本文選題：亞硫酸體系鍍金 + 黑盤�。� 參考：《哈爾濱工業(yè)大學(xué)》2016年博士論文

【摘要】：印制電路板(PCB)終飾工藝是其制造流程中最后的表面處理步驟,不僅為線路表面提供保護(hù)層,更是保證印刷電路板在裝配和使用中能夠有效連接的關(guān)鍵技術(shù)。本文以PCB終飾工藝為研究背景,針對(duì)化學(xué)鍍鎳/置換鍍金(ENIG)工藝存在的缺陷,開發(fā)鈀催化化學(xué)鍍金方法,并將該工藝用于PCB終飾,作為化學(xué)鍍鎳/化學(xué)鍍鈀/置換鍍金(ENEPIG)工藝的組成部分。傳統(tǒng)的ENIG工藝過程中,金的沉積是通過鎳金置換反應(yīng)來進(jìn)行,由于Ni-P表面的胞狀結(jié)構(gòu)以及氰根離子的滲透作用,使表面電荷分布不均勻,在置換反應(yīng)過程中造成局部位置的嚴(yán)重腐蝕。這種出現(xiàn)Ni-P層過腐蝕的ENIG鍍層在焊接過程中容易出現(xiàn)“黑盤”問題。本研究以亞硫酸體系鍍金溶液在ENIG工藝中的應(yīng)用為切入點(diǎn),通過鍍液穩(wěn)定性和鍍層均勻性的表征,對(duì)配位劑組成和工藝條件進(jìn)行了優(yōu)化。優(yōu)化后的鍍液穩(wěn)定,在Ni-P表面施鍍10 min,所得鍍層厚度為0.05μm,相對(duì)標(biāo)準(zhǔn)偏差(RSD)值小于10%,鍍層表面粗糙度為20.8 nm。通過對(duì)金層在Ni-P表面的沉積過程及鍍層形貌的表征和分析,建立金層在Ni-P表面的生長(zhǎng)模型,發(fā)現(xiàn)亞硫酸體系鍍金液在Ni-P表面鍍金過程依然是置換反應(yīng),無“基體催化”效果,不能夠解決PCB“黑盤”問題。此外,在使用亞硫酸-硫代硫酸鹽的體系在Ni-P表面鍍金過程中,發(fā)現(xiàn)鍍層中有雜質(zhì)S存在。通過實(shí)驗(yàn)證明了S雜質(zhì)主要存在于Ni-P表面,在鍍金過程中隨著Au層厚度的增加,S雜質(zhì)含量逐漸降低。在上述研究的基礎(chǔ)上,通過在ENIG工藝中加入鈀層解決Ni-P腐蝕問題。首先對(duì)置換鍍鈀、次磷酸鍍鈀以及甲酸鍍鈀的工藝過程及鍍層形貌進(jìn)行表征,發(fā)現(xiàn)這幾種常用鍍鈀工藝存在不同的缺陷:置換鍍層存在孔隙、次磷酸鈉鍍鈀層以胞狀結(jié)構(gòu)存在、甲酸鍍鈀層由晶體顆粒組成,這幾種鍍鈀層并不適合作為Ni-P表面的阻擋層。另外,使用甲酸鹽作為還原劑在Ni-P表面鍍鈀的過程是“兩段式”反應(yīng),通過實(shí)驗(yàn)證明了這個(gè)過程中首先進(jìn)行的是Ni和Pd2+的置換反應(yīng),然后在Pd上進(jìn)行自催化沉積過程。本文在明確了鍍鈀層形貌與組成之間的關(guān)系后,設(shè)計(jì)制備以Na H2PO2和HCOONa復(fù)配的雙還原劑新型鍍鈀技術(shù),獲得通過調(diào)整Na H2PO2的量來控制Pd-P層中磷含量的方法。工藝優(yōu)化后制備鍍層磷含量能夠低于1 wt%,經(jīng)過SEM和AFM測(cè)試,證實(shí)了該工藝得到的低磷Pd-P鍍層具有平整光潔的表面。在Ni-P表面鍍覆了低磷Pd-P層之后,其“胞狀”結(jié)構(gòu)被掩蓋,鍍層耐蝕性能顯著提高。在制備合適的Pd-P鍍層之后,將亞硫酸鍍金體系用于Pd-P鍍層表面鍍金,組成整個(gè)ENEPIG工藝過程。通過對(duì)反應(yīng)過程電位變化、鍍液金屬離子濃度變化以及鍍層生長(zhǎng)速率的測(cè)試分析,證明了金在Pd-P鍍層表面的沉積反應(yīng)類型為基體催化化學(xué)鍍金,無鈀金置換反應(yīng)發(fā)生。在鍍覆了薄層Pd-P的Ni-P表面,金的沉積反應(yīng)包括鎳金置換沉積和基體催化化學(xué)沉積。提高Pd-P層厚度能夠降低置換反應(yīng)比例,當(dāng)鍍覆Pd-P層厚度為0.1μm時(shí),鍍金過程對(duì)Ni-P的置換比例為34.2%。在Ni-P層和金層中間加入Pd-P層,能夠抑制“黑盤”產(chǎn)生的原因包括:減少了沉積金層過程中鍍金液對(duì)Ni的置換侵蝕;對(duì)Ni-P“胞狀”結(jié)構(gòu)之間的縫隙進(jìn)行覆蓋填充,使其在沉積Au層過程中不發(fā)生嚴(yán)重的局部腐蝕;使ENEPIG工藝表面無富磷層、無S雜質(zhì),有利于提高焊接牢度。最后對(duì)ENEPIG鍍層耐蝕性、可焊性及焊接牢度進(jìn)行表征,驗(yàn)證了本文研制的ENEPIG工藝具有良好的實(shí)用性。
[Abstract]:The finishing process of printed circuit board (PCB) is the last surface treatment step in its manufacturing process. It not only provides protection layer for the line surface, but also the key technology to ensure the effective connection of printed circuit board in assembly and use. In this paper, the defects of electroless nickel / replacement gold plating (ENIG) process are introduced with the research background of the PCB finishing process. The method of palladium catalyzed chemical gold plating was developed and used in PCB finishing as part of the electroless nickel plating / electroless palladium / replacement gold plating (ENEPIG) process. In the traditional process of ENIG, gold deposition was carried out through the nickel gold replacement reaction. The surface charge of the Ni-P surface and the penetration of cyanogen ions made the surface charge. The distribution is not uniform and the local position is seriously corroded during the replacement process. The Ni-P layer of ENIG coating is prone to "black disk" problem during the welding process. This study is based on the application of gold plating solution in the sulfite system in the ENIG process as the breakthrough point, by the stability of the plating bath and the characterization of the uniformity of the coating, the coordination of the coordination of the plating solution to the coordination of the plating solution is made. The composition and technological conditions were optimized. The optimized plating bath was stable and 10 min was plated on the Ni-P surface. The thickness of the coating was 0.05 mu m, the relative standard deviation (RSD) value was less than 10%, the surface roughness of the coating was 20.8 nm., and the growth of gold layer on the Ni-P surface was established by the deposition process of gold layer on the surface of Ni-P and the analysis of the appearance of the coating. It is found that the gold plating process in the sulfite system is still a replacement reaction on the Ni-P surface, without the "matrix catalysis" effect and can not solve the PCB "black disk" problem. In addition, the presence of impurity S in the coating is found in the gold plating process on the Ni-P surface using sulfite thiosulfate system. It is proved by experiments that the S impurity is mainly stored. In the Ni-P surface, the content of S impurities gradually decreases with the increase of the thickness of the Au layer during the gold plating process. On the basis of the above study, the palladium layer is added to the Ni-P corrosion problem by adding the palladium layer in the ENIG process. First, the process of replacement palladium plating, palladium plating and palladium plating of the formic acid are characterized, and these commonly used palladium plating are found. There are different defects in the process: the replacement coating has a pore, the palladium layer of sodium hypophosphite is in a cellular structure, the palladium coating of the formic acid is composed of crystal particles. These palladium plating layers are not suitable to be used as the barrier layer on the surface of Ni-P. In addition, the process of using formate as a reductant on Ni-P surface is a "two stage" reaction, through experimental evidence. It is clear that the first process is the replacement reaction of Ni and Pd2+, and then the process of autocatalytic deposition on Pd. After making clear the relationship between the morphology and composition of the palladium plating layer, a new palladium plating technology was designed to prepare a double reductant with Na H2PO2 and HCOONa, and the amount of Na H2PO2 was adjusted to control the phosphorus content in the Pd-P layer. The phosphorus content of the deposited coating can be less than 1 wt% after the process optimization. After SEM and AFM tests, it is proved that the low phosphorus Pd-P coating obtained by this process has a smooth and smooth surface. After coating the low phosphorus Pd-P layer on the Ni-P surface, the "cell" structure is covered up and the corrosion resistance of the coating can be significantly improved. After the preparation of the suitable Pd-P coating, the coating will be prepared. The gold plating system of sulfite is used for gold plating on the surface of Pd-P coating to form the whole process of ENEPIG process. By analyzing the change of the potential of the reaction process, the change of metal ion concentration and the growth rate of the coating, it is proved that the type of deposition reaction of gold on the surface of the Pd-P coating is the matrix plating chemical gold plating, no palladium replacement reaction occurred. On the Ni-P surface of the thin layer of Pd-P, the deposition reaction of gold includes nickel gold replacement deposition and matrix catalytic chemical deposition. Increasing the thickness of Pd-P layer can reduce the proportion of replacement reaction. When the thickness of the coating Pd-P layer is 0.1 u m, the replacement proportion of the gold plating process to Ni-P is 34.2%. in the Ni-P layer and the gold layer, which can inhibit the "black disk" production. The reasons include: reducing the replacement erosion of gold plating solution to Ni during the deposition of gold deposits, covering and filling the cracks between the Ni-P "cell" structures so that they do not have serious local corrosion during the deposition of the Au layer, so that the surface of the ENEPIG process has no phosphorous rich layer, no S impurities, and it is beneficial to improve the fastness of the welding. Finally, the corrosion resistance of the ENEPIG coating is improved. Characterization of weldability and welding fastness proves that the ENEPIG process developed in this paper has good practicability.
【學(xué)位授予單位】：哈爾濱工業(yè)大學(xué)
【學(xué)位級(jí)別】：博士
【學(xué)位授予年份】：2016
【分類號(hào)】：TB306;TN41

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