TWI612180B - Continuous purification system for chemical displacement gold plating solution and impurity nickel and impurity copper - Google Patents
Continuous purification system for chemical displacement gold plating solution and impurity nickel and impurity copper Download PDFInfo
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Abstract
本發明係一種化學置換鍍金溶液及雜質鎳及雜質銅的連續純化系統，包含無電鍍金鍍浴槽、分離單元、雜質移除單元、迴流混合單元及鍍液儲存筒，可在含鎳膜層之基板上藉化學的置換反應以生成金膜層而形成含金膜層之基板，其中金膜層是沉積在鎳膜層的表面上。利用主要螯合劑以螯合金離子而形成具20~18nm顆粒大小結構的金錯合物，並藉分離單元中具孔隙大小為20~18nm的PE逆滲透膜而分離金錯合物，同時還利用雜質移除單元的螯合型離子交換樹脂而選擇性吸收鎳雜質及銅雜質。因此，本發明可達到每分鐘0.0075~0.0084µm的沉積速率而沉積出厚度高達0.12µm的優良金膜層。The invention relates to a chemical displacement gold plating solution and a continuous purification system of impurity nickel and impurity copper, comprising an electroless gold plating bath, a separation unit, an impurity removing unit, a reflux mixing unit and a plating liquid storage tank, which can be in a nickel-containing film layer. A substrate is subjected to a chemical displacement reaction to form a gold film layer to form a substrate containing a gold film layer, wherein the gold film layer is deposited on the surface of the nickel film layer. The gold chelate compound having a particle size structure of 20 to 18 nm is formed by using a main chelating agent as a chelate alloy ion, and the gold complex is separated by a reverse osmosis membrane of PE having a pore size of 20 to 18 nm in the separation unit, and is also utilized. The chelating type ion exchange resin of the impurity removing unit selectively absorbs nickel impurities and copper impurities. Therefore, the present invention can achieve a deposition rate of 0.0075 to 0.0084 μm per minute to deposit an excellent gold film layer having a thickness of up to 0.12 μm.
Description
本發明係有關於一種化學置換鍍金溶液及雜質鎳及雜質銅的連續純化系統，尤其是利用主要螯合劑而與金離子螯合成具20~18nm顆粒大小結構的金錯合物，並藉分離單元中具孔隙大小為20~18nm的PE逆滲透膜而分離金錯合物，同時還利用雜質移除單元的螯合型離子交換樹脂而選擇性吸收鎳雜質及銅雜質，可達到每分鐘0.0075~0.0084µm的沉積速率而沉積出厚度高達0.12µm的優良金膜層，滿足一般實務上金膜層的厚度需求。The invention relates to a continuous purification system for chemically replacing gold plating solution and impurity nickel and impurity copper, in particular, using a main chelating agent to chelate gold ions with a gold complex having a particle size structure of 20-18 nm, and using a separation unit. The PE reverse osmosis membrane with pore size of 20~18nm is used to separate the gold complex, and the chelating ion exchange resin of the impurity removal unit is also used to selectively absorb nickel impurities and copper impurities, which can reach 0.0075~ per minute. An excellent gold film layer with a thickness of up to 0.12 μm is deposited at a deposition rate of 0.0084 μm, which satisfies the thickness requirement of the gold film layer in general practice.
在一般的電路板製程中，除了需要在基板上形成電路層外，還需要形成高品質的連接墊，用以連接電子元件，形成電氣迴路。這類的連接墊常常使用鎳膜層當作中間媒介層，並在鎳膜層上形成金膜層，因為電子元件比較容易焊接至金膜層。In a general circuit board process, in addition to forming a circuit layer on a substrate, it is also necessary to form a high-quality connection pad for connecting electronic components to form an electrical circuit. Such a connection pad often uses a nickel film layer as an intermediate dielectric layer and forms a gold film layer on the nickel film layer because electronic components are relatively easy to solder to the gold film layer.
在習知技術中，鎳膜層上形成金膜層的方式可使用包含金離子的鎳可置換金溶液，並藉化學置換反應而將金屬鎳置換成金屬金，亦即，在不施加任何電流下，金離子與金屬鎳藉氧化還原反應而相互置換。In the prior art, a gold film layer is formed on the nickel film layer by using a nickel replaceable gold solution containing gold ions, and replacing the metal nickel with metal gold by a chemical displacement reaction, that is, without applying any current. Next, the gold ions and the metal nickel are mutually replaced by a redox reaction.
上述習知技術的缺點在於鎳可置換金溶液的普遍問題是會發生侵蝕現象，尤其是會完全覆蓋金膜層的表面。例如，當浸泡時間不足時，會在經過一段時間後發生這種侵蝕現象。主要是取決於化學配方以及浸泡時間的控制是否到達適當範圍內，而且該現象會損害到表面的外觀。A disadvantage of the above prior art is that a common problem with nickel replaceable gold solutions is that erosion can occur, especially covering the surface of the gold film layer. For example, when the immersion time is insufficient, this erosion occurs after a certain period of time. It mainly depends on whether the chemical formulation and the control of the soaking time reach the proper range, and this phenomenon will damage the appearance of the surface.
習知技術的另一問題是由鎳引起，不過有時是來自PCB的光阻層的凹陷的銅或來自底下的Ni-P層的磷，因為鎳、銅、磷都會溶解在鎳可置換金溶液中，進而影響表面金純化，甚至是會超過鎳雜質容許量的150 ~ 200 ppm，導致電阻的大幅增加。Another problem with the prior art is that it is caused by nickel, but sometimes it is the recessed copper from the photoresist layer of the PCB or the phosphorus from the underlying Ni-P layer, because nickel, copper, and phosphorus are all dissolved in the nickel replaceable gold. The solution, which in turn affects the surface gold purification, even exceeds the allowable amount of nickel impurities from 150 to 200 ppm, resulting in a substantial increase in electrical resistance.
此外，本發明之鎳可置換金溶液不含金-還原劑，比如抗壞血酸(ascorbic acid)、甲醛(formaldehyde)、二甲氨基苯甲醛(Dimethylaminobenzaldehyde)，所以在反應進行後，來自還原劑的副產物不會累積在鍍浴中而影響到金膜層的品質。In addition, the nickel replaceable gold solution of the present invention does not contain a gold-reducing agent, such as ascorbic acid, formaldehyde, or Dimethylaminobenzaldehyde, so after the reaction proceeds, by-products from the reducing agent Does not accumulate in the plating bath and affects the quality of the gold film layer.
因此，需要一種新式化學置換鍍金溶液及雜質鎳及雜質銅的連續純化系統，利用主要螯合劑而與金離子螯合成具20~18nm顆粒大小結構的金錯合物，並藉分離單元中具孔隙大小為20~18nm的PE逆滲透膜而分離金錯合物，同時還利用雜質移除單元的螯合離子交換樹脂而選擇性吸收鎳雜質及銅雜質，不僅可達到每分鐘0.0075~0.0084µm的沉積速率而沉積出厚度高達0.12µm的優良金膜層，滿足一般實務上金膜層的厚度需求，而且還可延長無電鍍金鍍液的使用時間，進而解決上述習知技術的問題。Therefore, there is a need for a new chemical displacement gold plating solution and a continuous purification system of impurity nickel and impurity copper, which are chelated with gold ions by a main chelating agent to form a gold complex having a particle size structure of 20 to 18 nm, and have pores in the separation unit. The PE reverse osmosis membrane with a size of 20~18nm separates the gold complex, and also selectively absorbs nickel impurities and copper impurities by using the chelating ion exchange resin of the impurity removal unit, which can reach not only 0.0075~0.0084μm per minute. An excellent gold film layer with a thickness of up to 0.12 μm is deposited at a deposition rate, which satisfies the thickness requirement of the gold film layer in general practice, and can also prolong the use time of the electroless gold plating bath, thereby solving the above-mentioned problems of the prior art.
本發明之主要目的在提供一種化學置換鍍金溶液及雜質鎳及雜質銅的連續純化系統，包含無電鍍金鍍浴槽、分離單元、雜質移除單元、迴流混合單元以及鍍液儲存筒，用以在含鎳膜層之基板上藉無電鍍的化學置換反應以生成金膜層而形成含金膜層之基板，其中金膜層是沉積在鎳膜層的表面上。The main object of the present invention is to provide a continuous purification system for chemically replacing gold plating solution and impurity nickel and impurity copper, comprising an electroless gold plating bath, a separation unit, an impurity removing unit, a reflux mixing unit and a plating liquid storage tank for The substrate containing the nickel film layer is subjected to a chemical displacement reaction by electroless plating to form a gold film layer to form a substrate containing the gold film layer, wherein the gold film layer is deposited on the surface of the nickel film layer.
無電鍍金鍍浴槽可容置無電鍍金鍍液，其中無電鍍金鍍液包含金錯合物以及主要螯合劑，主要螯合劑為四(2-羥丙基)乙二胺(Tetra (2-hydrxypropyl) ethylenediamine)，濃度為5 ~ 20 g/L；而金錯合物的金濃度為0.6 ~ 2.0 g/L。The electroless gold plating bath can accommodate an electroless gold plating solution, wherein the electroless gold plating solution contains a gold complex and a main chelating agent, and the main chelating agent is tetrakis(2-hydroxypropyl)ethylenediamine (Tetra (2- Hydrxypropyl) ethylenediamine), concentration 5 ~ 20 g / L; and gold complex gold concentration of 0.6 ~ 2.0 g / L.
分離單元連接無電鍍金鍍浴槽，用以將無電鍍金鍍浴槽中的無電鍍金鍍液抽離，並對無電鍍金鍍液中的金錯合物進行選擇性分離(selective segregation)處理，藉以形成並傳送含高濃度金錯合物的濃縮溶液及含低濃度金錯合物的滲透溶液。The separation unit is connected to the electroless gold plating bath for extracting the electroless gold plating solution in the electroless gold plating bath, and performing selective segregation treatment on the gold complex in the electroless gold plating solution. Thereby, a concentrated solution containing a high concentration of gold complex and an osmotic solution containing a low concentration of gold complex are formed and transported.
雜質移除單元連接分離單元，可接收滲透溶液，並對滲透溶液中的鎳雜質及銅雜質進行滲透、吸收處理而移除，進而形成純化溶液。The impurity removing unit is connected to the separation unit, and can receive the permeation solution, and remove and absorb the nickel impurities and the copper impurities in the permeation solution to form a purification solution.
迴流混合單元連接分離單元及雜質移除單元，分別接收濃縮溶液以及純化溶液，同時接收由外部已配置好的新鮮的無電鍍金鍍液，並經迴流、混合處理後形成所需的無電鍍金鍍液並輸送至鍍液儲存筒而儲存。鍍液儲存筒的無電鍍金鍍液進一步輸送至無電鍍金鍍浴槽。The reflux mixing unit is connected to the separation unit and the impurity removal unit, respectively receives the concentrated solution and the purification solution, and simultaneously receives the fresh electroless plating gold plating solution which has been configured externally, and is reflowed and mixed to form the desired electroless gold plating. The plating solution is transferred to a plating solution storage tank for storage. The electroless gold plating solution of the plating solution storage tank is further transported to the electroless gold plating bath.
無電鍍金鍍液是供含鎳膜層之基板浸泡以進行化學置換反應，而含鎳膜層之基板包含基板、電路層及鎳膜層，電路層是在基板上，而鎳膜層是在電路層上。此外，鎳膜層的表面上的金屬鎳是在與無電鍍金鍍液接觸時，經置換反應而生成金膜層，進而形成含金膜層之基板。The electroless gold plating solution is for immersing the substrate containing the nickel film layer for chemical replacement reaction, and the substrate containing the nickel film layer comprises a substrate, a circuit layer and a nickel film layer, the circuit layer is on the substrate, and the nickel film layer is On the circuit layer. Further, the metallic nickel on the surface of the nickel film layer is a substrate which is subjected to a substitution reaction to form a gold film layer upon contact with the electroless gold plating solution, thereby forming a gold film layer.
本發明可有效的回收、再利用金錯合物，避免浪費，同時改善金膜層的品質，尤其是利用主要螯合劑而與金離子螯合成具20~18nm顆粒大小結構的金錯合物，並藉分離單元中具孔隙大小為20~18nm的PE逆滲透膜而分離金錯合物，同時還利用雜質移除單元的螯合離子交換樹脂而選擇性吸收鎳雜質及銅雜質，不僅可達到每分鐘0.0075~0.0084µm的沉積速率而沉積出厚度高達0.12µm的優良金膜層，滿足一般實務上金膜層的厚度需求，而且還可延長無電鍍金鍍液的使用時間。The invention can effectively recover and reuse the gold complex, avoid waste, and at the same time improve the quality of the gold film layer, in particular, the gold chelate compounded with the gold ion to form a gold complex with a particle size of 20-18 nm by using a main chelating agent. The gold complex is separated by a PE reverse osmosis membrane having a pore size of 20 to 18 nm in the separation unit, and the chelating ion exchange resin of the impurity removal unit is used to selectively absorb nickel impurities and copper impurities, which can not only be achieved. An excellent gold film layer with a thickness of up to 0.12 μm is deposited at a deposition rate of 0.0075 to 0.0084 μm per minute, which satisfies the thickness requirement of the gold film layer in general practice, and also prolongs the use time of the electroless gold plating solution.
以下配合圖示及元件符號對本發明之實施方式做更詳細的說明，俾使熟習該項技藝者在研讀本說明書後能據以實施。The embodiments of the present invention will be described in more detail below with reference to the drawings and the reference numerals, which can be implemented by those skilled in the art after having studied this specification.
請參閱第一圖，本發明實施例化學置換鍍金溶液及雜質鎳及雜質銅的連續純化系統的整體示意圖。如第一圖所示，本發明實施例化學置換鍍金溶液及雜質鎳及雜質銅的連續純化系統包含無電鍍金鍍浴槽10、分離單元20、雜質移除單元30、迴流混合單元40以及鍍液儲存筒50，用以在含鎳膜層之基板A上生成金膜層而形成含金膜層之基板B，其中金膜層是沉積在鎳膜層上，達到連續性純化無電鍍金鍍液而達到循環、再利用之目的。Please refer to the first figure for an overall schematic diagram of a chemical purification gold plating solution and a continuous purification system of impurity nickel and impurity copper according to an embodiment of the present invention. As shown in the first figure, the continuous purification system of the chemical displacement gold plating solution and the impurity nickel and impurity copper according to the embodiment of the present invention comprises an electroless gold plating bath 10, a separation unit 20, an impurity removing unit 30, a reflux mixing unit 40, and a plating solution. a storage cylinder 50 for forming a gold film layer on the substrate A containing the nickel film layer to form a substrate B containing a gold film layer, wherein the gold film layer is deposited on the nickel film layer to achieve continuous purification of the electroless gold plating solution And achieve the purpose of recycling and reuse.
具體而言，無電鍍金鍍浴槽10容置來自鍍液儲存筒50的無電鍍金鍍液L1，而且含鎳膜層之基板A是被輸送到無電鍍金鍍浴槽10中，比如利用輸送帶60及輸入滾筒61的方式輸送，其中輸送帶60承載含鎳膜層之基板A，而且含鎳膜層之基板A是浸泡到無電鍍金鍍浴槽10的無電鍍金鍍液中，藉以進行化學電鍍而在含鎳膜層之基板A上經置換反應生成金膜層，形成含金膜層之基板B，接著，利用輸出滾筒62捲動輸送帶60而將含金膜層之基板B帶離開無電鍍金鍍浴槽10。Specifically, the electroless gold plating bath 10 accommodates the electroless gold plating solution L1 from the plating solution storage cylinder 50, and the substrate A containing the nickel film layer is transported into the electroless gold plating bath 10, for example, using a conveyor belt. 60 and the input roller 61, wherein the conveyor belt 60 carries the substrate A containing the nickel film layer, and the substrate A containing the nickel film layer is immersed in the electroless gold plating bath of the electroless gold plating bath 10, thereby performing chemistry Electroplating is performed on the substrate A containing the nickel film layer to form a gold film layer, thereby forming a substrate B containing the gold film layer, and then the transfer belt 60 is wound by the output roller 62 to take the substrate B containing the gold film layer away. Electroless gold plating bath 10.
要注意的是，上述的輸送帶60、輸入滾筒61、輸出滾筒62只是用以說明將含鎳膜層之基板A傳送到無電鍍金鍍浴槽10並將形成的含金膜層之基板B帶離無電鍍金鍍浴槽10的示範性實例而已，並非用以限定本發明的範圍，亦即，傳送含鎳膜層之基板A、含金膜層之基板B的任何方式都應涵蓋於本發明。It should be noted that the conveyor belt 60, the input roller 61, and the output roller 62 are only used to illustrate that the substrate A containing the nickel-containing film layer is transferred to the electroless gold plating bath 10 and the substrate B with the gold film layer formed is formed. An exemplary embodiment of the electroless gold plating bath 10 is not intended to limit the scope of the present invention, that is, any manner of transporting the substrate A containing the nickel film layer and the substrate B containing the gold film layer should be encompassed by the present invention. .
如第二圖所示，含鎳膜層之基板A包含基板A1、電路線A2、鎳膜層A3，其中電路線A2是在基板A1上，而鎳膜層A3是在電路線A2上。一般，電路線A2是由金屬銅構成。As shown in the second figure, the substrate A containing the nickel film layer includes the substrate A1, the circuit line A2, and the nickel film layer A3, wherein the circuit line A2 is on the substrate A1, and the nickel film layer A3 is on the circuit line A2. Generally, the circuit line A2 is made of metallic copper.
上述的無電鍍金鍍液L1是一種用於鍍浴化學的鍍液，可對鎳膜層A3進行鎳置換反應而生成金膜層B1，形成含金膜層之基板B。上述生成金膜層B1的製程一般稱作化學電鍍(chemical electroplating)或無電電鍍(electroless plating)。The electroless gold plating solution L1 described above is a plating solution for plating bath chemistry, and the nickel film layer A3 is subjected to a nickel substitution reaction to form a gold film layer B1 to form a substrate B containing a gold film layer. The above process for producing the gold film layer B1 is generally referred to as chemical electroplating or electroless plating.
無電鍍金鍍液L1主要是包含金錯合物及主要螯合劑(chelating agent)，其中主要螯合劑為四(2-羥丙基)乙二胺(tetra (2-hydroxypropyl) ethylenediamine)，且無電鍍金鍍液L1可用於氰化金(cynide gold)鍍浴或無氰化金(non-cynide gold)鍍浴，尤其是當作主要螯合劑的四(2-羥丙基)乙二胺為本發明最為關鍵的成份。在用於氰化金鍍浴時，金錯合物可為氰化金鉀(gold(I) potassium cyanide)，而用於無氰化金鍍浴時，金錯合物可為二亞硫酸金(I)三鈉(gold trisodium disulphite)。此外，針對氰化金鍍浴或無氰化金鍍浴，無電鍍金鍍液L1還額外包含其他特定的成份。The electroless gold plating solution L1 mainly contains a gold complex and a main chelating agent, wherein the main chelating agent is tetra (2-hydroxypropyl) ethylenediamine, and no The electroplated gold plating solution L1 can be used for a cyanide gold plating bath or a non-cynide gold plating bath, especially as a main chelating agent for tetrakis(2-hydroxypropyl)ethylenediamine. The most critical component of the invention. When used in a gold cyanide plating bath, the gold complex can be gold(I) potassium cyanide, and when used in a gold-free cyanide plating bath, the gold complex can be gold dithionite. (I) gold trisodium disulphite. In addition, for the gold cyanide plating bath or the non-cyanide gold plating bath, the electroless gold plating bath L1 additionally contains other specific components.
舉例而言，用於氰化金鍍浴的無電鍍金鍍液L1是包含氰化金鉀、四(2-羥丙基)乙二胺、檸檬酸氨(ammonium citrate)、蘋果酸(malic acid)、甘胺酸(glycine)以及氫氧化鈉(sodium hydroxide)，其中氰化金鉀的金濃度為0.6 ~ 1.2 g/L，四(2-羥丙基)乙二胺的濃度為5 ~ 20 g/L。再者，用於無氰化金鍍浴的無電鍍金鍍液是包含二亞硫酸金(I)三鈉、四(2-羥丙基)乙二胺、檸檬酸鈉(sodium citrate)、蘋果酸以及硫酸鈉(sodium sulfite)，其中二亞硫酸金(I)三鈉的金濃度為1.0 ~ 2.0 g/L，四(2-羥丙基)乙二胺的濃度為10 ~ 15 g/L。For example, the electroless gold plating solution L1 used for the gold cyanide plating bath comprises gold potassium cyanide, tetrakis(2-hydroxypropyl)ethylenediamine, ammonium citrate, malic acid. ), glycine and sodium hydroxide, wherein the gold concentration of potassium cyanide is 0.6 ~ 1.2 g / L, and the concentration of tetrakis (2-hydroxypropyl) ethylene diamine is 5 ~ 20 g/L. Furthermore, the electroless gold plating bath for the cyanide-free gold plating bath comprises gold (I) trisodium disulfite, tetrakis(2-hydroxypropyl)ethylenediamine, sodium citrate, apple Acid and sodium sulfite, wherein the gold concentration of gold (I) disodium disulfite is 1.0 ~ 2.0 g / L, and the concentration of tetrakis (2-hydroxypropyl) ethylene diamine is 10 ~ 15 g / L .
無電鍍金鍍液L1的主要功能在於利用電鍍金鍍液L1中的金離子與鎳膜層A3的表面上的金屬鎳進行置換反應而生成金屬金的金膜層B1於鎳膜層A3的表面上。進一步而言，沉積出金膜層B1的驅動因素是來自電極電位差，亦即，發生在鎳膜層A3的表面上的氧化還原反應，其中無電鍍金鍍液L1中的氧化物及/或螯合劑會與在鎳膜層A3反應而釋放電子，而無電鍍金鍍液L1中的金離子是當作電子補捉體，用接收被釋放的電子而在鎳膜層A3的表面上進行還原反應，進而還原出金屬金，形成金膜層B1，達成電子平衡。因此整體而言，鎳膜層A3的金屬鎳被氧化成鎳離子，而金離子被還原成金屬金的金膜層B1。較佳的，這種金膜層B1具有良好的附著力，而且在金膜層B1形成過程中未通上任何電流，所以不會對基板A1上的電路線A2產生任何影響。The main function of the electroless gold plating solution L1 is to form a gold film layer B1 of metal gold on the surface of the nickel film layer A3 by performing a substitution reaction with gold ions on the surface of the nickel film layer A3 by gold ions in the plating gold plating solution L1. on. Further, the driving factor for depositing the gold film layer B1 is the electrode potential difference, that is, the redox reaction occurring on the surface of the nickel film layer A3, wherein the oxide and/or the chelate in the electroless gold plating solution L1 The mixture reacts with the nickel film layer A3 to release electrons, and the gold ions in the electroless gold plating solution L1 act as electron trapping bodies, and perform reduction reaction on the surface of the nickel film layer A3 by receiving the released electrons. Further, metal gold is reduced to form a gold film layer B1, and an electron balance is achieved. Therefore, as a whole, the metallic nickel of the nickel film layer A3 is oxidized to nickel ions, and the gold ions are reduced to the gold film layer B1 of the metal gold. Preferably, the gold film layer B1 has good adhesion, and no current is applied during the formation of the gold film layer B1, so that it does not have any influence on the circuit line A2 on the substrate A1.
更加具體而言，無電鍍金鍍液L1中金錯合物的金離子會與主要螯合劑相互螯合後形成金錯合物，且金錯合物是具有20~18nm結構的顆粒大小。More specifically, the gold ions of the gold complex in the electroless gold plating bath L1 are chelated with the main chelating agent to form a gold complex, and the gold complex is a particle size having a structure of 20 to 18 nm.
再回到第一圖，分離單元20是連接無電鍍金鍍浴槽10，用以將無電鍍金鍍浴槽10中的無電鍍金鍍液L1抽離，並對無電鍍金鍍液L1中的金錯合物進行選擇性分離(selective segregation)處理，形成並傳送含高濃度金錯合物的濃縮溶液L2及含低濃度金錯合物的滲透溶液L3。較佳的，無電鍍金鍍液L1中的金錯合物是經由具20 ~ 18 nm孔隙大小的逆滲透膜而選擇性分離，比如由聚乙烯(polyethylene，PE)構成的逆滲透膜。要注意的是，一般的聚醯胺(polyamide，PA)薄膜的孔隙大小為1.2 nm或0.2 nm，而聚四氟乙烯(polytetrafluoroethylene， PTFE)薄膜的孔隙大小為100 nm，且陶瓷(ceramic)薄膜的孔隙大小為約120 nm，所以皆不適用於本發明。Returning to the first figure, the separation unit 20 is connected to the electroless gold plating bath 10 for extracting the electroless gold plating solution L1 from the electroless gold plating bath 10 and for gold in the electroless gold plating solution L1. The complex compound is subjected to a selective segregation treatment to form and deliver a concentrated solution L2 containing a high concentration of gold complex and an osmotic solution L3 containing a low concentration of gold complex. Preferably, the gold complex in the electroless gold plating bath L1 is selectively separated by a reverse osmosis membrane having a pore size of 20 to 18 nm, such as a reverse osmosis membrane composed of polyethylene (PE). It should be noted that the general polyamide (PA) film has a pore size of 1.2 nm or 0.2 nm, and the polytetrafluoroethylene (PTFE) film has a pore size of 100 nm and a ceramic film. The pore size is about 120 nm, so neither of them is suitable for use in the present invention.
雜質移除單元30連接分離單元20，用以接收滲透溶液L3，並對滲透溶液L3中的鎳雜質及銅雜質進行滲透、吸收處理而移除，進而形成純化溶液L4。較佳的，雜質移除單元30是利用螯合離子交換樹脂而達到選擇性吸收鎳雜質及銅雜質。The impurity removing unit 30 is connected to the separation unit 20 for receiving the permeation solution L3, and is removed by permeating and absorbing the nickel impurities and copper impurities in the permeation solution L3 to form a purification solution L4. Preferably, the impurity removing unit 30 utilizes a chelating ion exchange resin to selectively absorb nickel impurities and copper impurities.
迴流混合單元40連接分離單元20及雜質移除單元30，分別接收來自分離單元20的濃縮溶液L2以及來自雜質移除單元30的純化溶液L4，同時接收由外部已配置好的新鮮的無電鍍金鍍液LA，經迴流、混合處理後輸送到鍍液儲存筒50，其中新鮮的無電鍍金鍍液LA包含新添加的金離子，而且金離子的含量是等於無電鍍金鍍浴槽10中置換反應的金膜層之生成量，藉以達到金離子的質量守恆。The reflux mixing unit 40 is connected to the separation unit 20 and the impurity removal unit 30, respectively receiving the concentrated solution L2 from the separation unit 20 and the purification solution L4 from the impurity removal unit 30 while receiving the fresh electroless gold plating which has been externally configured. The plating solution LA is sent to the plating solution storage cylinder 50 after being refluxed and mixed, wherein the fresh electroless gold plating bath LA contains newly added gold ions, and the content of gold ions is equal to the displacement reaction in the electroless gold plating bath 10 The amount of gold film formed to achieve the conservation of gold ions.
因此，鍍液儲存筒50所儲存的無電鍍金鍍液L1具有穩定的金離子濃度以供應無電鍍金鍍浴槽10，使得金膜層可維持穩定的生成速率，比如高達每分鐘0.0075~0.0084 µm的沉積速率，進而沉積出厚度高達0.12 µm的優良金膜層。須知，一般實務上的金膜層需要0.05 µm、0.074 µm、0.10 µm的厚度，所以本發明確實能滿足所需厚度。Therefore, the electroless gold plating solution L1 stored in the plating solution storage cylinder 50 has a stable gold ion concentration to supply the electroless gold plating bath 10, so that the gold film layer can maintain a stable formation rate, for example, up to 0.0075 to 0.0084 μm per minute. The deposition rate, in turn, deposits an excellent gold film layer with a thickness of up to 0.12 μm. It should be noted that the gold film layer in general practice requires a thickness of 0.05 μm, 0.074 μm, and 0.10 μm, so the present invention can surely satisfy the required thickness.
本發明的特點在於利用大分子的化學藥劑而與金離子螯合後獲得金錯合物，使得螯合後的金錯合物是具有將近20~18nm結構的顆粒大小，可方便在分離單元中利用具孔隙大小為20~18nm的PE逆滲透膜而將金錯合物分離，達到回收、再利用的目的，尤其是，無電鍍金鍍液的配方是特別包含大分子的四(2-羥丙基)乙二胺(tetra (2-hydrxypropyl) ethylenediamine)以及檸檬酸鈉(sodium citrate)，其中四(2-羥丙基)乙二胺的分子量為292 g/mol，而檸檬酸鈉的分子量為258 g/mol。The invention is characterized in that the gold complex is obtained by chelation with gold ions by using a macromolecular chemical, so that the chelated gold complex is a particle size having a structure of nearly 20-18 nm, which is convenient in the separation unit. The gold complex is separated by a PE reverse osmosis membrane having a pore size of 20 to 18 nm, thereby achieving the purpose of recovery and reuse. In particular, the formulation of the electroless gold plating bath is a tetra(2-hydroxyl group) which particularly contains macromolecules. Propyl)di(2-hydrxypropyl)ethylenediamine and sodium citrate, wherein the molecular weight of tetrakis(2-hydroxypropyl)ethylenediamine is 292 g/mol, and the molecular weight of sodium citrate It is 258 g/mol.
本發明的另一特點在於所使用的無電鍍金鍍液不含任何金-還原劑，比如抗壞血酸(ascorbic acid)、甲醛、Dimethylaminobenzaldehyde，所以來自還原劑的副產物也不會累積在無電鍍金鍍液中，能確保金膜層的穩固品質，因為一直都是沉積出純金，尤其是，雜質移除單元已利用螯合型離子交換樹脂而選擇性吸收鎳雜質及銅雜質。此外，無電鍍金鍍液可使用一段很長的時間，比如在鳳凰使用模式(phoenix use mode)中，而即便是有鎳雜質溶解，也能經由本發明中雜質移除單元的處理而連續性恢復無電鍍金鍍液。Another feature of the present invention is that the electroless gold plating solution used does not contain any gold-reducing agent, such as ascorbic acid, formaldehyde, and Dimethylaminobenzaldehyde, so by-products from the reducing agent do not accumulate in electroless gold plating. In the liquid, the solid quality of the gold film layer can be ensured because pure gold is always deposited. In particular, the impurity removing unit has utilized the chelating type ion exchange resin to selectively absorb nickel impurities and copper impurities. In addition, the electroless gold plating solution can be used for a long period of time, such as in a phoenix use mode, and even if nickel impurities are dissolved, continuity can be handled by the impurity removal unit of the present invention. Restore electroless gold plating solution.
以上所述者僅為用以解釋本發明之較佳實施例，並非企圖據以對本發明做任何形式上之限制，是以，凡有在相同之發明精神下所作有關本發明之任何修飾或變更，皆仍應包括在本發明意圖保護之範疇。The above is only a preferred embodiment for explaining the present invention, and is not intended to limit the present invention in any way, and any modifications or alterations to the present invention made in the spirit of the same invention. All should still be included in the scope of the intention of the present invention.
10‧‧‧無電鍍金鍍浴槽
20‧‧‧分離單元
30‧‧‧雜質移除單元
40‧‧‧迴流混合單元
50‧‧‧鍍液儲存筒
60‧‧‧輸送帶
61‧‧‧輸入滾筒
62‧‧‧輸出滾筒
A‧‧‧含鎳膜層之基板
A1‧‧‧基板
A2‧‧‧電路線
A3‧‧‧鎳膜層
B‧‧‧含金膜層之基板
B1‧‧‧金膜層
LA‧‧‧新鮮的無電鍍金鍍液
L1‧‧‧無電鍍金鍍液
L2‧‧‧濃縮溶液
L3‧‧‧滲透溶液
L4‧‧‧純化溶液10‧‧‧Electroless gold plating bath
20‧‧‧Separation unit
30‧‧‧ impurity removal unit
40‧‧‧Reflow mixing unit
50‧‧‧ plating solution storage cylinder
60‧‧‧ conveyor belt
61‧‧‧ input roller
62‧‧‧Output roller
A‧‧‧ substrate with nickel film
A1‧‧‧Substrate
A2‧‧‧ circuit line
A3‧‧‧ Nickel film
B‧‧‧ substrate with gold film
B1‧‧‧ gold film
LA‧‧‧Fresh electroless gold plating bath
L1‧‧‧ electroless gold plating solution
L2‧‧‧ concentrated solution
L3‧‧‧ osmotic solution
L4‧‧‧purified solution
第一圖顯示依據本發明實施例化學置換鍍金溶液及雜質鎳及雜質銅的連續純化系統的整體示意圖。 第二圖顯示用於本發明之基板的示意圖。The first figure shows an overall schematic diagram of a continuous purification system for chemically replacing gold plating solutions and impurity nickel and impurity copper in accordance with an embodiment of the present invention. The second figure shows a schematic view of a substrate for use in the present invention.
10‧‧‧無電鍍金鍍浴槽 10‧‧‧Electroless gold plating bath
20‧‧‧分離單元 20‧‧‧Separation unit
30‧‧‧雜質移除單元 30‧‧‧ impurity removal unit
40‧‧‧迴流混合單元 40‧‧‧Reflow mixing unit
50‧‧‧鍍液儲存筒 50‧‧‧ plating solution storage cylinder
60‧‧‧輸送帶 60‧‧‧ conveyor belt
61‧‧‧輸入滾筒 61‧‧‧ input roller
62‧‧‧輸出滾筒 62‧‧‧Output roller
A‧‧‧含鎳膜層之基板 A‧‧‧ substrate with nickel film
B‧‧‧含金膜層之基板 B‧‧‧ substrate with gold film
LA‧‧‧新鮮的無電鍍金鍍液 LA‧‧‧Fresh electroless gold plating bath
L1‧‧‧無電鍍金鍍液 L1‧‧‧ electroless gold plating solution
L2‧‧‧濃縮溶液 L2‧‧‧ concentrated solution
L3‧‧‧滲透溶液 L3‧‧‧ osmotic solution
L4‧‧‧純化溶液 L4‧‧‧purified solution
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010036514A1 (en) * | 2000-04-27 | 2001-11-01 | Shigeki Iwamoto | Partial plating system |
| US20050003677A1 (en) * | 2003-07-01 | 2005-01-06 | Motorola, Inc. | Activation plate for electroless and immersion plating of integrated circuits |
| TWI232895B (en) * | 2000-10-20 | 2005-05-21 | Boc Group Inc | Object plating method and system |
| US20070104929A1 (en) * | 2005-10-25 | 2007-05-10 | Samsung Electro-Mechanics Co., Ltd. | Method for plating printed circuit board and printed circuit board manufactured therefrom |
| US20130104740A1 (en) * | 2011-10-26 | 2013-05-02 | Shell Oil Company | Method for preparing a palladium-gold alloy gas separation membrane sytem |
| TWI455750B (en) * | 2012-06-04 | 2014-10-11 | Arps Inc | Surface treatment wet process phosphorus-containing electroless nickel plating liquid component recycling system |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20010036514A1 (en) * | 2000-04-27 | 2001-11-01 | Shigeki Iwamoto | Partial plating system |
| TWI232895B (en) * | 2000-10-20 | 2005-05-21 | Boc Group Inc | Object plating method and system |
| US20050003677A1 (en) * | 2003-07-01 | 2005-01-06 | Motorola, Inc. | Activation plate for electroless and immersion plating of integrated circuits |
| US20070104929A1 (en) * | 2005-10-25 | 2007-05-10 | Samsung Electro-Mechanics Co., Ltd. | Method for plating printed circuit board and printed circuit board manufactured therefrom |
| US20130104740A1 (en) * | 2011-10-26 | 2013-05-02 | Shell Oil Company | Method for preparing a palladium-gold alloy gas separation membrane sytem |
| TWI455750B (en) * | 2012-06-04 | 2014-10-11 | Arps Inc | Surface treatment wet process phosphorus-containing electroless nickel plating liquid component recycling system |
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