TW201432089A - A method for plating a substrate with a metal - Google Patents

A method for plating a substrate with a metal Download PDF

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Publication number
TW201432089A
TW201432089A TW102148703A TW102148703A TW201432089A TW 201432089 A TW201432089 A TW 201432089A TW 102148703 A TW102148703 A TW 102148703A TW 102148703 A TW102148703 A TW 102148703A TW 201432089 A TW201432089 A TW 201432089A
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Taiwan
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autocatalytic
acid
plating
plating bath
substrate
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TW102148703A
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Chinese (zh)
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Anders Remgard
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Pk Plating Technology Ab
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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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1651—Two or more layers only obtained by electroless plating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/1601—Process or apparatus
    • C23C18/1633—Process of electroless plating
    • C23C18/1646—Characteristics of the product obtained
    • C23C18/165—Multilayered product
    • C23C18/1653—Two or more layers with at least one layer obtained by electroless plating and one layer obtained by electroplating
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/18—Pretreatment of the material to be coated
    • C23C18/1803—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces
    • C23C18/1824—Pretreatment of the material to be coated of metallic material surfaces or of a non-specific material surfaces by chemical pretreatment
    • C23C18/1837—Multistep pretreatment
    • C23C18/1844—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
    • C23C18/31—Coating with metals
    • C23C18/42—Coating with noble metals
    • 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
    • C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
    • C23C18/54—Contact plating, i.e. electroless electrochemical plating
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/12—Semiconductors
    • C25D7/123—Semiconductors first coated with a seed layer or a conductive layer

Abstract

The invention relates to a method for plating a substrate with a metal. The method comprises the steps of: mixing: a metal salt, a complexing agent, a surfactant, and an acid in water thereby forming a non-autocatalytic aqueous plating bath, and subjecting the substrate to the non-autocatalytic aqueous plating bath. The method may further include an additional plating step.

Description

以金屬鍍覆基材的方法 Method for plating a substrate with metal 技術領域 Technical field

本發明係有關於一種以水性鍍覆浴來鍍覆基材的方法。本發明亦有關於一種根據該方法來塗佈的物件以及一種以一金屬鍍覆一基材的水性鍍覆浴。 The present invention relates to a method of plating a substrate with an aqueous plating bath. The invention also relates to an article coated according to the method and an aqueous plating bath for plating a substrate with a metal.

發明背景 Background of the invention

已有許多用於鍍覆金屬於在基材上的習知技術。例如，電鍍、浸鍍以及自催化無電電鍍可以被使用。 There are many conventional techniques for plating metals onto substrates. For example, electroplating, immersion plating, and autocatalytic electroless plating can be used.

電鍍涉及一電解池的生成，其中鍍覆金屬代表一陽極，基材代表一陰極，且外部電荷被提供至該池中以促進該基材的塗佈。 Electroplating involves the formation of an electrolytic cell in which the plated metal represents an anode, the substrate represents a cathode, and external charges are supplied to the cell to facilitate coating of the substrate.

浸鍍(置換鍍覆)為自一包含塗佈金屬的溶液沉積一金屬塗佈於基底金屬上。一第一金屬離子被一第二金屬離子所取代，該第二金屬離子具有比該被取代的金屬離子更低的氧化電位。於浸鍍中，當該基底金屬作為還原劑時，一還原劑並不被需要以還原該金屬離子成金屬。由浸鍍所獲得的沉積物的厚度是有限的，因為當該基底金屬的整個表面都被塗佈時，沉積會停止。 Immersion plating (displacement plating) is the deposition of a metal from a solution comprising a coating metal onto a base metal. A first metal ion is replaced by a second metal ion having a lower oxidation potential than the substituted metal ion. In immersion plating, when the base metal acts as a reducing agent, a reducing agent is not required to reduce the metal ions to form a metal. The thickness of the deposit obtained by immersion plating is limited because the deposition stops when the entire surface of the base metal is coated.

自催化無電電鍍指的是鍍覆至一基底基材上之 金屬離子的自催化或化學還原。該製程和浸鍍的不同之處在於金屬的沉積為自催化或連續的。自催化無電電鍍比電鍍更吸引人的益處在於，於具有一不規則形狀的基材上鍍覆一實質上均勻的金屬塗佈的能力。無電塗佈也幾乎是無孔的，其比電鍍的基材能夠允許更強的耐銹蝕性。一般而言，無電電鍍浴包含金屬鹽類、錯合劑、還原劑以及用於增加亮度、穩定性以及沉積速率的不同添加劑。 Autocatalytic electroless plating refers to plating onto a substrate. Autocatalytic or chemical reduction of metal ions. The process differs from immersion in that the deposition of the metal is autocatalytic or continuous. A more attractive benefit of autocatalytic electroless plating than electroplating is the ability to plate a substantially uniform metal coating on a substrate having an irregular shape. Electroless coating is also almost non-porous, which allows for greater rust resistance than electroplated substrates. In general, electroless plating baths contain metal salts, complexing agents, reducing agents, and different additives for increasing brightness, stability, and deposition rate.

典型的自催化無電電鍍之應用為於微波組件上 的導電及環境保護層、於印刷電路板(PCB)及晶圓上的可焊接以及可鍵結的表面、太陽能電池的鍍覆層、催化劑床、以及用於多晶圓堆疊中之多層三維矽架構的相互連接件。於這些應用中之組件的材料和表面包含鎳、矽、銅和銅合金。 Typical autocatalytic electroless plating applications for microwave components Conductive and environmental protection layers, solderable and bondable surfaces on printed circuit boards (PCBs) and wafers, solar cell plating, catalyst beds, and multilayer 3D germanium for multi-wafer stacking The interconnected parts of the architecture. The materials and surfaces of the components in these applications contain nickel, ruthenium, copper and copper alloys.

鍍覆鎳的表面非常容易是被動的，因此一活化 作用係經常被用於銀鍍覆之前。該活化作用係使用電鍍或非電鍍方法而被進行。就電鍍而言，同時活化/觸擊鎳(nickel strike)的流程(被稱為伍茲鎳觸擊(Wood′s nickel strike))經常被使用。這是一種使用包含氯化鎳和鹽酸之溶液的電鍍製程。就非電鍍製程而言，直接自催化銀鍍覆可能被使用在新鮮沉積之無電鎳表面上或被使用在於稀釋酸中處理過的表面上。然而，該製程起初是非常緩慢而且不平坦的，其時常在銀層中導致一不良覆蓋、不良的黏著以及厚度不同的鍍覆。為了克服這個缺點，一金或鈀的中間 層可能使用浸泡種類或自催化種類的製程而形成於該基材表面上。然而，對於有著複雜幾何(例如在孔洞中的狹小的角落)的表面而言，要得到金或鈀的良好覆蓋是困難的。此外，該金或鈀層對於隨後的自催化銀鍍覆過程中之濃縮的氣體流是敏感的，亦即，該層可以被蝕刻掉。 Nickel-plated surfaces are very easy to passive, so an activation The action system is often used before silver plating. This activation is carried out using an electroplating or electroless plating method. In the case of electroplating, a process of simultaneously activating/strikeing a nickel strike (known as Wood's nickel strike) is often used. This is an electroplating process using a solution containing nickel chloride and hydrochloric acid. For non-electroplating processes, direct autocatalytic silver plating may be used on freshly deposited electroless nickel surfaces or on surfaces treated with dilute acid. However, the process was initially very slow and uneven, which often resulted in poor coverage, poor adhesion, and plating of varying thicknesses in the silver layer. In order to overcome this shortcoming, the middle of a gold or palladium The layer may be formed on the surface of the substrate using a process of soaking species or autocatalytic species. However, for surfaces with complex geometries such as narrow corners in the holes, it is difficult to obtain good coverage of gold or palladium. Furthermore, the gold or palladium layer is sensitive to the concentrated gas flow during subsequent autocatalytic silver plating, i.e., the layer can be etched away.

對於在矽太陽能電池上的直接鍍覆而言，一無電鎳的種子層經常被使用。為了減低導電手指與射極之間的接觸電阻，其可能將鎳替換為銀。銀為最佳的導電材料，但是為了更有競爭性，對於矽和銀之間的良好黏著力有一需求。如果表面是乾淨的且去氧化的，銅及銅合金可以使用自催化無電電鍍來直接鍍覆銀。然而在狹小的角落中、孔洞中及/或在粗糙的表面上，在該自催化無電電鍍的出氣過程中可能導致不滿意的覆蓋性。例如，這種不滿意的覆蓋性可能在撓性導波管的波紋的自催化銀鍍覆過程中被觀察到。 For direct plating on tantalum solar cells, an electroless nickel seed layer is often used. In order to reduce the contact resistance between the conductive finger and the emitter, it is possible to replace nickel with silver. Silver is the best conductive material, but in order to be more competitive, there is a need for good adhesion between tantalum and silver. If the surface is clean and deoxidized, copper and copper alloys can be directly plated with silver using autocatalytic electroless plating. However, in narrow corners, in holes and/or on rough surfaces, unsatisfactory coverage may result in the outgassing of the autocatalytic electroless plating. For example, such unsatisfactory coverage may be observed during the autocatalytic silver plating of the corrugations of the flexible waveguide.

因此，對於一種允許在基材上的金屬改良沉積的方法存在一需求。 Therefore, there is a need for a method that allows for improved deposition of metals on a substrate.

本發明係有關於一種以金屬鍍覆一基材的方法，該方法包含下列步驟：混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中藉此提供一非自催化水性鍍覆浴；以及以該非自催化水性鍍覆浴處理該基材。本發明更有關於一種根據該方法所塗佈的物件。本發明更有關於一種用於以金屬鍍覆基材的非自催化水性鍍覆浴，該非自 催化水性鍍覆浴可藉由混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中而被獲得。 The present invention relates to a method for plating a substrate with a metal, the method comprising the steps of: mixing a metal salt, a binder, a surfactant, and an acid in water to provide a non-autocatalytic aqueous plating. a bath; and treating the substrate with the non-autocatalytic aqueous plating bath. The invention further relates to an article coated in accordance with the method. The invention further relates to a non-autocatalytic aqueous plating bath for coating a substrate with a metal, the non-self The catalytic aqueous plating bath can be obtained by mixing a metal salt, a binder, a surfactant, and an acid in water.

詳細說明 Detailed description

本發明的一目的是為了克服或至少減輕與現有技術相關聯的一些缺點。 It is an object of the present invention to overcome or at least alleviate some of the disadvantages associated with the prior art.

上述提及的目的由一種以金屬鍍覆一基材的方法而被達成。該方法包含步驟：混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中，藉此提供一非自催化水性鍍覆浴；以及以該非自催化水性鍍覆浴處理該基材。 The above mentioned object is achieved by a method of plating a substrate with a metal. The method comprises the steps of: mixing a metal salt, a binder, a surfactant, and an acid in water to provide a non-autocatalytic aqueous plating bath; and treating the substrate with the non-autocatalytic aqueous plating bath .

該基材可能藉由浸泡於該水性鍍覆浴於一段想要長度的時間中，例如從三十秒到十分鐘、從三十秒到一分鐘或者從四到六分鐘而被該水性鍍覆浴處理。 The substrate may be plated by the aqueous plating bath for a desired length of time, such as from thirty seconds to ten minutes, from thirty seconds to one minute, or from four to six minutes. Bath treatment.

驚訝地發現於此所描述的方法導致在有簡單幾何的基材上以及有複雜幾何(有高度特定的表面區域，例如狹小的角落、孔洞、或者在總體而言不規則的表面上)的基材上之優異的鍍覆。有具有高度特定表面區域的幾何也可以被鍍覆的這個事實在該塗佈的表面也容易被觀察到，該塗佈的表面擁有一個更加強烈的白色，其被相信是由於在這些區域內該金屬核，例如銀核的存在，該金屬核是在一個額外的鍍覆步驟，其可能為自催化銀鍍覆的初始 階段下存在。這和那些藉由使用金或鈀的中間層一般所能達成的事情是相衝突的，其隨後的自催化銀鍍覆永遠在這種區域中有一個比較慢的開始。在這種區域之中的一個緩慢鍍覆的開始可能會不利於該基材的鍍覆。例如，當開始是緩慢的時候，該基材表面可能變得被動或者是一包含氰化物的自催化銀浴可能蝕刻掉此區域中之一層薄金層。這兩種狀況皆導致不良的覆蓋。 Surprisingly, it has been found that the methods described herein result in a basis on a substrate having a simple geometry and on a complex geometry (having a highly specific surface area, such as a narrow corner, a hole, or a generally irregular surface). Excellent plating on the material. The fact that a geometry with a highly specific surface area can also be plated is also easily observed on the coated surface, which has a more intense white color, which is believed to be due to the presence in these areas. The presence of a metal core, such as a silver core, in an additional plating step, which may be the initial of autocatalytic silver plating Exist in the stage. This is in conflict with what is generally achieved by the use of an intermediate layer of gold or palladium, and its subsequent autocatalytic silver plating always has a relatively slow start in this region. The beginning of a slow plating in such areas may be detrimental to the plating of the substrate. For example, when the start is slow, the surface of the substrate may become passive or an autocatalytic silver bath containing cyanide may etch away one of the thin gold layers in this area. Both of these conditions result in poor coverage.

該非自催化水性鍍覆浴可能由混合該金屬鹽、該 錯合劑、該界面活性劑以及該酸於水中而獲得。添加的酸的量允許其方便的調整該浴的pH值。在混合該浴的組成之後，接近的視覺檢視可能揭示如桿狀的簇團、如簇團的粒子及/或如核的粒子的生成。在該浴已被允許以持續一段時間之後或者在該鍍覆製程的過程之中，該簇團、如簇團的粒子及/或如核的粒子很容易被觀察到。據信該簇團、如簇團的粒子及/或如核的粒子包含金屬，例如銀。儘管不希望被任何特定的理論所限制，據信該簇團、像簇團的粒子和/或像如核的粒子對於該鍍覆的結果可能藉由黏著在基材的一部份(例如角落、孔洞或總體而言於粗糙表面的底部之中)上而有一個有益的影響。 The non-autocatalytic aqueous plating bath may be mixed with the metal salt, The complexing agent, the surfactant, and the acid are obtained in water. The amount of acid added allows it to conveniently adjust the pH of the bath. Upon mixing the composition of the bath, close visual inspection may reveal the formation of clusters such as rods, such as clusters of particles and/or particles such as nuclei. The clusters, such as clusters of particles and/or particles such as nuclei, are readily observed after the bath has been allowed to continue for a period of time or during the plating process. It is believed that the clusters, such as clustered particles and/or particles such as nuclei, comprise a metal, such as silver. Although not wishing to be bound by any particular theory, it is believed that the clusters, clusters of particles, and/or particles such as nuclei may adhere to a portion of the substrate (eg, corners) for the result of the plating. , holes or generally in the bottom of the rough surface) have a beneficial effect.

除了該浴的置換功能，其還有一催化的能力， 但非自催化，亦即，銀沉積可以發生在具有高度表面能量的純銀表面上，像是多孔的銀表面，然而該沉積層的最大厚度會小於0.2微米。其更據信在鍍覆的過程中，在該浴中之如桿狀的簇團的生長和尺寸減縮之間會達成一個平 衡。 In addition to the replacement function of the bath, it also has a catalytic ability. However, it is not autocatalytic, that is, silver deposition can occur on a surface of pure silver having a high surface energy, such as a porous silver surface, however the maximum thickness of the deposited layer is less than 0.2 microns. It is further believed that during the plating process, a flattening between the growth and size reduction of the rod-like clusters in the bath is achieved. Balance.

因此，於此還提供了一種用於鍍覆基材的方 法，其包含以下步驟：以一由混合一金屬鹽、一錯合劑、一界面活性劑以及一酸於水中而獲得的非自催化水性鍍覆浴處理該基材。 Therefore, a method for plating a substrate is also provided herein. The method comprises the steps of treating the substrate with a non-autocatalytic aqueous plating bath obtained by mixing a metal salt, a binder, a surfactant, and an acid in water.

在於此所揭示的方法中的非自催化水性鍍覆浴 可能被視為一用於處理該基材的預浸水性浴。在本文件中，「非自催化水性鍍覆浴」和「預浸水性浴」的表達方式被互換地使用。因為微孔、孔隙、孔洞或不規則物的完全或非常有限的的存在，因此該沉積的金屬層有著非常有限的表面粗糙度，因而促進該基材有關於，例如，附著性、反應性、印刷電路板的鍵結值以及金屬層厚度耐受值的性質。該提升的黏著性促進了額外層的鍍覆。一先前較為被動的表面(例如一鎳表面)之增加的反應性使得及/或促進了進一步的鍍覆。該提升的金屬厚度耐受值是有利的，因為已經發現，於此所揭示的方法允許在印刷電路板中生產相同的或者基本上相同的金屬層厚度，而不管襯墊尺寸。這和傳統的鍍覆方法相反，於傳統的一方法中，一小的襯墊與一厚的鍍覆金屬層相關聯，反之亦然。 Non-autocatalytic aqueous plating bath in the method disclosed herein It may be considered a pre-soaked bath for treating the substrate. In this document, the expressions of "non-autocatalytic water-based plating bath" and "pre-soaked water bath" are used interchangeably. Because of the complete or very limited presence of micropores, pores, pores or irregularities, the deposited metal layer has a very limited surface roughness, thereby promoting the substrate with respect to, for example, adhesion, reactivity, The bond value of the printed circuit board and the nature of the metal layer thickness tolerance. This increased adhesion promotes plating of additional layers. The increased reactivity of a previously more passive surface, such as a nickel surface, causes and/or promotes further plating. This elevated metal thickness tolerance is advantageous because it has been found that the methods disclosed herein allow for the production of the same or substantially the same metal layer thickness in a printed circuit board regardless of the pad size. This is in contrast to conventional plating methods in which a small liner is associated with a thick plated metal layer and vice versa.

於此所揭示的方法允許例如基材(例如基材表面) 的活化處理，係由沉積一金屬層於該基材上而進行，藉此促進該基材之進一步的鍍覆。該沉積的金屬可能有一障蔽功能。進一步來說，沉積於該基材上的金屬層(其可能為一銀層)提供優異的覆蓋且為均勻、非孔洞的，以及展現 出優異的電性質。該沉積的金屬層可能有一大約0.03至0.15微米的厚度。該方法可能被應用在不同的基材上，這樣的基材包含鎳、矽、錫、銅以及銅合金或由此等材料所構成。接著，另一金屬層可能藉由進行一額外的鍍覆步驟而被提供於該經處理的基材上，而導致一較厚的基材塗佈。 The methods disclosed herein allow, for example, a substrate (eg, a substrate surface) The activation treatment is carried out by depositing a metal layer on the substrate, thereby promoting further plating of the substrate. The deposited metal may have a barrier function. Further, the metal layer deposited on the substrate (which may be a silver layer) provides excellent coverage and is uniform, non-porous, and exhibits Excellent electrical properties. The deposited metal layer may have a thickness of between about 0.03 and 0.15 microns. The method may be applied to different substrates, such as nickel, tantalum, tin, copper, and copper alloys or materials thereof. Next, another metal layer may be provided on the treated substrate by performing an additional plating step, resulting in a thicker substrate coating.

於此所揭示的方法可能被視為一種用於處理一 基材表面的方法或者被視為一種用於密封一基材(例如一基材表面)的方法。因此，於此所揭示的方法可能被用於一基材的密封。特別是，於此所揭示的方法可能被用於一金屬基材的密封或是用於在基材之一金屬塗層的密封。該密封可能包括一基材或一基材之金屬塗層之孔、微孔或孔洞的密封。舉例言之，於一經鋅酸鹽處理的鋁基材上的一薄的孔洞銅層可能使用於此所揭示的方法被密封並且進一步以一更密的銅層鍍覆於該沉積之銀層的頂部上。這對鍍覆層提供了更好的環境阻力和更好的導電性。此外，在包含鋅之基材上的一銅層可能使用於此所揭示的方法而被密封。 The method disclosed herein may be considered as a method for processing one The method of the surface of the substrate is either considered as a method for sealing a substrate, such as a substrate surface. Thus, the methods disclosed herein may be used for the sealing of a substrate. In particular, the methods disclosed herein may be used for sealing a metal substrate or for sealing a metal coating on one of the substrates. The seal may include a seal of a hole, a micropore or a hole in a metal coating of a substrate or a substrate. For example, a thin porous copper layer on a zincate treated aluminum substrate may be sealed using the methods disclosed herein and further plated with a denser copper layer on the deposited silver layer. On the top. This provides better environmental resistance and better conductivity for the coating. Additionally, a layer of copper on the substrate comprising zinc may be sealed using the methods disclosed herein.

在以該非自催化水性鍍覆浴處理之前，該基材 可能藉由清洗或蝕刻而被準備。 The substrate before being treated with the non-autocatalytic aqueous plating bath It may be prepared by washing or etching.

當由使用該預浸水性浴而得的該沉積金屬層(雖 然非常薄)是幾乎非孔洞的時候，其提供一增進的障蔽功能。此提供了幾個重要的益處：增進的失去光澤的抗性；微孔的減少及/或消除；增加厚度的均勻性；降低整體金屬 厚度(例如銀的厚度)的可能性，或者降低一鍍覆塗層(例如銀塗層)的整體厚度的可能性。 When the deposited metal layer is obtained by using the prepreg aqueous bath (although It is very thin) when it is almost non-porous, it provides an enhanced barrier function. This provides several important benefits: enhanced tarnish resistance; reduction and/or elimination of micropores; increased thickness uniformity; reduced overall metal The possibility of a thickness, such as the thickness of silver, or the possibility of reducing the overall thickness of a plated coating, such as a silver coating.

眾所周知的是，如果CuO存在於該基材的表面 上，該銀鍍覆之銅基材係因暴露在濕度和H2S下而很容易會失去光澤。銅於銀中的溶解度低，因此銅至銀表面的遷移主要是沿著孔，其可能發現於晶粒界面處。這意味著，如果該銀層為非孔洞的，其雖然非常薄但仍可以作為一銅的遷移障礙。該預浸水性浴據推測是藉由在該銅表面上增加銀沉積層之成核速率以及側向生長而創造由一銀之密封層所覆蓋的表面。該遷移障礙因此提供一增進的失去光澤的抗性。 It is well known that if CuO is present on the surface of the substrate, the silver-plated copper substrate is liable to lose gloss due to exposure to humidity and H 2 S. The solubility of copper in silver is low, so the migration of copper to silver surfaces is primarily along the pores, which may be found at the grain boundaries. This means that if the silver layer is non-porous, it is very thin but still acts as a copper migration barrier. The prepreg bath is presumably to create a surface covered by a silver seal layer by increasing the nucleation rate of the silver deposit on the copper surface and lateral growth. This migration barrier thus provides an enhanced tarnish resistance.

來自於該預浸水性浴的金屬沉積層(例如一銀沉 積層)，也將作為一來自於相反方向的障礙，亦即，保護該Cu-Ag界面不受到源自於接續之自催化銀鍍覆的電池侵蝕，其降低在該自催化銀沉積下之微孔的生成。 a metal deposit from the prepreg bath (eg, a silver sink) The layering) will also act as an obstacle from the opposite direction, ie, protecting the Cu-Ag interface from battery erosion from successive autocatalytic silver plating, which reduces the micro-catalytic silver deposition The generation of holes.

於此所描述的方法從經濟上以及從環保上的觀 點來看是有利的，因為其允許減少整體的塗佈厚度，例如一銀塗層的厚度，其為該預浸水性浴的障蔽功能的結果。 例如，這應用於印刷電路板，以及微波組件。 The economic and environmental aspects of the method described here This is advantageous because it allows to reduce the overall coating thickness, such as the thickness of a silver coating, as a result of the barrier function of the prepreg bath. For example, this applies to printed circuit boards, as well as microwave components.

於此所描述的方法中之以非自催化水性鍍覆浴 處理的基材可能包含矽、鎳、錫、銅或銅合金或由此等材料所構成。 Non-autocatalytic aqueous plating bath in the method described herein The treated substrate may comprise tantalum, nickel, tin, copper or a copper alloy or a material such as this.

於此所描述之方法中的非自催化水性鍍覆浴中 的金屬鹽可能包含一種、二種、或者多種金屬鹽。該金屬 鹽可能為一銀鹽以及可能選自於AgNO3、AgCN、AgClO4、Ag2SO4、AgSO4、Ag2O、KAg(CN)2、NaAg(CN)2、Ag(C2H3O2)、丁二醯亞胺銀錯合物及其等之混合物所構成之組群中。 The metal salt in the non-autocatalytic aqueous plating bath in the process described herein may comprise one, two, or more metal salts. The metal salt may be a silver salt and may be selected from AgNO 3 , AgCN, AgClO 4 , Ag 2 SO 4 , AgSO 4 , Ag 2 O, KAg(CN) 2 , NaAg(CN) 2 , Ag(C 2 H a group consisting of 3 O 2 ), butyl quinone imine silver complex and mixtures thereof.

於此所描述之方法中的非自催化水性鍍覆浴的 錯合劑可能包含一種、兩種、或者更多種的錯合劑。該錯合劑可能選自於由EDTA、羅謝爾鹽(Rochelle′s salt)、檸檬酸、檸檬酸鈉、丁二酸、丙酸、乙醇酸、醋酸鈉、乳酸、焦磷酸鈉、3-吡啶磺酸、酒石酸鉀、乙二胺、磷酸鈉、檸檬酸鉀、硼酸鈉、氰化鈉、氰化鉀、三伸乙四胺、甲胺及其等之混合物所構成的組群中。 Non-autocatalytic aqueous plating bath in the method described herein The miscible agent may contain one, two, or more of a combination agent. The complexing agent may be selected from the group consisting of EDTA, Rochelle's salt, citric acid, sodium citrate, succinic acid, propionic acid, glycolic acid, sodium acetate, lactic acid, sodium pyrophosphate, 3-pyridine A group consisting of a mixture of sulfonic acid, potassium tartrate, ethylenediamine, sodium phosphate, potassium citrate, sodium borate, sodium cyanide, potassium cyanide, triethylenetetramine, methylamine, and the like.

部份錯合劑也可能有一些還原能力。這樣的弱 還原劑並沒有能力去提供於此所揭示的自催化無電電鍍製程，也不落於於此所使用的「還原劑」之詞的意義中。因此，一弱還原劑的存在不足以使得一水性鍍覆浴以一自催化的方式運作。藉由監測該鍍覆製程可以很容易地確定該還原劑是一種弱還原劑還是強還原劑。如果該鍍覆製程自行停止，則該還原劑是一種弱還原劑。然而，如果該鍍覆製程是自發生(self-propagating)及連續，則該還原劑是一種強還原劑。總體而言，一強的還原劑會導致該基材上的一厚且均勻的金屬層之生成。 Some of the wrong agents may also have some reducing power. Such weak The reducing agent does not have the ability to provide the autocatalytic electroless plating process disclosed herein, nor does it fall within the meaning of the term "reducing agent" as used herein. Therefore, the presence of a weak reducing agent is not sufficient to operate an aqueous plating bath in an autocatalytic manner. By monitoring the plating process, it can be readily determined whether the reducing agent is a weak reducing agent or a strong reducing agent. If the plating process is stopped by itself, the reducing agent is a weak reducing agent. However, if the plating process is self-propagating and continuous, the reducing agent is a strong reducing agent. In general, a strong reducing agent results in the formation of a thick and uniform metal layer on the substrate.

應該會被理解的是，部份錯合劑也可能作為弱 還原劑。因此，於此所揭示的該錯合劑包括非還原劑的錯合劑以及具有一低還原能力的錯合劑。可能於一自催化鍍 覆製程中作為還原劑的錯合劑並不包含在本發明的範圍內。 It should be understood that some of the wrong agents may also be weak reducing agent. Thus, the intercalating agents disclosed herein include a non-reducing agent miscending agent and a complexing agent having a low reducing ability. Possible autocatalytic plating A compounding agent as a reducing agent in the coating process is not included in the scope of the present invention.

於此所描述的方法中之水性鍍覆浴之酸可能包 含一種、兩種或者多種酸。該酸可能為一羧酸，例如，檸檬酸。在該錯合劑為一種酸的情況下，其可能和該錯合劑是相同或者不同。 The acidity of the aqueous plating bath in the method described herein may include Contains one, two or more acids. The acid may be a monocarboxylic acid such as citric acid. In the case where the binder is an acid, it may be the same or different from the binder.

於此所描述之方法中之非自催化水性鍍覆浴的 界面活性劑可能為一非離子界面活性劑。例如，該界面活性劑可能為壬基酚草酸酯。 Non-autocatalytic aqueous plating baths in the methods described herein The surfactant may be a nonionic surfactant. For example, the surfactant may be nonylphenol oxalate.

於此所描述之方法中之非自催化水性鍍覆浴可 能進一步包含一以氧化乙烯(亦即，一聚烯烴氧化物)為基礎的聚合物，如聚乙二醇(PEG)。該聚合物可能具有一範圍從100到4000的平均分子量。 The non-autocatalytic aqueous plating bath in the method described herein may It can further comprise a polymer based on ethylene oxide (i.e., a polyolefin oxide), such as polyethylene glycol (PEG). The polymer may have an average molecular weight ranging from 100 to 4000.

於此所描述之方法中之非自催化水性鍍覆浴可 能進一步包含硼酸。 The non-autocatalytic aqueous plating bath in the method described herein may It can further contain boric acid.

於此所描述之方法中之非自催化水性鍍覆浴可能操作在15℃至95℃的溫度下，例如操作在15至65℃。 The non-autocatalytic aqueous plating bath in the process described herein may be operated at a temperature of from 15 ° C to 95 ° C, for example at 15 to 65 ° C.

於此所描述之方法中之水性覆鍍浴的pH值可能介於4到12之間，例如介於5到8之間。可以被理解的是“介於4到12之間，例如介於5到8之間”相當於被理解成“從4至12，例如從5至8”。進一步來說，該pH值的範圍可能從5至10、從8至10、或從9至10。該pH值也可能為大約9.5。較佳的pH值(特別是對銀鍍覆)包括從8至10、從9到10、大約6以及大約9.5的數值。 The pH of the aqueous plating bath in the methods described herein may range from 4 to 12, such as between 5 and 8. It can be understood that "between 4 and 12, for example between 5 and 8" is equivalent to being understood as "from 4 to 12, for example from 5 to 8". Further, the pH may range from 5 to 10, from 8 to 10, or from 9 to 10. This pH may also be about 9.5. Preferred pH values (especially for silver plating) include values from 8 to 10, from 9 to 10, about 6 and about 9.5.

於此所描述的方法可能用來提供於一基材上形 成一金屬沉積層、一金屬層或一金屬薄膜。 The method described herein may be used to provide a shape on a substrate Formed as a metal deposit, a metal layer or a metal film.

於此所描述的方法可能進一步包含一額外的鍍 覆步驟。該額外的鍍覆步驟可能為自催化無電電鍍、浸鍍或電鍍。該額外的鍍覆步驟直接進行於於此所描述的將該基材以預浸水性浴處理的步驟之後，或者直接進行於隨後的沖洗之後。該額外的鍍覆步驟(例如自催化無電電鍍)可能涉及銀的鍍覆。 The method described herein may further comprise an additional plating Overlay steps. This additional plating step may be autocatalytic electroless plating, immersion plating or electroplating. This additional plating step is carried out directly after the step of treating the substrate with a pre-soaked aqueous bath as described herein, or directly after subsequent rinsing. This additional plating step, such as autocatalytic electroless plating, may involve silver plating.

由於於此所描述的方法中之以非自催化水性鍍 覆浴處理之基材的基材表面粗糙度是非常有限或者是不存在的，因此有助於隨後的額外的鍍覆步驟。例如，該增進的基材反應性(其也可能稱為基材活化)導致了更快的總體製程。此外，該改良的基材附著性允許用於製造比其他者更薄的一金屬層。例如，可能利用於此所描述的方法而很容易地形成具有從0.03至0.15微米厚度的一銀層。這和由電流的方法所產生的厚層是相對的，其中該層的厚度一般為好幾微米。因此，於此所描述的方法從經濟上以及從環境上的觀點來看都是有利的。此外，當該自催化反應將於金屬鍍覆的基材上同時開始時，在額外的鍍覆步驟(例如自催化金屬鍍覆)之前使用於此所描述的預浸水性浴係提供該所得之總金屬厚度的增加的均勻性。 Non-autocatalytic aqueous plating due to the method described herein The surface roughness of the substrate of the bath-treated substrate is very limited or non-existent, thus contributing to the subsequent additional plating steps. For example, this enhanced substrate reactivity (which may also be referred to as substrate activation) results in a faster overall process. In addition, the improved substrate adhesion allows for the fabrication of a thinner metal layer than others. For example, a layer of silver having a thickness from 0.03 to 0.15 microns can be readily formed using the methods described herein. This is in contrast to thick layers produced by current methods, where the thickness of the layer is typically several microns. Therefore, the methods described herein are advantageous from an economic and environmental standpoint. In addition, when the autocatalytic reaction begins simultaneously on a metallized substrate, the pre-impregnated aqueous bath system described herein is used prior to an additional plating step (eg, autocatalytic metal plating) to provide the resulting Increased uniformity of total metal thickness.

因此，於此提供一種以金屬鍍覆一基材的方 法，包含下列步驟：混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中藉此形成一非自催化水性鍍覆浴； 以該非自催化水性鍍覆處理該基材中；隨後進行自催化無電電鍍。 Therefore, there is provided a method of plating a substrate with a metal. The method comprises the steps of: mixing a metal salt, a binder, a surfactant, and an acid in water to form a non-autocatalytic aqueous plating bath; The substrate is treated with the non-autocatalytic aqueous plating; followed by autocatalytic electroless plating.

於此也提供一種以金屬鍍覆一基材的方法，包 含下列步驟：以一非自催化水性鍍覆浴處理該基材，該非自催化水性鍍覆浴係藉由混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中而獲得，隨後進行自催化無電電鍍而被獲得。 There is also provided a method of plating a substrate with a metal, the package The method comprises the steps of: treating the substrate with a non-autocatalytic aqueous plating bath obtained by mixing a metal salt, a compounding agent, a surfactant, and an acid in water. Subsequent autocatalytic electroless plating is obtained.

該自催化無電電鍍可能涉及銀鍍覆。 The autocatalytic electroless plating may involve silver plating.

該自催化無電電鍍可能使用一鍍覆浴而進行，該 鍍覆浴***作以使得在該浴中存在至少兩相。此被揭示於WO 2006/065221。 The autocatalytic electroless plating may be performed using a plating bath, which The plating bath is operated such that at least two phases are present in the bath. This is disclosed in WO 2006/065221.

於此也提供一種以金屬鍍覆一基材的方法，包 含下列步驟：混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中，藉此形成一非自催化水性鍍覆浴；以該非自催化水性鍍覆浴處理該基材；隨後進行浸鍍。 There is also provided a method of plating a substrate with a metal, the package The method comprises the steps of: mixing a metal salt, a binder, a surfactant, and an acid in water to form a non-autocatalytic aqueous plating bath; treating the substrate with the non-autocatalytic aqueous plating bath; Dip plating.

於此也提供一種用於鍍覆一基材的方法，包含 下列步驟：以該非自催化水性鍍覆浴處理該基材，該非自催化水性鍍覆浴係藉由混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中而獲得，隨後進行浸鍍。 There is also provided a method for plating a substrate, comprising The following step: treating the substrate with the non-autocatalytic aqueous plating bath obtained by mixing a metal salt, a binder, a surfactant, and an acid in water, followed by Dip plating.

該浸鍍可能涉及金鍍覆。 This immersion plating may involve gold plating.

於此也提供一種以金屬鍍覆一基材的方法，包 含下列步驟：混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中藉此形成一非自催化水性鍍覆浴；以該非自催化水性鍍覆浴處理該基材；隨後進行電鍍。 There is also provided a method of plating a substrate with a metal, the package The method comprises the steps of: mixing a metal salt, a binder, a surfactant, and an acid in water to form a non-autocatalytic aqueous plating bath; treating the substrate with the non-autocatalytic aqueous plating bath; plating.

於此也提供一種以金屬鍍覆一基材的方法，包 含下列步驟：以該非自催化水性鍍覆浴處理該基材，該非自催化水性鍍覆浴係藉由混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中而被獲得，隨後進行電鍍。 There is also provided a method of plating a substrate with a metal, the package The method comprises the steps of: treating the substrate with the non-autocatalytic aqueous plating bath obtained by mixing a metal salt, a binder, a surfactant, and an acid in water, Electroplating is then carried out.

已經被發現的是，含有錫的基材可使用於此所 描述的方法而方便地被電鍍。該含有錫的基材可能隨後被放置在非自催化水性鍍覆浴中，隨後接著使用電極在同一鍍覆浴中進行電鍍。 It has been found that substrates containing tin can be used here. The method described is conveniently electroplated. The tin-containing substrate may then be placed in a non-autocatalytic aqueous plating bath followed by electroplating in the same plating bath using electrodes.

令人驚訝地發現的是，從該預浸水性浴中得到 的沉澱物之如桿狀的簇團、如簇團的粒子或如核的粒子也影響隨後在整個鍍覆製程中的鍍覆步驟，例如自催化鍍覆。這種現象可以被觀察到，並稱為該製程的“自我治愈”的能力，因為不僅在初始階段且在整個鍍覆製程中，它具有覆蓋缺陷以及以黏著的銀填充缺陷的能力。此對於抑制例如，在印刷電路板應用中的銅-銀界面的微孔的形成上以及對於覆蓋困難的幾何(其對於部份基材(例如無電鍍鎳的組件)而言，金屬離子的接近是困難)而言是重要的。在矽上，來自銀預浸浴中的該簇團的粒子及/或核粒子可能隨後額外地被自催化銀鍍覆以及被熱處理，以燒結並形成具有優異的附著性以及低接觸電阻的銀矽化物。一個典型的應用就是以矽為基底之太陽能電池的鍍覆。因此，根據於此所描述的方法，以一水性鍍覆浴處理一基材也會對於基材所遭受的額外的鍍覆步驟有一有益的影響。 Surprisingly found that it is obtained from the prepreg bath The precipitates such as rod-like clusters, such as clustered particles or particles such as nuclei, also affect subsequent plating steps throughout the plating process, such as autocatalytic plating. This phenomenon can be observed and is referred to as the "self-healing" capability of the process because it has the ability to cover defects and fill defects with adhered silver not only in the initial stage but throughout the plating process. This is for the prevention of, for example, the formation of micropores in the copper-silver interface in printed circuit board applications and for the geometry of difficult coverage (for parts of substrates such as electroless nickel-plated components), the proximity of metal ions It is difficult) it is important. On the crucible, the particles and/or core particles from the cluster in the silver pre-dip bath may then be additionally autocatalyzed by silver plating and heat treated to sinter and form silver with excellent adhesion and low contact resistance. Telluride. A typical application is the plating of solar cells based on germanium. Thus, in accordance with the methods described herein, treating a substrate with an aqueous plating bath can also have a beneficial effect on the additional plating steps experienced by the substrate.

於此所描述的方法可能進一步包含一熱處理步 驟。 The method described herein may further comprise a heat treatment step Step.

因為金屬層(特別是銀層)很容易失去光澤，建 議在該金屬層上加上一抗失去光澤層。提供這種抗失去光澤層的組成是本領域已知的技術。例如，可使用EVABRITETM WST。因此，於此所描述的方法可能包含添加一抗失去光澤層或薄膜於此方法中所形成的金屬層上的步驟。 Since the metal layer (especially the silver layer) is easily tarnished, it is recommended to add a tarnish layer to the metal layer. Providing such an anti-tarnish layer composition is a technique known in the art. For example, a EVABRITE TM WST. Thus, the methods described herein may involve the addition of a primary anti-glare layer or film to the metal layer formed in the process.

於此還提供了根據於此所描述的方法塗佈的一 物件。例如，該物件可能為微波組件、印刷電路板、醫療裝置(例如用於心電圖的電極)、天線(例如用於行動電話的天線)、太陽能電池、催化床或者晶圓。該物件可能包含矽、鎳、錫、銅或一銅合金或由此等組份所構成。於此還提供了根據於此所述的方法所形成的一銀矽化物。 Also provided herein is a coating applied in accordance with the methods described herein. object. For example, the item may be a microwave component, a printed circuit board, a medical device (eg, an electrode for an electrocardiogram), an antenna (eg, an antenna for a mobile phone), a solar cell, a catalytic bed, or a wafer. The article may comprise tantalum, nickel, tin, copper or a copper alloy or a component thereof. Also provided herein is a silver halide formed according to the methods described herein.

於此還提供了一非自催化水性鍍覆浴。該非自 催化水性鍍覆浴可能藉由混合一金屬鹽、一錯合劑、一界面活性劑、和一酸於水中而被製備。 A non-autocatalytic aqueous plating bath is also provided herein. The non-self The catalytic aqueous plating bath may be prepared by mixing a metal salt, a binder, a surfactant, and an acid in water.

該非自催化水性鍍覆浴藉由混合一金屬鹽、一 錯合劑、一界面活性劑、和一酸於水中而可得到。 The non-autocatalytic aqueous plating bath is prepared by mixing a metal salt A miscible agent, a surfactant, and an acid are available in water.

如於此所描述的，該非自催化水性鍍覆浴的接近 的視覺檢視可能看出如桿狀的簇團、如簇團的粒子及/或如核的粒子的存在。 As described herein, the proximity of the non-autocatalytic aqueous plating bath Visual inspection may reveal the presence of clusters of rods, such as clusters of particles and/or particles such as nuclei.

該非自催化水性鍍覆浴的金屬鹽可能包含一 種、兩種、或者多種的金屬鹽。該金屬鹽可能為一銀鹽，其選自於AgNO3、AgCN、AgClO4、Ag2SO4、AgSO4、Ag2O、 KAg(CN)2、NaAg(CN)2、Ag(C2H3O2)、及丁二醯亞胺銀錯合物。 The metal salt of the non-autocatalytic aqueous plating bath may contain one, two, or more metal salts. The metal salt may be a silver salt selected from the group consisting of AgNO 3 , AgCN, AgClO 4 , Ag 2 SO 4 , AgSO 4 , Ag 2 O, KAg(CN) 2 , NaAg(CN) 2 , Ag (C 2 H 3 O 2 ), and butyl quinone imine silver complex.

該水性鍍覆浴中的錯合劑可能包含一種、兩種、或者多種的錯合劑。該錯合劑可能選自於EDTA、羅謝爾鹽(Rochelle′s salt)、檸檬酸、檸檬酸鈉、丁二酸、丙酸、乙醇酸、醋酸鈉、乳酸、焦磷酸鈉、3-吡啶磺酸、酒石酸鉀、乙二胺、磷酸鈉、檸檬酸鉀、硼酸鈉、氰化鈉、氰化鉀、三伸乙四胺、及甲胺。 The complexing agent in the aqueous plating bath may contain one, two, or more of a combination agent. The complexing agent may be selected from the group consisting of EDTA, Rochelle's salt, citric acid, sodium citrate, succinic acid, propionic acid, glycolic acid, sodium acetate, lactic acid, sodium pyrophosphate, 3-pyridinium Acid, potassium tartrate, ethylenediamine, sodium phosphate, potassium citrate, sodium borate, sodium cyanide, potassium cyanide, triamethylenetetramine, and methylamine.

該錯合劑可能是如於此所述的錯合劑。 The miscible agent may be a complexing agent as described herein.

該非自催化水性鍍覆浴中的界面活性劑可能包含一種、兩種、或者多種的界面活性劑。該界面活性劑可能為一非離子界面活性劑。例如，該界面活性劑可能為壬基酚草酸酯。 The surfactant in the non-autocatalytic aqueous plating bath may comprise one, two, or more surfactants. The surfactant may be a nonionic surfactant. For example, the surfactant may be nonylphenol oxalate.

該非自催化水性鍍覆浴可能進一步包含一以氧化乙烯(亦即，一聚烯烴氧化物)為基礎的聚合物，如聚乙二醇(PEG)。該聚合物可能具有一範圍從100到4000的平均分子量。 The non-autocatalytic aqueous plating bath may further comprise a polymer based on ethylene oxide (i.e., a polyolefin oxide), such as polyethylene glycol (PEG). The polymer may have an average molecular weight ranging from 100 to 4000.

該非自催化水性鍍覆浴可能進一步包含硼酸。 The non-autocatalytic aqueous plating bath may further comprise boric acid.

該非自催化水性鍍覆浴可能在15℃至95℃的溫度下操作，例如在15至65℃操作。 The non-autocatalytic aqueous plating bath may be operated at a temperature of from 15 ° C to 95 ° C, for example at 15 to 65 ° C.

該非自催化水性覆鍍浴的pH值可能介於4到12之間，例如介於5到8之間。可以被理解的是”介於4到12之間，例如介於5到8之間”相當於被理解成”從4至12，例如從5至8”。進一步來說，該pH值的範圍可能從5至10、從8至 10、或從9至10。該pH值也可能為大約9.5。較佳的pH值(特別是對銀鍍覆)包括從8至10、從9到10、大約6以及大約9.5的數值。 The pH of the non-autocatalytic aqueous plating bath may be between 4 and 12, such as between 5 and 8. It can be understood that "between 4 and 12, for example between 5 and 8" is equivalent to being understood as "from 4 to 12, for example from 5 to 8". Further, the pH may range from 5 to 10, from 8 to 10, or from 9 to 10. This pH may also be about 9.5. Preferred pH values (especially for silver plating) include values from 8 to 10, from 9 to 10, about 6 and about 9.5.

該非自催化水性鍍覆浴的酸可能包含一種、兩種 或者多種的酸。該酸可能為一羧酸，例如，檸檬酸。在該錯合劑為一種酸的情況下，該酸可能和該錯合劑是相同或者不同。 The acid of the non-autocatalytic aqueous plating bath may contain one kind or two kinds Or a variety of acids. The acid may be a monocarboxylic acid such as citric acid. In the case where the complexing agent is an acid, the acid may be the same or different from the complexing agent.

其他的態樣 Other aspects

於此提供一種用於使用水性鍍覆浴以一金屬鍍覆一基材的非自催化方法，該浴包含至少一金屬、至少一錯合劑、至少一酸、以及至少一界面活性劑，其中至少部分金屬是以簇團的形式存在。 There is provided a non-autocatalytic method for plating a substrate with a metal using an aqueous plating bath, the bath comprising at least one metal, at least one binder, at least one acid, and at least one surfactant, wherein at least Some of the metals are in the form of clusters.

於此也提供一種非自催化水性鍍覆浴，該浴包含至少一金屬鹽、至少一錯合劑、至少一酸、以及至少一界面活性劑，其中至少部分金屬鹽是以簇團的形式存在。該水性浴可能進一步包含至少一聚烯烴基氧化物。該水性鍍覆浴可能當作一預浸水性浴而被使用，意思是該浴在一額外的鍍覆步驟中之添加一額外的金屬層之前係被使用以提供一第一塗佈或金屬層。因此該預浸水性浴在該額外的鍍覆步驟之前活化該基材的表面。該預浸浴包含金屬簇團的核，例如銀簇團，其具有吸附至該基材的能力以及用於為一額外的鍍覆步驟(例如自催化銀鍍覆)提供一活化表面的能力。依據基底基材的種類，該預浸浴可以將簇團吸附與置換反應結合。 Also provided herein is a non-autocatalytic aqueous plating bath comprising at least one metal salt, at least one binder, at least one acid, and at least one surfactant, wherein at least a portion of the metal salt is in the form of clusters. The aqueous bath may further comprise at least one polyolefin-based oxide. The aqueous plating bath may be used as a prepreg bath, meaning that the bath is used to provide a first coating or metal layer prior to the addition of an additional metal layer in an additional plating step. . The prepreg bath therefore activates the surface of the substrate prior to the additional plating step. The prepreg bath contains cores of metal clusters, such as silver clusters, which have the ability to adsorb to the substrate and the ability to provide an activation surface for an additional plating step, such as autocatalytic silver plating. The prepreg bath can combine cluster adsorption with a displacement reaction depending on the type of base substrate.

該簇團或簇團粒子可能有一大約或者小於100奈 米的尺寸。 The cluster or cluster particles may have about one or less than 100 nanometers The size of the meter.

進一步來說，於此提供一非自催化水性鍍覆浴， 該浴包含至少一金屬鹽、至少一錯合劑、至少一酸、以及至少一界面活性劑，其中至少部分金屬鹽是以簇團的形式存在。該水性浴可能進一步包含至少一聚烯烴基氧化物。 該水性鍍覆浴可能當作一預浸水性浴而被使用，意思是該浴在一額外的鍍覆步驟中之添加一額外的金屬層之前係被使用以提供一第一塗佈或金屬層。因此該預浸水性浴在該額外的鍍覆步驟之前活化該基材的表面。該預浸浴包含金屬簇團的核，例如銀簇團，其具有吸附至該基材的能力以及用於為一額外的鍍覆步驟(例如自催化銀鍍覆)提供一活化表面的能力。依據基底基材的種類，該預浸浴可以將簇團吸附與置換反應結合。 Further, a non-autocatalytic aqueous plating bath is provided herein, The bath comprises at least one metal salt, at least one binder, at least one acid, and at least one surfactant, wherein at least a portion of the metal salt is in the form of clusters. The aqueous bath may further comprise at least one polyolefin-based oxide. The aqueous plating bath may be used as a prepreg bath, meaning that the bath is used to provide a first coating or metal layer prior to the addition of an additional metal layer in an additional plating step. . The prepreg bath therefore activates the surface of the substrate prior to the additional plating step. The prepreg bath contains cores of metal clusters, such as silver clusters, which have the ability to adsorb to the substrate and the ability to provide an activation surface for an additional plating step, such as autocatalytic silver plating. The prepreg bath can combine cluster adsorption with a displacement reaction depending on the type of base substrate.

本發明由以下的實施例加以說明，但並不受限 於以下的實施例。 The invention is illustrated by the following examples, but is not limited In the following examples.

實施例Example

一銀預浸浴是由銀氰化物和氰化鈉所組成，而得到一3克/升的銀含量。0.1克/升壬基酚草酸酯。0.2克/升PEG。pH值藉由一羧酸的添加而被調整至9。使用該銀預浸的例子如下所示： A silver pre-dip bath consists of silver cyanide and sodium cyanide to give a silver content of 3 g/l. 0.1 g / liter of nonylphenol oxalate. 0.2 g / liter of PEG. The pH was adjusted to 9 by the addition of a monocarboxylic acid. An example of using this silver prepreg is as follows:

1.一鈹銅製得之有彈性的波導管被如下的方式鍍銀：酸性清洗劑，(Ronaclean PC 960)，40℃，5分鐘；清洗；微蝕，(Circuposit Etch 3330)，25℃，3分鐘；清洗； 銀預浸，(活化及障蔽功能)，室溫，20分鐘，pH值6.0；清洗；自催化銀，(ESM(無電銀混合)200，PK鍍覆)，63℃，30分鐘；清洗。在顯微鏡40倍放大率下的檢驗下驗證該覆蓋性非常好。該波導管在260℃於烘箱中加熱1小時後以檢查附著性，附著性非常好。 1. A flexible waveguide made of copper is silver plated as follows: Acid cleaner, (Ronaclean PC 960), 40 ° C, 5 minutes; cleaning; microetching, (Circuposit Etch 3330), 25 ° C, 3 Minute; cleaning; Silver prepreg, (activation and barrier function), room temperature, 20 minutes, pH 6.0; cleaning; autocatalytic silver, (ESM (electroless silver mixed) 200, PK plating), 63 ° C, 30 minutes; The coverage was verified to be very good under the test at 40 times magnification of the microscope. The waveguide was heated in an oven at 260 ° C for 1 hour to check the adhesion, and the adhesion was very good.

2.一鍍銅的PCB樣品，具有從0.8至8.0mm的襯 墊尺寸，被如下的方式鍍銀：酸性清潔劑，(Ronaclean PC 960)，40℃，5分鐘；清洗；微蝕，(Circuposit Etch 3330)25℃，3分鐘；清洗；銀預浸，(活化及障蔽功能)，3℃，4分鐘，pH值9；清洗；自催化銀，(ESM100，PK鍍覆)3℃，6分鐘，pH值10.3；清洗。該銀厚度是藉由對所有的襯墊做X射線的檢測而得，且所得到的銀厚度發現為14-2μm。 2. A copper plated PCB sample with a lining from 0.8 to 8.0 mm The pad size was silver plated as follows: Acid Cleaner, (Ronaclean PC 960), 40 ° C, 5 minutes; cleaning; microetching, (Circuposit Etch 3330) 25 ° C, 3 minutes; cleaning; silver prepreg, (activation And barrier function), 3 ° C, 4 minutes, pH 9; cleaning; autocatalytic silver, (ESM100, PK plating) 3 ° C, 6 minutes, pH 10.3; The thickness of the silver was obtained by X-ray inspection of all the spacers, and the obtained silver thickness was found to be 14-2 μm.

3.一鋅基材被如下的方式鍍覆：活化，1%硫 酸；清洗；觸擊電鍍氰化銅直到被覆蓋；清洗；預浸銀(孔密封)，40℃，30秒，pH9；清洗；電鍍酸銅2μm；清洗。 在顯微鏡放大100倍下檢驗，顯示無孔洞的跡象。 3. A zinc substrate is plated as follows: activation, 1% sulfur Acid; cleaning; touch plating copper cyanide until covered; cleaning; pre-dip silver (hole sealing), 40 ° C, 30 seconds, pH 9; cleaning; electroplating acid copper 2 μm; Examination at a microscope magnification of 100 times showed no signs of holes.

4.一由鋁製成的微波組件被如下的方式鍍鎳和 銀：蝕刻NaOH；清洗；蝕刻HNO3；清洗；鋅酸鹽；蝕刻HNO3；清洗；鋅酸鹽；清洗；無電鎳(Durni-Coat DNC 471)，90℃，1小時15分鐘，pH4.6；清洗；銀預浸，(活化及障蔽功能)，室溫，4分鐘，pH7.0；清洗；自催化銀，(ESM 200,PK鍍覆)63℃，2小時，pH10.3；清洗。鍍覆後的檢驗顯示：優良的覆蓋性和附著性，鎳厚度為12μm， 銀厚度2.7μm。電性試驗顯示，相較於使用電解銀鍍覆之相同的組件，其具有更低的損耗。 4. A microwave assembly made of aluminum is plated with nickel and silver in the following manner: etching NaOH; cleaning; etching HNO 3 ; cleaning; zincate; etching HNO 3 ; cleaning; zincate; cleaning; electroless nickel (Durni -Coat DNC 471), 90 ° C, 1 hour 15 minutes, pH 4.6; cleaning; silver pre-dip, (activation and barrier function), room temperature, 4 minutes, pH 7.0; cleaning; autocatalytic silver, (ESM 200 , PK plating) 63 ° C, 2 hours, pH 10.3; cleaning. The post-plating inspection showed excellent coverage and adhesion with a nickel thickness of 12 μm and a silver thickness of 2.7 μm . Electrical tests have shown lower losses compared to the same components used for electrolytic silver plating.

5.一銀矽接觸層(其用於後續的一矽晶體太陽能電池的前側金屬化)係以如下的方式進行：藉由雷射之ARC開啟；蝕刻氧化物(HF)6vol%，2分鐘；清洗；銀晶種(銀預浸2分鐘，60℃，pH6.6)；清洗；自催化銀障蔽，(ESM300，PK鍍)5分鐘，60℃，pH10.2；清洗；熱處理，(銀-矽化物生成以及銀燒結)，400℃，10分鐘。 5. A silver ruthenium contact layer (which is used for subsequent front side metallization of a crystalline solar cell) is carried out in the following manner: ARC opening by laser; etching oxide (HF) 6 vol%, 2 minutes; Cleaning; silver seed crystal (silver pre-dip 2 minutes, 60 ° C, pH 6.6); cleaning; autocatalytic silver barrier, (ESM300, PK plating) 5 minutes, 60 ° C, pH 10.2; cleaning; heat treatment, (silver - Telluride formation and silver sintering), 400 ° C, 10 minutes.

熱處理後，該銀層表現出優異的附著性而且可容易的被進一步鍍覆。 After the heat treatment, the silver layer exhibits excellent adhesion and can be easily further plated.

Claims (26)

一種以金屬鍍覆一基材的方法，該方法包含下列步驟：混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中藉此形成一非自催化水性鍍覆浴；以及以該非自催化水性鍍覆浴處理該基材。 A method for plating a substrate with a metal, the method comprising the steps of: mixing a metal salt, a binder, a surfactant, and an acid in water to form a non-autocatalytic aqueous plating bath; The substrate is treated with the non-autocatalytic aqueous plating bath. 如請求項1所述的方法，其中該非自催化水性鍍覆浴是催化性的且包含如桿狀的簇團。 The method of claim 1, wherein the non-autocatalytic aqueous plating bath is catalytic and comprises clusters such as rods. 如請求項1或2所述的方法，其特徵在於該基材包含矽、鎳、錫、銅或一銅合金或由該等組份所構成。 The method of claim 1 or 2, wherein the substrate comprises or consists of ruthenium, nickel, tin, copper or a copper alloy. 如請求項1至3中任一項所述的方法，其特徵在於該金屬鹽為一銀鹽。 The method of any one of claims 1 to 3, wherein the metal salt is a silver salt. 如請求項4所述的方法，其特徵在於該銀鹽是選自於由AgNO3、AgCN、AgClO4、Ag2SO4、AgSO4、Ag2O、KAg(CN)2、NaAg(CN)2、Ag(C2H3O2)和丁二醯亞胺銀錯合物所構成之組群中。 The method of claim 4, wherein the silver salt is selected from the group consisting of AgNO 3 , AgCN, AgClO 4 , Ag 2 SO 4 , AgSO 4 , Ag 2 O, KAg(CN) 2 , NaAg (CN). 2. A group consisting of Ag(C 2 H 3 O 2 ) and succinimide silver complex. 如請求項1至5中任一項所述的方法，其特徵在於該錯合劑是選自於由EDTA、羅謝爾(Rochelle′s salt)、檸檬酸、檸檬酸鈉、丁二酸、丙酸、乙醇酸、醋酸鈉、乳酸、焦磷酸鈉、3-吡啶磺酸、酒石酸鉀、乙二胺、磷酸鈉、檸檬酸鉀、硼酸鈉、氰化鈉、氰化鉀、三伸乙四胺以及甲胺所構成之組群中。 The method of any one of claims 1 to 5, wherein the complexing agent is selected from the group consisting of EDTA, Rochelle's salt, citric acid, sodium citrate, succinic acid, and C. Acid, glycolic acid, sodium acetate, lactic acid, sodium pyrophosphate, 3-pyridine sulfonic acid, potassium tartrate, ethylenediamine, sodium phosphate, potassium citrate, sodium borate, sodium cyanide, potassium cyanide, triethylenetetramine And in the group consisting of methylamine. 如請求項1至6中任一項所述的方法，其特徵在於該酸為一羧酸。 The method of any one of claims 1 to 6, wherein the acid is a monocarboxylic acid. 如請求項1至7中任一項所述的方法，其特徵在於該界面活性劑為一非離子界面活性劑。 The method of any of claims 1 to 7, wherein the surfactant is a nonionic surfactant. 如請求項1至8中任一項所述的方法，其特徵在於該非自催化水性鍍覆浴進一步包含一聚烯烴基氧化物。 The method of any of claims 1 to 8, wherein the non-autocatalytic aqueous plating bath further comprises a polyolefin-based oxide. 如請求項1至9中任一項所述的方法，其特徵在於該非自催化水性鍍覆浴進一步包含硼酸。 The method of any of claims 1 to 9, wherein the non-autocatalytic aqueous plating bath further comprises boric acid. 如請求項1至10中任一項所述的方法，其特徵在於該鍍覆浴在一15至95℃的溫度下操作。 The method of any of claims 1 to 10, characterized in that the plating bath is operated at a temperature of from 15 to 95 °C. 如請求項1至11中任一項所述的方法，其特徵在於該鍍覆浴的pH值範圍從4至12，從5至10或者從9至10。 The method of any of claims 1 to 11, characterized in that the pH of the plating bath ranges from 4 to 12, from 5 to 10 or from 9 to 10. 如請求項1至12中任一項所述的方法，其特徵在於該方法進一步包含一額外的鍍覆步驟，其選自於由自催化無電電鍍、浸鍍或電鍍所構成之組群中。 The method of any of claims 1 to 12, wherein the method further comprises an additional plating step selected from the group consisting of autocatalytic electroless plating, dip plating or electroplating. 如請求項13所述的方法，其特徵在於該額外的鍍覆步驟為自催化無電電鍍。 The method of claim 13 wherein the additional plating step is autocatalytic electroless plating. 如請求項14所述的方法，其特徵在於該額外的鍍覆步驟為銀的自催化無電電鍍。 The method of claim 14 wherein the additional plating step is autocatalytic electroless plating of silver. 如請求項1至15中任一項所述的方法，其特徵在於該方法進一步包含一熱處理步驟。 The method of any of claims 1 to 15, wherein the method further comprises a heat treatment step. 如請求項1至16中任一項所述的方法，包含該基材的密封。 The method of any of claims 1 to 16, comprising sealing the substrate. 一種根據由請求項1至17中任一項界定的方法所塗佈的物件。 An article coated according to the method defined in any one of claims 1 to 17. 一種用於以金屬鍍覆一基材的非自催化水性鍍覆浴，該 非自催化水性鍍覆浴可藉由混合一金屬鹽、一錯合劑、一界面活性劑、以及一酸於水中而被獲得。 A non-autocatalytic aqueous plating bath for plating a substrate with a metal, The non-autocatalytic aqueous plating bath can be obtained by mixing a metal salt, a binder, a surfactant, and an acid in water. 如請求項19所述的非自催化水性鍍覆浴，其特徵在於該金屬鹽為一銀鹽，其選自於由AgNO3、AgCN、AgClO4、Ag2SO4、AgSO4、Ag2O、KAg(CN)2、NaAg(CN)2、Ag(C2H3O2)以及丁二醯亞胺銀錯合物所構成之組群中。 The non-autocatalytic aqueous plating bath according to claim 19, wherein the metal salt is a silver salt selected from the group consisting of AgNO 3 , AgCN, AgClO 4 , Ag 2 SO 4 , AgSO 4 , Ag 2 O , a group consisting of KAg(CN) 2 , NaAg(CN) 2 , Ag(C 2 H 3 O 2 ), and silver succinimide complex. 如請求項19或20所述的非自催化水性鍍覆浴，其特徵在於該錯合劑是選自於由EDTA、羅謝爾鹽(Rochelle′s salt)、檸檬酸、檸檬酸鈉、丁二酸、丙酸、乙醇酸、醋酸鈉、乳酸、焦磷酸鈉、3-吡啶磺酸、酒石酸鉀、乙二胺、磷酸鈉、檸檬酸鉀、硼酸鈉、氰化鈉、氰化鉀、三伸乙四胺以及甲胺所構成之組群中。 The non-autocatalytic aqueous plating bath according to claim 19 or 20, wherein the complexing agent is selected from the group consisting of EDTA, Rochelle's salt, citric acid, sodium citrate, and dibutyl Acid, propionic acid, glycolic acid, sodium acetate, lactic acid, sodium pyrophosphate, 3-pyridine sulfonic acid, potassium tartrate, ethylenediamine, sodium phosphate, potassium citrate, sodium borate, sodium cyanide, potassium cyanide, triple extension In the group consisting of ethylenetetramine and methylamine. 如請求項19至21任一項所述的非自催化水性鍍覆浴，其特徵在於該酸為一羧酸。 The non-autocatalytic aqueous plating bath according to any one of claims 19 to 21, wherein the acid is a monocarboxylic acid. 如請求項19至22任一項所述的非自催化水性鍍覆浴，其特徵在於該界面活性劑為一非離子界面活性劑。 The non-autocatalytic aqueous plating bath according to any one of claims 19 to 22, wherein the surfactant is a nonionic surfactant. 如請求項19至23任一項所述的非自催化水性鍍覆浴，其進一步包含聚烯烴基氧化物。 The non-autocatalytic aqueous plating bath of any one of claims 19 to 23, further comprising a polyolefin-based oxide. 如請求項19至24任一項所述的非自催化水性鍍覆浴，其進一步包含硼酸。 The non-autocatalytic aqueous plating bath of any one of claims 19 to 24, further comprising boric acid. 如請求項19至25任一項所述的非自催化水性鍍覆浴，其特徵在於該非自催化水性鍍覆浴的pH值範圍從4至12，從5至10或者從9至10。 The non-autocatalytic aqueous plating bath according to any one of claims 19 to 25, wherein the non-autocatalytic aqueous plating bath has a pH ranging from 4 to 12, from 5 to 10 or from 9 to 10.
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