子促成102%層厚度分布（分散） 150毫克/升的氯離子促成125 %層厚度分布（分散） 175毫克/升的氯離子促成132%層厚度分布（分散） (7) (7)1332533 250毫克/升的氯離子促成99%層厚度分布（分散） 如上面例子表單所示，利用本發明電鍍浴可得明顯改 善的層厚度分布。 根據本發明的實現之一項優點也爲經濟應用性。若使 用所述惰性陽極系統，可以使用氧化銅或另一種銅化合物 來再生耗竭的銅。其中，所用氧化銅的價格高度地取決於 氯含量，其中氧化銅愈貴，氯含量愈低。根據本發明，使 用特別高的氯含量，其可促成使用特別便宜的氧化銅於再 生目的。此外也爲此理由，本發明經證明可用高度經濟方 式來應用。 本發明的其他優點和特性可得自下面僅利用圖1所作 的說明部份。 【實施方式】 陽離子基體2本身係由載體材料4與塗層5(亦即活性層） 所構成。該載體材料4較佳者爲不銹鋼、鈦或類似者，而 該塗層5較佳者由銥混合氧化物，鉑或類似者所製成。塗 層5可直接施加在該載體材料4之上或與其相隔開。於根據 圖1的示範具體實例中，該塗層5係與該載體材料4相隔開 ，其中在該載體材料4與塗層5之間的距離係以a表出。此 距離a可爲例如數個十分之一毫米。於根據圖1的示範具體 實例中，塗層7係由—基材所載著，該基材可由不銹鋼、 鈦或類似者所構成。 陽極1的篩網3爲一種兩部份物件，如圖1中所看出者 -10- (8.) (8.)1332533 。該篩網3的第一部份係由非傳導性材料，諸如塑膠（如 聚丙烯）、玻璃纖維或礦物纖維，或由多孔型非傳導性隔 膜所構成的織物6所形成。篩網3的第二部份係由鈦製柵格 或網絡7所組成。該篩網3係與陽極基體2相隔開，其中在 該陽極基體2與該聚丙烯製織物之間的距離b可在0.01至10 毫米之間。該篩網3的第二部份，亦即鈦製柵格或網絡7也 與該篩網3的第一部份，亦即聚丙烯製織物6，相隔開，其 中該距離c也爲0.1毫米與10毫米之間。其他尺寸也爲可能 者，決定於該電鍍浴的應用領域。於此，上述距離標示不 可視爲對本發明的限制。 【圖式簡單說明】 圖1爲本發明多相陽極的示意側視圖。此陽極1係由一 方的陽極基體2，與另一方的篩網所組成。 圖2爲顯示出層厚度分布與氯離子含量關係的曲線圖 〇 圖3爲氯離子含量保持相同之下，層厚度分布與鉬濃 度的關係之曲線圖。 【主要元件符號說明】 1 :陽極 2 :陽極基體 3 :篩網 4 :載體材料 -11 - (9) (9)133-2533-4- (2) (2) 1332533 Additives function as, for example, brighteners, increased hardness and/or dispersion. Here, it is preferred to use an organic compound as an additive. In shovel operation, a gas such as oxygen or chlorine is produced on the insoluble anode. These gases may induce oxidation of the additives contained in the plating bath, which may result in partial or even complete decomposition of such additives. This situation is a double defect. On the one hand, the additives must be continuously replaced, and on the other hand, the degradation products of the additives cause interference, making it necessary to frequently renew or purify or regenerate the electroplating bath, which is neither economical nor ecologically sound. In order to solve this problem, EP 1 102 875 B1 proposes an alkaline electroplating bath which separates the anode from the cathode by means of an ion exchange membrane. This design has the advantage of separating the organic compound from the anode, which almost prevents oxidation of the additive. However, the drawback of this design is that more instruments are needed because the plating bath requires a closed box in which the anolyte encases the anode and the catholyte encases the cathode. In addition, higher tension is required, which makes the economic efficiency of the design questionable. In general, however, one of the drawbacks of the decision is that the solution proposed by EP 1 1 02 8 75 B1 cannot be used at all in any case, for example in the form of the anode used, which cannot be used for the internal coating of the pipe. Thus, DE 102 61 493 A1 proposes an anode different from the design of EP 1 102 8 75 B1, which is composed of an anode substrate on the one hand and a screen for the anode substrate on the other hand, such an anode. The use of this can lead to a reduction in the required instrument, but it can only result in a reduced layer thickness distribution for the workpiece, that is to say the cathode, in an unfavorable manner. Moreover, the drawback is that despite the presence of a screen, a gas, such as oxygen, can be generated at the anode, which may -5-(3) 1332533 cause oxidation of the agent, which is included in the plating bath, such as an additive. As a result, the configuration described in DE 1 02 6 1 493 A1 also presents a situation in which the medicament is excessively consumed, which is uneconomical and requires more instruments. WO 2004/038070 A2 discloses the use of pulsed reverse current for the deposition of copper from an acid copper electroplating bath. The electrolyte used therein as an example has a chloride ion content of between 10 and 500 mg/liter, usually about 80 mg/liter. Φ US 2002/0036 1 44 discloses a copper electrolyte with polyvinylpyrrolidone for copper deposition. The electrolyte disclosed therein contains 70 mg/L of HC1, corresponding to a chloride ion content of 68 mg/L. US 2003/085 1 33 A1 discloses an electrolyte for electrodeposition of copper, which may contain 20 and 200 mg/ Chloride ion content between liters. US 6,610,192 discloses copper electrolytes. Wherein the electrolyte may contain from 1 to 3 g/l, preferably from 150 to 250 g/l of acid. It also reveals that HC1 is a stable acid. The chloride ion content in the examples is about 50 mg/liter. Φ US 5,972,192 describes copper electrolytes containing chloride ions for pulsed ore mining. SUMMARY OF THE INVENTION In accordance with the above state of the art, it is therefore an object of the present invention to provide an improved electroplating bath that utilizes direct current, pulsed current or pulsed reverse current to overcome the aforementioned drawbacks. The object is achieved by an electroplating bath, in particular an acid electroplating bath, provided by the invention, the electroplating bath having an anode, a cathode and an electrolyte-6-(4) 1332533, wherein the anode is biphasic or multiphase And wherein the electrolyte contains more than 7 mg/L of chloride ion and further 5 to 5000 mg/L, preferably 2〇〇- to 1200 mg/L, at least one selected from the group consisting of molybdenum, vanadium, chromium, and giant , tungsten, or titanium as an element in its group of ionic forms. Wherein, the elements mentioned may be used in the form of their anion or polyanion of oxyacids, in highly acidic solutions, or in the form of cations or polyanions of their anhydrides, such as gadolinate. • Surprisingly, it has been found that biphasic or multiphase anodes with high chloride ion content, such as more than 70 mg/l chloride, can lead to excellent coating results. The invention is particularly suitable for implementation with copper electrolytes because high chloride ion content can result in a finer copper crystal structure and a better distribution of layer thickness. - Again, the higher current density that can be applied induces faster copper deposition. The realization of the present invention also contributes to the cheaper quality of copper oxide, which makes the realization of the present invention particularly economical. The element Φ consisting of molybdenum, vanadium, pin, molybdenum, tungsten, bell or titanium is in the form of oxygen. The addition of anionic or polyanionic forms of the acid, in highly acidic solutions, or in the form of cations of their anhydrides or additions of heteropolyanions such as ruthenium metalate forms, may result in further improvements in the crystal layer and layer thickness distribution. The advantages obtained by the present invention are not as expected because the chloride ion content of the electrolyte having the active electrode system is typically in the order of about 80 mg/liter, otherwise the copper electrode will become dull. In addition, if an active electrode system is used, a higher chloride ion content will result in an increase in degradation products, which would require at least one activated carbon treatment in a relatively short period of time. (5) (5) 1332533 These defects, known from the prior art for higher chloride ion content, can be solved by implementation according to the invention, since the invention uses a two-phase or multi-phase 'inert electrode system with high chloride ion content The reason. In the present invention, the electrolyte contains 90 mg/liter to 5000 mg/liter, preferably 1 mg/liter to 3 mg/liter, and more preferably 120 mg/liter to 25 mg/liter chloride. . "Two-phase or multi-phase" anode, in the meaning of the present invention, refers to an anode formed by a screen having an anode substrate on one side and a cathode substrate on the other hand. In the present invention, the anode substrate is the first phase and the screen is the second phase. The anode substrate itself is composed of a carrier material on the one hand and an active layer on the other side. In the present invention, the support material may be titanium, tantalum, stainless steel or other inert metal. The active layer can be a coating or can be applied directly to the carrier material. As the active layer, those which are suitable are, in particular, ruthenium, platinum, other noble metals, their compounds and especially their mixed oxides. The screen of the anode is preferably spaced apart from the carrier material and is comprised of plastic or metal. The screen can be a fabric or a grid or a network. In a first specific example, the screen is comprised of a titanium grid or network. In a second specific embodiment, the screen is formed from a polypropylene fabric. Preferably, a two-piece screen is used, wherein the first portion of the screen is formed from a titanium grid or mesh and the second portion of the screen is a polypropylene fabric. In the present invention, the polypropylene fabric is placed between one of the anode bodies and the other of the titanium grid or network. The anode with a two-piece screen is a three-phase one. A two-phase or multi-phase electrode system prevents the electrolyte from being contaminated too much by oxygen and thus the consumption of the agent is too high. The electroplating bath of the invention thus proves to be particularly economical -8 - (6) (6) 1332533. Further, the additive is only destroyed to a small extent by a very small amount of oxygen, which can significantly delay the required purification of the electrolyte, such as by activated carbon treatment or conventional oxidation treatment. In this aspect, the tests performed have demonstrated that the operating time of the electroplating bath of the present invention is increased by 300% compared to the electromineral bath known in the prior art. The present invention further provides an electroplating method in which the above-described characteristics are exhibited. Electroplating bath. Among them, the deposition is preferably carried out by using direct current. By this, a particularly fine crystal structure can be obtained which can lead to improved physical properties of the deposited layer. Among them, the electroplating bath of the present invention can be used in both horizontal and vertical devices. In place of direct current, the electroplating bath of the present invention is also suitable for coating metal with pulsed electroplating. Depending on the chloride ion content, different layer thickness distributions can be obtained, which are generally better than the layer thickness distribution known in the prior art. For example, as described below, the average layer thickness of 10 holes with different diameters on a printing plate based on the chloride ion content and other program parameters is: (Drilling center to surface relationship) 75 mg /L of chloride ion promotes 72% layer thickness distribution (dispersion) 1 〇〇 mg / liter of chloride ion promotes 89% layer thickness distribution (dispersion) 125 mg / liter of chloride ion contributes to 102% layer thickness distribution (dispersion) 150 mg /L of chloride ion contributes to 125% layer thickness distribution (dispersion) 175 mg / liter of chloride ion contributes to 132% layer thickness distribution (dispersion) (7) (7) 1332533 250 mg / liter of chloride ions contribute to 99% layer thickness distribution (Dispersion) As shown in the example form above, a significantly improved layer thickness distribution can be obtained by using the electroplating bath of the present invention. An advantage of the implementation according to the invention is also economic applicability. If the inert anode system is used, copper oxide or another copper compound can be used to regenerate the depleted copper. Among them, the price of copper oxide used is highly dependent on the chlorine content, wherein the more expensive the copper oxide, the lower the chlorine content. According to the invention, a particularly high chlorine content is used which contributes to the use of particularly inexpensive copper oxide for regenerative purposes. Also for this reason, the invention has proven to be applicable in a highly economical manner. Other advantages and features of the present invention can be derived from the illustrative portions that are only made using Figure 1 below. [Embodiment] The cationic substrate 2 itself is composed of a carrier material 4 and a coating layer 5 (i.e., an active layer). The carrier material 4 is preferably stainless steel, titanium or the like, and the coating 5 is preferably made of cerium mixed oxide, platinum or the like. The coating 5 can be applied directly onto or spaced apart from the carrier material 4. In the exemplary embodiment according to Fig. 1, the coating 5 is separated from the carrier material 4, wherein the distance between the carrier material 4 and the coating 5 is indicated by a. This distance a can be, for example, a few tenths of a millimeter. In the exemplary embodiment according to Fig. 1, the coating 7 is carried by a substrate which may be composed of stainless steel, titanium or the like. The screen 3 of the anode 1 is a two-part object, as seen in Figure -10- (8.) (8.) 1332533. The first portion of the screen 3 is formed of a non-conductive material such as a plastic (e.g., polypropylene), fiberglass or mineral fiber, or a fabric 6 comprised of a porous, non-conductive membrane. The second portion of the screen 3 is comprised of a titanium grid or network 7. The screen 3 is spaced from the anode substrate 2, wherein the distance b between the anode substrate 2 and the polypropylene fabric can be between 0.01 and 10 mm. The second portion of the screen 3, i.e., the titanium grid or network 7, is also spaced from the first portion of the screen 3, i.e., the polypropylene fabric 6, wherein the distance c is also 0.1 mm. Between 10 mm. Other sizes are also possible, depending on the application area of the plating bath. Here, the above distance indication is not to be construed as limiting the invention. BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a schematic side view of a multiphase anode of the present invention. This anode 1 is composed of one side of the anode base 2 and the other of the screens. Fig. 2 is a graph showing the relationship between the layer thickness distribution and the chloride ion content. Fig. 3 is a graph showing the relationship between the layer thickness distribution and the molybdenum concentration under the same chlorine ion content. [Explanation of main component symbols] 1 : Anode 2 : Anode substrate 3 : Screen 4 : Carrier material -11 - (9) (9) 133-2533
5 :塗層 6 :織物 7 :柵格或網絡 a、b、c :距離5 : Coating 6 : Fabric 7 : Grid or network a, b, c : distance