TWI296289B - Electroplating solution containing organic acid complexing agent - Google Patents
Electroplating solution containing organic acid complexing agent Download PDFInfo
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- TWI296289B TWI296289B TW092103070A TW92103070A TWI296289B TW I296289 B TWI296289 B TW I296289B TW 092103070 A TW092103070 A TW 092103070A TW 92103070 A TW92103070 A TW 92103070A TW I296289 B TWI296289 B TW I296289B
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/60—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of tin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/30—Electroplating: Baths therefor from solutions of tin
- C25D3/32—Electroplating: Baths therefor from solutions of tin characterised by the organic bath constituents used
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Mechanical Engineering (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
- Electrodes Of Semiconductors (AREA)
Description
(1) I296289 i、發明說明 明明應敘明：發明所屬之技術領域、先前技術、内容、實施方式及圖式簡單說 域 本發明係關於金屬的沉積；更特定言之，係關於在由可 電Μ基材如金屬，或由具有可電鍍和不可電鍍部份之複合 物件所組成之物品或物件上之錫或錫-鉛合金的沉積。本 發明亦描述一種可在電沉積過程中抑制多數此類複合物 件溶化的方法，此與在單位質量中具有大表面積且對熔化 敏感之小型電.器組件的電鍍有關。本文特別感興趣的是諸 如具有金屬部份與陶瓷、玻璃或塑膠部份之表面黏著電容 器和電阻器的電器組件。 先前技術 電器組件的大小近年來已經顯著地減小，這種尺寸的減 小已經使得這些組件的電鏡明顯地更加困難。此外，許多 表面黏著技術（SMT)組件具有敏感的陶瓷部份，其會被強 酸或強鹼溶液所破壞。為了避免此問題，¥性或接近中性 pH的電鍛 >谷液是較佳的。 _ 特別調配成與敏感的陶变SMTs相容之中性或接近中性 pH的錫和錫/鉛合金電解液描述於美國專利第4，163,700號 、第 4,329,207號、第 4,640,746號、第 4,673,470和第 4,681，670號中。 這些專利中所述的調配物包括如檸檬酸鹽、葡萄糖酸鹽或 焦磷酸鹽等組份的錯合劑，用來與錫和/或鲜錯合，並使 錯合物在所需的高pHs下溶解於溶液中。 先前技藝溶液的使用具有組件會在電沉積過程中搞合 或凝聚的持續性問題。當以錫或錫合金電鍍具有平坦表面 1296289 _ 门、 I發明說明續頁 之小組件時，該組件在電鍍過程中有群集傾向是相當平常 的。當滾桶電鍍SMT組件時，有多達進料的10%會耦合（亦 即黏在一起）並非異常。在一些情況下，整個進料會熔融 在一起形成大塊。此問題的程度視電鍍溶液組成和電鍍方 法及組件的幾何形狀而定。此問題在錫-鉛合金電鍍中特 別明顯。(1) I296289 i, the description of the invention clearly stipulates: the technical field, prior art, content, embodiments and drawings of the invention. The present invention relates to the deposition of metals; more specifically, Electrode substrates such as metals, or deposition of tin or tin-lead alloys on articles or articles consisting of composite articles having electroplatable and non-platable portions. The present invention also describes a method for inhibiting the melting of most such composite materials during electrodeposition, which is related to electroplating of small electrical components having a large surface area per unit mass and sensitive to melting. Of particular interest herein are electrical components such as those having a metal portion and a ceramic, glass or plastic portion that adheres to the capacitor and resistor. The size of prior art electrical components has decreased significantly in recent years, and this reduction in size has made the electron microscopy of these components significantly more difficult. In addition, many surface mount technology (SMT) components have sensitive ceramic parts that can be destroyed by strong acid or strong alkaline solutions. In order to avoid this problem, an electric forging > valley liquid of a neutral or near neutral pH is preferred. _ Tin and tin/lead alloy electrolytes specially formulated to be compatible with sensitive ordinary SMTs at neutral or near neutral pH are described in U.S. Patent Nos. 4,163,700, 4,329,207, 4,640,746, 4,673,470 and No. 4,681,670. The formulations described in these patents include a combination of components such as citrate, gluconate or pyrophosphate to align with tin and/or fresh and to provide the complex at the desired high pHs. Dissolved in the solution. The use of prior art solutions has the persistence of components that can engage or coalesce during electrodeposition. When plating with a tin or tin alloy with a flat surface 1296289, it is quite common for the component to have a clustering tendency during electroplating. When the drum is plated with SMT components, up to 10% of the feed will couple (ie stick together) is not anomalous. In some cases, the entire feed will melt together to form a large mass. The extent of this problem depends on the composition of the plating solution and the plating method and the geometry of the component. This problem is particularly noticeable in tin-lead alloy plating.
特別調配成與敏感的陶瓷SMTs相容之中性或接近中性 pH的錫和錫/鉛合金電鍍液有一些好處，但其並非針對零 件熔化的問題。此外，頃發現對陶瓷的侵蝕乃強烈地受電 解液組成及pH的影響。先前技藝之電解液已被發現即使 在接近中性的pH下也會傷害新的低火陶瓷；而且尚有關 於在薄鍍零件上之錫晶鬚成長的問題，因此一種防晶鬚錫 鍍層是所希望的。本發明現提供一種溶液和方法可以克服 此問題，並提#所希望的鍍層。 、 發J月内容 ' ，Specially formulated into tin and tin/lead alloy plating solutions that are compatible with sensitive ceramic SMTs at neutral or near neutral pH, there are some benefits, but not for the melting of parts. In addition, it has been found that the erosion of ceramics is strongly influenced by the composition and pH of the electrolyte. Previously known electrolytes have been found to damage new low-fire ceramics even at near-neutral pH; and there is also the problem of tin whisker growth on thin-plated parts, so an anti- whisker tin coating is Hoped. The present invention now provides a solution and method that overcomes this problem and provides the desired coating. , send J month content ' ,
本發明係關於一種用於與一或多種金屬在可電鍍基材 上的沉積有關尚溶液。此溶液包含水、量足以在可電鍍基 材上提供金屬鍍層的金屬離子、和錯合劑。該錯合劑較佳 地是一種具有介於4和1 8個碳原子間的有機化合物，其包 括至少兩個羥基和含至少一個氧原子的五或六環。該錯合 劑是以足以錯合金屬並使其溶在溶液中的量存在。此外， 該錯合劑可抑制溶液中之金屬離子的氧化。當金屬離子具 有可在溶液中以至少兩種不同價態存在的能力時，錯合劑 可避免金屬由較低價態氧化至較高價態。若需要的話，在 -6- 1296289 (3) 溶液中可包含一種適當的pH調整劑以使溶 2和1 0的範圍間。在最佳pH範圍中，該溶液 鍍部份和不可電鍍部份之複合物件的電鍍 ，且不會對不可電鑛部份有不利的影響。 錯合劑較佳地具有下列結構之一： 發明說明續頁 液的p Η維持在 對於具有可電 是特別有用的This invention relates to a solution for the deposition of one or more metals on a plateable substrate. This solution contains water, a metal ion in an amount sufficient to provide a metal coating on the electroplatable substrate, and a binder. The binder is preferably an organic compound having between 4 and 18 carbon atoms and comprising at least two hydroxyl groups and five or six rings containing at least one oxygen atom. The intermixing agent is present in an amount sufficient to mismatch the metal and dissolve it in the solution. In addition, the complexing agent inhibits oxidation of metal ions in the solution. When the metal ion has the ability to exist in at least two different valence states in solution, the complexing agent can prevent the metal from oxidizing from a lower valence state to a higher valence state. If desired, a suitable pH adjuster may be included in the -6- 1296289 (3) solution to allow for the range between 2 and 10 . In the optimum pH range, the plating of the plated portion and the non-platable portion of the composite is plated without adversely affecting the non-electrical portion. The complexing agent preferably has one of the following structures: Description of the Invention Continued p Η of the liquid is maintained particularly useful for having electricity
RCRC
I (T-CR)m cr2or 其中每一個R是相同或不同的，且為氫或1」 低碳烷基；T是R、OR或0= P(OR)2- ; Z是0 = 且Z在結構中每次的出現可以是相同或不同 ，或者錯合劑是此結構的一種可溶解鹽。最 括抗壞血酸、異抗壞血酸、脫氫抗壞血酸、 血酸、半乳糖鉍酸、葡萄糖醛酸和6 -磷酸葡 類。典型的鹽類包括驗金屬或驗土金屬。這 以約25至200公克/升的量存在。 本發明亦關於一種在複合物件上電鍍金 ，該複合物件包括可電鍍和不可電鍍部份。 此物件的大部分與一種本文所述之溶液接声 中通入電流，以在物件的可電鍍部分提供金 會對物件的不可電鍍部分有不利的影響。較 L 3個碳原子的 :或 RO- ; η是 2-4 的；而m是1 · 3 佳的化合物包 葡萄糖型抗壞 萄糖、或其鹽 些錯合劑通常 屬鍍層的方法 本方法包括使 I，然後在溶液 屬電鍍層而不 佳的金屬電鍍 1296289 (4) 發明說明續頁 層是錫金屬或錫-錯合金，而較佳的物件為電子組件。 實施方式 現今已發現複合物件電子組件的熔化可經由提供一種 本文所揭示之包括一或多種錯合劑的電解液而將其大部 分排除，尤其抗壞血酸和相關化合物作為此類錯合劑是最 佳的。 雖然該錯合劑亦可用在電鍍其他金屬，特別是那些具有 多重價態金屬的溶液中，但是其在電鍍錫或錫-鉛鍍層的 溶液中是較有用的。這些錯合劑幫忙使溶液中的金屬維持 在其較低價態之一，因而促進電鍍步驟並避免金屬的氧化 (其會影響溶液正當操作）。在這些系統中四價錫也會被錯 合。 上述調配物的任一種錯合劑均可用在本發明中，較有利 的錯合劑是有機酸，較佳的試劑包括抗壞血酸、異抗壞血 酸_、脫氫抗壞血酸、葡萄糖型抗壞血酸、、半乳糖醛酸、和 葡萄糖醛酸。遠些酸的鹽類也可以使用，較佳的鹽類是鹼 金屬或鹼土金屬鹽類。可以使用葡萄糖酸酮，因為這些、匕 合物會在鍍浴中轉化成抗壞血酸；葡萄糖酸庚酯類由於在 溶液中會轉化成類似的酸性物種也是適用的。任一種這些 試劑均可在約25至200公克/升的典型量下使用。最佳的錯 合劑是抗壞血酸或一種抗壞血酸鹽，因為這些化合物是價 格較低且易購得的。 抗壞血酸是以純粹的抗壞血酸、一種抗壞血酸鹽如抗壞 血酸鈉或鉀、和/或抗壞血酸-金屬錯合物，例如抗壞血酸 1296289 _ I發明說明續頁 錫包含在溶液中。當希望使用其他酸性的組份如有機酸或 有機酸鹽維持所要的溶液ρ Η時，後者是較佳的。抗壞血 酸存在的量應至少足以使存在溶液中的金屬溶解在特定 pH的溶液中，因此所需抗壞血酸的量係與金屬濃度成比 例。在1 5公克/升的錫濃度時，較佳的抗壞血酸濃度是約 45至200公克/升。 任何可電鍍的基材都可用本發明的溶液電鍍。通常，這 些基材是由諸如銅、錄、鋼鐵或不鏽鋼等金屬製成。在現 今的市售產品中，需要電鍍的零件是以愈來愈小的尺寸製 造，尤其電子組件是此類零件的一個典型實例；而且，這 些零件是具有可電鍍和不可電鍍部分的複合物件。當金屬 部分是金屬或金屬性時，不可電鍍部分通常是陶瓷、玻璃 或塑膠。本溶液特別適用於電鍍此類複合物件。 電鍍溶液可以具有在2 - 1 0間的任何ρ Η，但為了使溶液與 被_電鍍的電子組件相容，pH較佳地是在缚3#7.5的範圍内 ，且更佳地是約4至5.5。當組件具有金屬的和無機的部份 時，較佳的pH範圍可使金屬鑛在金屬的部分而不會對無 機的部分有不利的影響。通常，非常高或非常低pH的溶 液會破壞被電鍍複合物件的陶瓷部分。 基本上雖然任何酸或鹼都可用作pH調整，但是這些溶 液最好不含可感知量的游離酸或游離鹼。由於溶液通常是 酸性的，因此使用鹼或鹼性組份將游離酸轉化成相當的鹽 類。用作此目的之較佳的鹼包括氫氧化鈉或氫氧化鉀及許 多其他的驗。 1296289 _ ⑹ I發明說明續頁I (T-CR)m cr2or wherein each R is the same or different and is hydrogen or 1" lower alkyl; T is R, OR or 0 = P(OR)2-; Z is 0 = and Z Each occurrence in the structure may be the same or different, or the complexing agent is a soluble salt of the structure. Most are ascorbic acid, isoascorbic acid, dehydroascorbic acid, blood acid, galactosic acid, glucuronic acid and 6-phosphate. Typical salts include metal or soil testing metals. This is present in an amount of from about 25 to 200 grams per liter. The invention also relates to a method of electroplating gold on a composite article comprising electroplatable and non-platable portions. The majority of the article is galvanically coupled to a solution as described herein to provide a gold in the electroplatable portion of the article that adversely affects the non-platable portion of the article. More than L 3 carbon atoms: or RO-; η is 2-4; and m is 1 · 3 preferred compound encapsulated glucose-type glucose, or a salt thereof, which is usually a coating method. The method includes I, and then in the solution of the plating is not good metal plating 1296289 (4) Description of the continuation layer is tin metal or tin-alloy, and the preferred object is an electronic component. Embodiments It has now been discovered that the melting of composite electronic components can be largely eliminated by providing an electrolyte comprising one or more of the intercalating agents disclosed herein, particularly ascorbic acid and related compounds are preferred as such intercalating agents. Although the dopant can also be used in electroplating other metals, particularly those having multiple valence metals, it is useful in electroplating tin or tin-lead plating solutions. These binders help maintain the metal in the solution in one of its lower valence states, thereby promoting the plating step and avoiding oxidation of the metal (which can affect proper solution operation). Tetravalent tin is also mismatched in these systems. Any of the above-mentioned formulations may be used in the present invention. The more advantageous complexing agent is an organic acid. Preferred agents include ascorbic acid, isoascorbic acid, dehydroascorbic acid, glucose ascorbic acid, galacturonic acid, and Glucuronic acid. Salts of far acidity can also be used, and preferred salts are alkali metal or alkaline earth metal salts. Gluconate can be used because these, the complexes are converted to ascorbic acid in a plating bath; the heptyl gluconate is also suitable for conversion to a similar acidic species in solution. Any of these agents can be used at typical amounts of from about 25 to 200 grams per liter. The best intermixing agent is ascorbic acid or an ascorbate because these compounds are relatively inexpensive and readily available. Ascorbic acid is pure ascorbic acid, an ascorbate such as sodium or potassium ascorbate, and/or ascorbic acid-metal complex, such as ascorbic acid 1296289 _ I. Illustrated continuation Tin is contained in solution. The latter is preferred when it is desired to maintain the desired solution ρ 使用 using other acidic components such as organic or organic acid salts. The amount of ascorbic acid present should be at least sufficient to dissolve the metal present in the solution in a solution of a particular pH, so the amount of ascorbic acid required is proportional to the metal concentration. At a tin concentration of 15 g/l, the preferred ascorbic acid concentration is about 45 to 200 g/l. Any electroplatable substrate can be electroplated with the solution of the present invention. Typically, these substrates are made of a metal such as copper, bronze, steel or stainless steel. In today's commercially available products, parts that need to be plated are manufactured in ever smaller sizes, especially electronic components are a typical example of such parts; moreover, these parts are composite parts having electroplatable and non-platable parts. When the metal portion is metallic or metallic, the non-platable portion is typically ceramic, glass or plastic. This solution is particularly suitable for electroplating such composite articles. The plating solution may have any ρ 在 between 2 and 10, but in order to make the solution compatible with the electroplated electronic component, the pH is preferably in the range of 3# 7.5, and more preferably about 4 To 5.5. When the assembly has metallic and inorganic moieties, the preferred pH range allows the metal ore to be in the metal portion without adversely affecting the inorganic portion. Typically, a very high or very low pH solution will destroy the ceramic portion of the electroplated composite. Essentially, although any acid or base can be used as a pH adjustment, these solutions preferably contain no appreciable amount of free acid or free base. Since the solution is usually acidic, the free acid is converted to a comparable salt using an alkali or basic component. Preferred bases for this purpose include sodium hydroxide or potassium hydroxide and many others. 1296289 _ (6) I invention description continuation page
溶液係調配成與被電鍍基材相容，且較佳地對基材沒有 不利的效果。當電鍍具有可電鍍和不可電鍍部分的複合物 件時，溶液應調配成不會侵蝕或弄裂基材的不可電鍍部分 。一種簡單的試驗可用來測量基材/溶液的相容性，將被 電鍍物件完全浸入計畫溶液中維持一段時間，該時間係等 於或大於電鍍過程中所用的時間。溶液的溫度可以是接近 電鍍過程中之溶液溫度，或是在加速試驗中所用的高溫。 該零件浸在溶液中經過所需時間後，接著將其取出並稱重 以測量在浸泡過程中溶液侵蝕該物件所產生的重量損失。 例如，現今用於電容器製品的複合物件是用低火陶瓷所 製，這些陶瓷較之習知陶瓷含有較大比例的玻璃，在電鍍 過程中有更易於受到侵蝕的傾向。一種簡單的比較試驗被 用來測量不同市售溶液與根據本發明之溶液的相容性：將 電容器放入含等量這些溶液的燒杯中，在5小時的浸泡後 測_量零件的重量損失。結果顯示於下表良： 溶液 -— 在溶液中浸泡5小時後的重量損失 (%) : 競爭者A(以葡萄糖酸鹽為主，pH值 1.0% 3.5的浸浴） 競爭者A(以葡萄糖酸鹽為主，pH值4 0.5% 的浸浴） - 競爭者B(以擰檬酸鹽為主，pH值4.2 5.0% 的浸浴） 本發明（抗壞血酸浴，pH值5) 0.0% -10 _ 1296289 _ (ΊΛ 發明說明續頁 此表顯示本發明對電容器基本上並無影響，而且與習知鍍 浴相比，對於此類組件的電鍍是實質的改良。 電鍍此類電器組件的一個特別有用的設計揭示於美國 專利第6，193,858號中，無須於本文中再加以敘述。對於需 要的範圍，該專利的全文係以參考的方式明確地揭示於本 文。 對於先前專利系統的改良已經揭示於公開的國際申請 書（Published International Application)第 W0 02/053809號中，其全 文係以參考的方式明確地併入本中。如這份申請書所揭示 ，電鍍室浸入電解液中代表一種明顯的改良，可外部溶解 的電極現已可用在其中。 頃發現含本發明之錯合劑的電解液能夠電沉積錫或錫-鉛合金，同時將電鍍零件的熔化或耦合減至最少，而且不 會對物件的不可電鍍部分有不利的影響。關於這一點，這 些_電解液是優於先前技藝者，尤其是以檸檬酸鹽為主的鍍 浴。錯合劑係角來使溶液中的錫和/或錯維持在電解液的 pH ;某些錯合劑，尤其是抗壞血酸，亦做為避免二~價鸽 氧化成四價錫的安定劑。 L-抗壞血酸（AA)可輕易地轉化成L-脫氫抗壞血酸（DAA) 。此外，DAA可以經由將兩個在相鄰碳上的酮基轉化成羥 基、連結那些原子的單鍵轉化成雙鍵而輕易地回復成AA 。AA轉化成DAA的容易性使得AA成為一種強還原劑。在 本發明的電鍍溶液中，A A可幫助錫離子在二價態及四價 態錯合，此避免或至少減少了會沉澱形成沉積物而對溶液 1296289 _ 發明說明續頁 性能有不利影響的錫氧化物的形成。 根據本發明之一個較佳的溶液包含水、一種二價錫鹽和 做為錯合劑的抗壞血酸，且視需要地包含一種二價鉛鹽、 一種增加電傳導性的鹽類、一種界面活性劑或一種促進陽 極溶解的試劑。 可用在本發明的二價錫鹽包括硫酸亞錫、氯化亞錫、氧 化亞錫、甲烷磺酸亞錫、抗壞血酸亞錫或任何其他適當的 二價錫來源。溶液中二價錫的濃度可以是由5至100公克/ 升，且最佳地是由10至50公克/升。如上所述，因為本發明 的錯合劑也會錯合四價錫鹽，因此沒有疑慮地添加四價錫 鹽到溶液中以取代二價錫鹽或與其一起併用是可能的。 可視需要添加以提供錫-鉛鍍層的鉛鹽包括任何溶液可 溶的二價鉛鹽，其包括例如甲烷磺酸鉛、醋酸鉛或抗壞血 酸鉛。 .若需要的話，溶液的導電性可以經由一種孽類的添加而 增加。若希望是純錫溶液，可以使用如硫酸鉀的單純鹽類 ;若希望是錫/錯合金，則甲烷磺酸鉀或醋酸鉀是較適當 的。必要時，金屬硫化物鹽類也可以使用。這些鹽類的任 一種都可用來促進陽極溶解並幫助電沉積。 一般用在錫或錫合金電解液中的界面活性劑可以包含 在溶液中以改善鍍層晶體結構，並改良高電流密度時之鍍 層品質。較佳的界面活性劑包括溶液可溶的環氧烧縮合化 合物、溶液可溶的四級銨-脂肪酸化合物、溶液可溶的氧 化胺化合物、溶液可溶的三級胺化合物或其混合物。一種 -12- 1296289 _ ⑼ I發明說明續頁 較佳的界面活性劑是環氧烷縮合化合物，其係以約0.01至 20公克/升的量存在。雖然一些添加劑在被電鍍物件的耦 合方面可以進行得比其他添加劑好，但因為在鍍層外觀上 對於此組份並無臨界條件，故其他習知的界面活性劑也可 以使用。此藝中具有一般技藝者可進行例行測試以決定任 何特別電鍍溶液的最適當界面活性劑。The solution is formulated to be compatible with the substrate to be plated, and preferably has no adverse effect on the substrate. When electroplating composite articles having electroplatable and non-platable parts, the solution should be formulated so as not to erode or crack the non-platable portion of the substrate. A simple test can be used to measure the substrate/solution compatibility by completely immersing the plated article in the solution solution for a period of time equal to or greater than the time spent in the plating process. The temperature of the solution can be close to the temperature of the solution during the plating process or the elevated temperature used in the accelerated test. After the part has been immersed in the solution for a desired period of time, it is then removed and weighed to measure the weight loss produced by the solution eroding the article during the soaking process. For example, today's composite articles for capacitor articles are made of low-fire ceramics which contain a greater proportion of glass than conventional ceramics and are more susceptible to erosion during electroplating. A simple comparative test was used to measure the compatibility of different commercially available solutions with solutions according to the invention: placing the capacitors in a beaker containing equal amounts of these solutions, measuring the weight loss of the parts after 5 hours of immersion . The results are shown in the table below: Solution - weight loss after soaking for 5 hours in solution (%): Competitor A (prime with gluconate, pH 1.0% 3.5) Competitor A (with glucose Acid salt-based, pH 4 0.5% bath) - Competitor B (based on citrate, pH 4.2 5.0% bath) The present invention (ascorbic acid bath, pH 5) 0.0% -10 _ 1296289 _ (ΊΛ Inventive Note Continued page This table shows that the present invention has essentially no effect on the capacitor, and the plating of such components is substantially improved compared to conventional plating baths. A useful design is disclosed in U.S. Patent No. 6,193,858, the disclosure of which is hereby incorporated by reference in its entirety in its entirety in its entirety in its entirety in In the published international application (Published International Application) No. WO 02/053809, the entire disclosure of which is hereby incorporated by reference in its entirety in its entirety in Significantly improved, externally dissolvable electrodes are now available. It has been found that electrolytes containing the presenting agent of the present invention are capable of electrodepositing tin or tin-lead alloys while minimizing melting or coupling of the plated parts, and not This has an adverse effect on the non-platable parts of the object. In this regard, these _ electrolytes are superior to those of the prior art, especially citrate-based plating baths. The wrong agent is used to make the tin in the solution. / or wrong to maintain the pH of the electrolyte; some of the wrong agents, especially ascorbic acid, also act as a stabilizer to avoid oxidation of the second-price pigeon to tetravalent tin. L-ascorbic acid (AA) can be easily converted into L-de Hydrogen ascorbic acid (DAA). In addition, DAA can be easily returned to AA by converting two ketone groups on adjacent carbons to a hydroxyl group, a single bond linking those atoms to a double bond. The ease with which AA is converted to DAA Making AA a strong reducing agent. In the electroplating solution of the present invention, AA can help the tin ions to align in the divalent state and the tetravalent state, which avoids or at least reduces the precipitation of precipitates and forms the solution 1296289 _ The formation of tin oxide having an adverse effect on the continuation of the sheet. A preferred solution according to the invention comprises water, a divalent tin salt and ascorbic acid as a binder, and optionally a divalent lead salt, a salt that increases electrical conductivity, a surfactant, or an agent that promotes anodic dissolution. The stannous salt useful in the present invention includes stannous sulfate, stannous chloride, stannous oxide, stannous methane sulfonate, ascorbic acid. Stannous or any other suitable source of divalent tin. The concentration of divalent tin in the solution may range from 5 to 100 grams per liter, and most preferably from 10 to 50 grams per liter. As described above, since the complexing agent of the present invention is also mismatched with the tetravalent tin salt, it is possible to add the tetravalent tin salt to the solution without doubt to replace the divalent tin salt or use it together. The lead salt which may be added as needed to provide a tin-lead plating layer includes any solution-soluble divalent lead salt including, for example, lead methanesulfonate, lead acetate or lead ascorbate. If desired, the conductivity of the solution can be increased by the addition of a hydrazine. If it is desired to use a pure tin solution, a simple salt such as potassium sulfate may be used; if it is desired to be a tin/stagger alloy, potassium methanesulfonate or potassium acetate is more suitable. Metal sulfide salts can also be used if necessary. Any of these salts can be used to promote anodic dissolution and aid in electrodeposition. Surfactants commonly used in tin or tin alloy electrolytes can be included in the solution to improve the crystal structure of the coating and to improve the quality of the coating at high current densities. Preferred surfactants include solution-soluble epoxidized condensation compounds, solution-soluble quaternary ammonium-fatty acid compounds, solution-soluble oxidized amine compounds, solution-soluble tertiary amine compounds, or mixtures thereof. A -12- 1296289 _ (9) I. Description of the Invention The preferred surfactant is an alkylene oxide condensation compound which is present in an amount of from about 0.01 to 20 grams per liter. While some additives may perform better than other additives in the coupling of the electroplated article, other conventional surfactants may also be used because there is no critical condition for the composition in the appearance of the coating. One of the most suitable surfactants in the art can be routinely tested to determine any particular plating solution.
當需要明亮的鍍層時，芳族醛可以足夠做為光亮劑的量 加入。必要時，其他習知的光亮劑可替代使用。 被電鍍基材較佳地是那些具有導電和非導電部分的複 合物件。當金屬部分是金屬或金屬性時，非導電零件通常 是陶瓷、玻璃或塑膠。本溶液對於電鍍此種複合物件是特 別有用的，不會對物件的非金屬部分有不利的影響，且不 會引起此零件的熔化。When a bright coating is desired, the aromatic aldehyde can be added in an amount sufficient to be a brightener. Other conventional brighteners may be used instead if necessary. The substrate to be plated is preferably those having conductive and non-conductive portions. When the metal portion is metallic or metallic, the non-conductive component is typically ceramic, glass or plastic. This solution is particularly useful for electroplating such composite articles, does not adversely affect the non-metallic portion of the article, and does not cause melting of the component.
當需要電鍍在複合基材電子組件上時，電鍍液的pH較 佳，是保持在約4至5.5的範圍間。pH可以利用鹼，例如氫 氧化鉀、氫氧化銨、氫氧化鈉或其類似物的添加來提升； 或以酸，如硫酸或甲烧石黃酸來降低。因為硫酸會產生不溶 於溶液的硫酸鉛（其有沉澱的傾向），烷或烷醇磺酸、如甲 烧續酸對錫-錯合金溶液是較佳的。如上所述，約4至5.5 的p Η會對此類金屬的黏聚產生最強的抑制作用；而且， 為了抑制並使黏聚作用最小，抗壞血酸的量不應遠超過錯 合錫所需的量。 用於錫和錫-錯溶液的典型抗氧化劑可以包括在本發明 的溶液中（例如揭示於美國專利地4,871，429號中的鄰苯二 -13 - 1296289 發明說明續頁 (10) 酚或對苯二酚）；然而，抗壞血酸已被發現在中性或接近 中性pH之電解溶液對於避免二價錫氧化成四價錫是有效 的。因此，抗壞血酸在本溶液中具有作為錯合劑和抗氧化 劑的雙重功能。When electroplating on composite substrate electronic components is required, the pH of the plating solution is preferably maintained between about 4 and 5.5. The pH can be increased by the addition of a base such as potassium hydroxide, ammonium hydroxide, sodium hydroxide or the like; or by an acid such as sulfuric acid or methicillin. Since sulfuric acid produces lead sulfate which is insoluble in the solution (which tends to precipitate), an alkane or an alkanolsulfonic acid such as a hydrogenated acid is preferred for the tin-alloy solution. As noted above, p 约 of about 4 to 5.5 produces the strongest inhibition of cohesion of such metals; moreover, in order to suppress and minimize cohesion, the amount of ascorbic acid should not exceed the amount required for the mismatched tin. . Typical antioxidants for tin and tin-wrong solutions can be included in the solution of the present invention (for example, o-phenyl 2-3-13296, disclosed in U.S. Patent No. 4,871,429 Hydroquinone); however, ascorbic acid has been found to be effective at avoiding the oxidation of divalent tin to tetravalent tin in an electrolytic solution at neutral or near neutral pH. Therefore, ascorbic acid has a dual function as a binder and an antioxidant in this solution.
同時頃發現經由將本發明的電鍍溶液調配到具有低電 鐘能力，複合物件之非導電部分的電鑛和複合物件的溶化 可以被減至最小或大部分消除。這些溶液係特別調配到在 低電流密度時不會沉積金屬，此與習知應用，將電解液調 配成在儘可能寬的電流密度範圍下沉積金屬相反。實際上 ，多數習知的錫電Μ溶液係藉由添加各種添加劑大範圍 地延展電沉積的電流密度範圍。頃發現零件的熔化可經由 限制電沉積的電流密度範圍到較高電流密度而減少。咸信 熔化的發生是由於金屬沉積在緊密接觸的兩零件間或零 件與饋電線間之電解液薄膜。因為沉積是發生在兩導電表 面，間的薄膜上，其必須在低電流密度時才i犖生，藉由將 電解液調配成在低電流密度下不會電鍍，則熔化可以減至 最少。 頃發現零件熔化係與電解浴組成密切相關，而適當晶粒 細化劑或界面活性劑的選擇對於將熔化減至最少是重要 的。關於此點，僅含金屬鹽和錯合劑的單純電解液已被發 現可電鍍表面黏著技術（SMT)組件而無熔化的情形，所得 的錫鍍層是一種深灰色冰銅，在商業用途上是不被接受的 。當典型的界面活性劑或晶粒細化劑被加到電解液以改 善鍍層品質時，在幾乎所有的情況下均觀察到非常強的熔 -14- 1296289 發明說明續頁 (ii) 化，此顯示來自界面活性劑和晶粒細化劑的陰極表面極化 作用強烈地影響零件熔化。而且，頃發現含有在低電流密 度下提供有限覆蓋之添加劑的電解液比含有在低電流密 度下提供高度覆蓋之添加劑者有較少的溶化傾向。At the same time, it has been found that by blending the electroplating solution of the present invention to have a low clock capability, the melting of the electro-mineral and composite articles of the non-conductive portion of the composite article can be minimized or largely eliminated. These solutions are specially formulated to not deposit metal at low current densities, as opposed to conventional applications, where the electrolyte is formulated to deposit metal over the widest range of current densities. In fact, most conventional tin oxide solutions broadly extend the current density range of electrodeposition by the addition of various additives. It has been found that the melting of the part can be reduced by limiting the range of current densities of the electrodeposition to higher current densities. The melting of the salt is due to the deposition of metal between the two parts in close contact or between the parts and the feed line. Since the deposition occurs on the film between the two conductive surfaces, it must be produced at a low current density. By formulating the electrolyte to be electroplated at a low current density, the melting can be minimized. It has been found that the part melting system is closely related to the composition of the electrolytic bath, and the choice of a suitable grain refiner or surfactant is important to minimize melting. In this regard, a simple electrolyte containing only metal salts and a complexing agent has been found to be electroplatable surface mount technology (SMT) components without melting. The resulting tin coating is a dark gray matte, which is not used for commercial purposes. Accepted. When a typical surfactant or grain refiner is added to the electrolyte to improve the quality of the coating, a very strong melt is observed in almost all cases. -1296289 It is shown that the surface polarization of the cathode from the surfactant and grain refiner strongly affects the melting of the part. Moreover, it has been found that electrolytes containing additives that provide limited coverage at low current densities have less tendency to dissolve than those that provide high coverage at low current densities.
一般相信在桶中或其他適當設備中電鍍個別組件的調 配溶液必須具有高電鍍能力，因此電流將穿過進料而在大 部份進料間沉積金屬。同時也很清楚的是在低電流密度下 的電鍍速度是可忽略的，因為並無實質量的金屬在此情況 下沉積；正確地說，多數的金屬是在高電流密度下於接近 電鍍桶周圍處沉積。因此，現已發現只要零件本身沒有低 電流密度區域如凹處或盲孔，則不需要提供具有高電鍍能 力的溶液在桶或其他適當裝置中電鍍個別組件。It is believed that the formulation solution for plating individual components in a barrel or other suitable device must have a high plating capability so that current will pass through the feed to deposit metal between the majority of the feed. It is also clear that the plating speed at low current densities is negligible because no solid metal is deposited in this case; to be precise, most metals are near the plating bath at high current densities. Deposited. Therefore, it has been found that as long as the part itself does not have low current density regions such as recesses or blind holes, it is not necessary to provide a solution having high plating ability to plate individual components in a tub or other suitable device.
而且，在低電流密度不會沉積金屬的電鍍溶液將使複合 物件上非導電部分的金屬沉積減至最少。由物件的導電末 端_延伸至非導電部分上的金屬沉積現象通常稱做潛變或 橋接。此現象的程度主要視非導電物質的組成而定，例如 具有一些電導度的陶瓷物質比是良好絕緣體的陶資/物質 有較多金屬潛變的傾向。咸信潛變是電沉積時電流由物件 的導電部份滲漏到"非導電’’複合部份所造成。藉由將金屬 沉積限制在高電流密度狀況，金屬在非導電部份上的沉積 可以減到最少或消除。 本發明的電鍍溶液也可幫忙降低或消除鍍層中晶鬚的 存在，這些是電鑛後鑛層中的細絲於某些熱條件下成長所 造成。此晶鬚頃發現是低電壓設備短路的一個原因。而且 -15- 1296289 發明說明續頁 (12) ，晶鬚可由鍍層中脫離，並在其他區域累積而進一步引發 短路問題或干擾機械操作。藉由本文揭示之電鍍溶液的使 用，晶鬚生成的程度明顯減少且可完全消除。 本發明的電鍍溶液可以調配成較佳地具有下列特質和 優點： 1.其會沉積一種白色無光澤至半透明的鑛層。 2 .其不會破壞被塗佈的組件。Moreover, plating solutions that do not deposit metal at low current densities will minimize metal deposition of non-conductive portions on the composite. The phenomenon of metal deposition extending from the conductive end of the article to the non-conductive portion is commonly referred to as creeping or bridging. The extent of this phenomenon depends mainly on the composition of the non-conductive material. For example, a ceramic material having some electrical conductivity has a tendency to have more metal creep than a ceramic/material having a good insulator. The salty latent change is caused by the leakage of current from the conductive part of the object to the "non-conductive' composite part during electrodeposition. By limiting metal deposition to high current density conditions, the deposition of metal on the non-conductive portion can be minimized or eliminated. The electroplating solution of the present invention can also help to reduce or eliminate the presence of whiskers in the coating which are caused by the growth of filaments in the post-electrode ore layer under certain thermal conditions. This whisker was found to be a cause of short circuit in low voltage equipment. Furthermore, -15- 1296289, Illustrated Continuation (12), whiskers can be detached from the coating and accumulated in other areas to further cause short-circuit problems or interfere with mechanical operations. With the use of the plating solution disclosed herein, the degree of whisker formation is significantly reduced and completely eliminated. The electroplating solution of the present invention can be formulated to preferably have the following characteristics and advantages: 1. It deposits a white matte to translucent layer. 2. It does not destroy the coated components.
3 .其不會在低電流密度時沉積金屬。 4 .當鍍層接著曝露到熱條件時，其可減少或甚至消除晶鬚 生成。3. It does not deposit metal at low current densities. 4. When the coating is subsequently exposed to thermal conditions, it reduces or even eliminates whisker formation.
當被電鍍零件是包含陶瓷或含鉛玻璃部分的複合物件 時，酸或鹼溶液在電鍍時會破壞陶瓷或玻璃部分，如SMT 電阻器、感應線圈和電容器等組件都是這種類型。為了將 對物件之陶瓷或玻璃部分的傷害減到最低，用於SMT組件 之_電鍍溶液的p Η必須在約2.5和9之間。為孑達到此p Η，錫 必須是錯合的塑式。先前技藝錯合劑一般包括檸檬酸鹽、 葡萄糖酸鹽和焦磷酸鹽；然而為了電鍍半透明鍍層/一般 使用一或多種有機添加劑。多數的熟知添加劑會大大增加 溶液的低電流密度覆蓋，導致被電鍍零件的熔化和零件非 導電部份的外鍍層。 電解液的低電流密度覆蓋可以藉由在高金屬濃度下操 作、在高溫下操作、選擇不會增加低電流密度覆蓋（LCDC) 或可降低LCDC和/或其任何組合的添加劑將其減少。例如 ，當錫是被電鍍金屬時，至少約2 5公克/升的高金屬離子 -16- 1296289 發明說明續頁 (13) 含量是較佳的。由於頃發現高溫通常會增加零件熔化，高 的鍍浴溫度是減低LCDC最不希望使用的方法。When the part to be plated is a composite containing ceramic or leaded glass parts, the acid or alkali solution will damage the ceramic or glass part during plating, such as SMT resistors, induction coils and capacitors. In order to minimize damage to the ceramic or glass portion of the article, the p Η of the plating solution used for the SMT assembly must be between about 2.5 and 9. In order to achieve this p Η, the tin must be in a wrong form. Prior art complexing agents typically include citrate, gluconate, and pyrophosphate; however, one or more organic additives are typically used to plate the translucent coating. Most of the well-known additives greatly increase the low current density coverage of the solution, resulting in the melting of the plated parts and the outer plating of the non-conductive parts of the part. The low current density coverage of the electrolyte can be reduced by operating at high metal concentrations, operating at elevated temperatures, selecting additives that do not increase low current density coverage (LCDC), or can reduce LCDC and/or any combination thereof. For example, when tin is electroplated metal, at least about 25 grams per liter of high metal ion -16 - 1296289 is preferred. Since high temperatures are often found to increase part melting, high bath temperature is the least desirable way to reduce LCDC.
鍍浴中有機添加劑的選擇在使電鍍能力維持在低等級 方面是特別重要的。最佳的添加劑可由對有興趣之特定電 鍍溶液的例行試驗來決定。這些添加劑包括習知的界面活 性劑和晶粒細化劑，如單或多芳環有機化合物的縮合化合 物及其他具有似染料性質但不是界面活性劑的有機縮合 物或反應產物。這些化合物在此藝中是習知的，故僅做嫁 保其不會提供電鍍溶液高電鍍能力的試驗。The choice of organic additives in the plating bath is particularly important in maintaining the plating ability at a low level. The optimum additive can be determined by routine experimentation with a particular plating solution of interest. These additives include conventional interfacial activators and grain refiners, such as condensation compounds of mono- or polyaromatic organic compounds and other organic condensates or reaction products having dye-like properties but not surfactants. These compounds are well known in the art and are therefore only tested to provide a high plating capability for the plating solution.
其他添加劑也可與界面活性劑和晶粒細化劑併用以降 低電解液的電鍵能力。當與各種界面活性劑和晶粒細化劑 一起使用時，氯化銨、抗壞血酸和間-硝基酚已被發現可 降低電鍍能力。明顯地，許多其他的添加劑也有此種功能 ，而這些其他添加劑的使用是本發明的一個主題。此藝中 具_有一般技藝者都可進行例行試驗以決定武用或不使用 最佳的添加劑組合於任何特定的電鍍溶液中。 當電鍍複合物件時，本溶液可用在揭示於美國專利第 6，193,858號和公開的國際申請書第W0 02/053809號的設備中 。本發明的電鍍溶液也可以用在美國專利第5,487,824號和 第5,565,079號所述之旋轉式電鍍裝置中並獲致改良的結果 ，由於錫在饋電線圈的沉積實質減少，使得需要置換和拆 除饋電線的維修明顯減少。 因此，在旋轉式電鍍裝置中使用具減低之LCDC的電解 液也是本發明的一個主題。使用電鍍桶時，因為較少的金 -17- 1296289 發明說明續頁 (14) 屬沉積在懸捶上，且金屬潛變及零件熔化減少，本發明的 使用也是有利的。所以，在桶電鍍中LCDC電解液的使用 也是本發明的一個主題。 雖然本發明在電鍍無導體的複合物件上是特別有用的 ，在電鍍混有導體之個別物件上，本發明的使用具有降低 饋電線上之電鍍和降低或消除金屬在複合物件之非導電 部分上沉積的明顯優點。Other additives may also be used with the surfactant and grain refiner to reduce the electrical bond capability of the electrolyte. When used with various surfactants and grain refiners, ammonium chloride, ascorbic acid and m-nitrophenol have been found to reduce plating ability. Obviously, many other additives also have this function, and the use of these other additives is a subject of the present invention. Anyone skilled in the art can perform routine tests to determine whether or not to use the best additive combination in any particular plating solution. When the composite article is electroplated, the solution can be used in an apparatus disclosed in U.S. Patent No. 6,193,858 and the International Application No. WO 02/053809. The electroplating solution of the present invention can also be used in a rotary electroplating apparatus as described in U.S. Patent Nos. 5,487,824 and 5,565,079, and as a result of the improvement, since the deposition of tin in the feed coil is substantially reduced, it is necessary to replace and dismantle the feeder. The maintenance is significantly reduced. Therefore, the use of an electrolytic solution having a reduced LCDC in a rotary plating apparatus is also a subject of the present invention. The use of the present invention is also advantageous when using electroplating tanks because of the less gold deposited on the sling and the metal creep and reduced melting of the parts. Therefore, the use of LCDC electrolyte in barrel plating is also a subject of the present invention. While the present invention is particularly useful in electroplating conductorless composite articles, the use of the present invention reduces plating on the feeder and reduces or eliminates metal on the non-conductive portion of the composite article on individual articles that are electroplated with conductors. The obvious advantages of deposition.
測試電解液之LCDC的一種有用的方法是使用標準265毫 升何式槽（huU cell)試驗。使用標準步驟運轉何式槽，典型 的條件是在1 A下運轉5分鐘、0.5 A下5分鐘或0.25 A下5分 鐘，每一種均使用槳式攪拌。若何式槽板的背面除了由面 板邊緣延伸小於1公分的部分外，大部分是未電鍍的，則 在1 A下製備的何式槽有LCDC ;此外，電解液最佳地在前 面低電流密度邊緣有未電鍍的部分，此未電鍍部分可以由 1/8”至3/4’’的英吋寬。顯現此類型之何式槽板結果的電解液 與在何式槽面板背面產生明顯電鍍的電解液相較，通常具 有較少的熔化傾向。使金屬無法沉積之限制電流密度'可以 經由在0.25 A製備何式槽板，並使用適當的何式槽板刻度 測定金屬鍍層邊緣之電流密度而測得。 此外，當在SBE裝置中使用具LCDC的電解液於無導體之 最新SMTs時，通常發現饋電線在電鍍循環終點大部分並未 鍍上錫，且電鍍零件未炼化至饋電線。相反的，當使用市 售的中性錫電鍍液在SBE無導體電鍍SMTs時，零件在電鍍 開始的三分鐘内即卡住，且發現饋電線已完全被錫所塗覆 •18- 1296289 發明說明續頁 (15) 。因此，具LCDC之錫或錫合金電解液的使用對於在SBE裝 置中成功電鍍無導體SMTs是必須的。 實例 下面的實例說明本發明之有用具體實施例。 實例1 : 由下列溶液和下列電鍍條件得到純的錫電鍍層。 抗壞血酸 100公克/升One useful method of testing the electrolyte's LCDC is to use a standard 265 milliliter huU cell test. The tank is operated using standard procedures, typically at 1 A for 5 minutes, 0.5 A for 5 minutes, or 0.25 A for 5 minutes, each using paddle agitation. If the back side of the trough plate is mostly unplated except for the portion extending less than 1 cm from the edge of the panel, the tank prepared at 1 A has LCDC; in addition, the electrolyte is optimally low in front front current density. The edge has an unplated portion, which may be from 1/8" to 3/4" wide. The electrolyte that exhibits this type of slot plate results in significant plating on the back of the slot panel. The electrolyte usually has less tendency to melt. The limiting current density that makes the metal undepositable can be determined by preparing a slot plate at 0.25 A and using the appropriate slot plate scale to determine the current density at the edge of the metal coating. In addition, when using the electrolyte with LCDC in the SBE device for the latest SMTs without conductors, it is generally found that the feeder is not plated with tin at the end of the plating cycle, and the plated parts are not refining to the feeder. Conversely, when using commercially available neutral tin plating baths for SBE non-conductor-plated SMTs, the parts were stuck within three minutes of the start of plating and the feeders were found to be completely coated with tin. 18-18296289 The description continues (15). Therefore, the use of tin or tin alloy electrolytes with LCDC is necessary for successful plating of conductorless SMTs in SBE devices. EXAMPLES The following examples illustrate useful embodiments of the invention. : Pure tin plating layer was obtained from the following solutions and the following plating conditions: Ascorbic acid 100 g / liter
錫（甲烷磺酸鹽形式） 15公克/升 界面活性劑 0.5毫升/升 以KOH調整pH至： 4.05 上述溶液會在至高20 ASF的電流密度下沉積半透明的錫。 實例2 : 將1.5公克/升的甲烷磺酸鉛加到實例1的溶液中並在相 同條件下電鍍，得半透明錫-鉛鍍層。 抗壞血酸 100公克/升 'Tin (methane sulfonate form) 15 g/l Surfactant 0.5 ml/L Adjust the pH to KOH: 4.05 The above solution will deposit translucent tin at a current density of up to 20 ASF. Example 2: 1.5 g/l of lead methanesulfonate was added to the solution of Example 1 and electroplated under the same conditions to obtain a translucent tin-lead plating. Ascorbic acid 100 g / l '
錫（甲烷磺酸鹽形式）15公克/升 鉛（甲烷磺酸癦形式）1.5公克/升 —· 甲烧石黃酸姜曱 40公克/升 界面活性劑 0.5毫升/升 以KOH調整pH至： 4.05 此溶液會在至高20 ASF的電流密度下也沉積半透明90% 的錫。 對照實例： 在2.5”長4”寬的桶中，用140毫升、2.5毫米半徑的導電球 -19- 1296289 發明說明續頁 (16) 作為導體，使用實例1的調配物電鍍錫到250片、8毫米半 徑的平面墊片上。在5 A、6.5V下電鍍進料15分鐘。在電 鍍循環的終點，沒有任何平面墊片熔化在一起。 使用下列調配物的電解液進行相同的電鍍循環： 檸檬酸 40公克/升 錫（甲烷磺酸鹽形式） 10公克/升 鉛（甲烷磺酸鹽形式） 1.5公克/升 曱烧石黃酸钟 40公克/升 界面活性劑. 2.5毫升/升 以KOH調整pH至： 4_2 在5 A和9 V下電鍍進料15分鐘。在電鍍循環的終點，只有 1 2片沒有連在一起，其餘的墊片係以多達1 0片的量成群凝 聚在一起，且很難分開。此實例清楚地證明本發明溶液的 優異性。 實例3 : ' 下列實例說明由本發明之電鍍溶液產生的鍍層與先前 技藝之電鍍溶液比較，錫晶鬚生成的減少。 如上所述，當鑛層曝露於熱處理或條件時（如那些在電 鍍零件運轉時所遭遇的），晶鬚生成的問題會產生。晶鬚 可能花費一週至5年的時間成長，且當其成長後，其可能 引起短路或其他問題。為了測量晶鬚生成是否會在這些鍍 層中發生，一種加速試驗已經被發展出來：一種熱循環試 驗，其係將電鍍零件放進一個溫度控制在-55°C的室中15 分鐘；接著在2 0秒内將其轉移至另一個溫度室，並在125 -20- 1296289 發明說明續頁 (17) °C的溫度下令其在其中經過另外的1 5分鐘。重覆此循環 500次，觀察是否有晶鬚在鍍層上生成。 用實例1的溶液以錫電鍍基材，然後對其進行上述的熱 循環試驗500個循環；另一個基材是以來自習知葡萄糖酸 鈉電鍍液的錫電鍍，電鍍後的基材亦進行相同的熱循環試 驗500個循環。Tin (methane sulfonate form) 15 g / liter lead (methane sulfonate methane form) 1.5 g / liter - · sauerin sulphate 40 g / liter surfactant 0.5 ml / liter KOH adjusted pH to: 4.05 This solution will also deposit translucent 90% tin at current densities up to 20 ASF. Comparative example: In a 2.5" long 4" wide barrel, using a 140 ml, 2.5 mm radius conductive ball -19- 1296289. Description of the continuation (16) as a conductor, using the formulation of Example 1 to electroplate tin to 250 pieces, 8 mm radius on the flat washer. The feed was electroplated at 5 A, 6.5 V for 15 minutes. At the end of the plating cycle, no flat gaskets melt together. The same plating cycle was carried out using the electrolyte of the following formulation: 40 g of citric acid per liter of tin (form of methane sulfonate) 10 g / liter of lead (form of methane sulfonate) 1.5 g / liter of samarium sulphate clock 40 G/L surfactant. 2.5 ml/L Adjust the pH to KOH: 4_2 Electroplating feed at 5 A and 9 V for 15 minutes. At the end of the plating cycle, only 12 pieces were not joined together, and the remaining gaskets were clustered together in groups of up to 10 pieces and were difficult to separate. This example clearly demonstrates the superiority of the solution of the present invention. Example 3: 'The following example illustrates the reduction in tin whisker formation compared to the prior art plating solution produced by the plating solution of the present invention. As noted above, problems with whisker formation can occur when the deposit is exposed to heat treatment or conditions, such as those encountered when the electroplated parts are in operation. Whiskers can take up to a week to five years to grow, and as they grow, they can cause short circuits or other problems. In order to measure whether whisker formation will occur in these coatings, an accelerated test has been developed: a thermal cycle test in which the plated parts are placed in a chamber controlled at -55 ° C for 15 minutes; Transfer it to another temperature chamber within 0 seconds and allow it to pass another 15 minutes in the temperature of 125 -20-1296289. Repeat this cycle for 500 times to see if whiskers are formed on the coating. The substrate was plated with tin using the solution of Example 1, and then subjected to the above thermal cycle test for 500 cycles; the other substrate was plated with tin from a conventional sodium gluconate plating solution, and the substrate after electroplating was also subjected to the same The thermal cycle test was 500 cycles.
結果顯示於圖1 -4中。在圖1和2中，根據本發明之電鍍 零件的表面顯示出非常小、非常短的晶鬚，其係相對無害 的。比較上，根據先前技藝的電鍍零件則顯示出長很多及 多很多的晶鬚生成，因此使電鍍物件有較多的可能引發短 路或可能的機械干擾（若較長的晶鬚被移出）。因此，本發 明的電鍍層是好很多的，特別是在小零件（如電子組件） 需要有錫鍍層的時候。 圖示簡單說明 本發明的進一步優點將以圖示說明，其/中：The results are shown in Figures 1-4. In Figures 1 and 2, the surface of the electroplated part according to the present invention exhibits very small, very short whiskers which are relatively harmless. In comparison, electroplated parts according to the prior art show a much longer and much more whisker formation, thus making electroplated articles more likely to cause short circuits or possible mechanical disturbances (if longer whiskers are removed). Therefore, the electroplated layer of the present invention is much better, especially when small parts such as electronic components are required to have a tin plating. BRIEF DESCRIPTION OF THE DRAWINGS Further advantages of the present invention will be illustrated by the following:
圖1是以根據先前技藝電鑛溶液的錫電鍛之基材的顯微 照片； _ — · · 圖2是以根據本發明電鍵溶液的錫電鑛之相同基材的顯 微照片； 圖3是以根據先前技藝電鍍溶液的錫電鍍之基材的一部 份表面的放大顯微照片；及 圖4是以根據本發明電鍍溶液的錫電鍍之基材的一部份 表面的放大顯微照片。 -21 -BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 is a photomicrograph of a substrate for electrical forging of tin according to the prior art electromineral solution; Figure 2 is a photomicrograph of the same substrate of tin-electric ore of the electro-bond solution according to the present invention; An enlarged micrograph of a portion of the surface of a substrate electroplated with tin according to prior art electroplating solutions; and FIG. 4 is an enlarged photomicrograph of a portion of the surface of a substrate electroplated with tin according to the present invention. . -twenty one -
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| US7275012B2 (en) * | 2002-12-30 | 2007-09-25 | Intel Corporation | Automated method and apparatus for processor thermal validation |
| CN100457977C (en) * | 2004-08-03 | 2009-02-04 | 上海新阳半导体材料有限公司 | Electroplating additive and its preparation method |
| US20070007144A1 (en) * | 2005-07-11 | 2007-01-11 | Schetty Robert A Iii | Tin electrodeposits having properties or characteristics that minimize tin whisker growth |
| US20070034118A1 (en) * | 2005-08-12 | 2007-02-15 | Jardine Leslie A | Dosage efficient, storage stable compositions for reducing chromium (VI) in cement |
| JP4539719B2 (en) * | 2006-02-01 | 2010-09-08 | 株式会社村田製作所 | Manufacturing method of ceramic electronic component and Sn plating bath |
| EP1918426A1 (en) * | 2006-10-09 | 2008-05-07 | Enthone, Inc. | Cyanide free electrolyte composition und process for plating silver or alloys thereof on substrates |
| US20110206909A1 (en) * | 2008-10-31 | 2011-08-25 | Sundew Technologies Llc | Coatings for suppressing metallic whiskers |
| KR101881596B1 (en) | 2008-12-02 | 2018-07-24 | 웨이브 라이프 사이언시스 재팬 인코포레이티드 | Method for the synthesis of phosphorous atom modified nucleic acids |
| JP4435862B1 (en) | 2009-02-06 | 2010-03-24 | 謙治 出分 | Silver-containing alloy plating bath and electrolytic plating method using the same |
| IN2012DN00720A (en) | 2009-07-06 | 2015-06-19 | Ontorii Inc | |
| JP4531128B1 (en) * | 2009-07-31 | 2010-08-25 | 謙治 出分 | Tin-containing alloy plating bath, electrolytic plating method using the same, and substrate on which the electrolytic plating is deposited |
| DK2620428T3 (en) | 2010-09-24 | 2019-07-01 | Wave Life Sciences Ltd | Asymmetric help group |
| EP3248982A1 (en) | 2011-07-19 | 2017-11-29 | Wave Life Sciences Ltd. | Thiosulfonate reagents for the synthesis of functionalized nucleic acids |
| CN104684893B (en) | 2012-07-13 | 2016-10-26 | 日本波涛生命科学公司 | Asymmetric auxiliary group |
| WO2015084778A1 (en) | 2013-12-05 | 2015-06-11 | Honeywell International Inc. | Stannous methansulfonate solution with adjusted ph |
| US10160969B2 (en) | 2014-01-16 | 2018-12-25 | Wave Life Sciences Ltd. | Chiral design |
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| JP2016125130A (en) * | 2015-01-08 | 2016-07-11 | 株式会社デンソー | Composite material, method for forming composite material, electrode plated by composite material, and connection structure |
| CN104593835B (en) * | 2015-02-04 | 2017-10-24 | 广东羚光新材料股份有限公司 | The neutral tin plating electrolyte electroplated for chip components and parts termination electrode |
| US10312177B2 (en) | 2015-11-17 | 2019-06-04 | Honeywell International Inc. | Thermal interface materials including a coloring agent |
| CN105401177A (en) * | 2015-12-14 | 2016-03-16 | 广东美的暖通设备有限公司 | Anti-corrosion treatment method for heat exchanger, heat exchanger and air conditioner |
| CN109072051B (en) | 2016-03-08 | 2023-12-26 | 霍尼韦尔国际公司 | Phase change material |
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| KR20180024765A (en) * | 2016-08-31 | 2018-03-08 | 주식회사 호진플라텍 | Tin-bismuth-lead ternary alloy solder composition using electroplating |
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| CN108866583B (en) * | 2018-08-28 | 2020-07-21 | 广州三孚新材料科技股份有限公司 | Tin or tin-lead alloy plating solution applied to leadless electronic component, and preparation method and plating method thereof |
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| JP2709510B2 (en) * | 1989-05-17 | 1998-02-04 | 上村工業 株式会社 | Tin, lead, tin-lead alloy electroplating bath and electroplating method |
| US5085744A (en) * | 1990-11-06 | 1992-02-04 | Learonal, Inc. | Electroplated gold-copper-zinc alloys |
| US6773573B2 (en) * | 2001-10-02 | 2004-08-10 | Shipley Company, L.L.C. | Plating bath and method for depositing a metal layer on a substrate |
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| WO2003071001A1 (en) | 2003-08-28 |
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