本文選題：甲磺酸 + 添加劑　； 參考：《哈爾濱工業(yè)大學(xué)》2016年博士論文

【摘要】：近年來,隨著人們對環(huán)境問題的關(guān)注和重視,甲磺酸因具有無毒及完全生物降解特點(diǎn),逐漸成為鍍錫應(yīng)用新方向。目前,國內(nèi)市場上的甲磺酸電鍍錫用添加劑幾乎被國外品牌壟斷,這對國內(nèi)電鍍錫產(chǎn)業(yè)發(fā)展極為不利。因此開發(fā)具有自主知識(shí)產(chǎn)權(quán)的鍍錫添加劑具有十分重要的現(xiàn)實(shí)意義。在本文中,利用量子化學(xué)計(jì)算和分子動(dòng)力學(xué)模擬(MD),結(jié)合電化學(xué)測量,鍍液性能測試和掃描電子顯微鏡等手段對甲磺酸鍍液體系穩(wěn)定性、添加劑優(yōu)選、鍍液性能優(yōu)化、錫初始成核過程以及添加劑在陰極表面作用進(jìn)行了研究。甲磺酸分子的電子特性和軌道信息表明磺酸基(-SO_3)是分子中親電和親核的活性位置,甲磺酸根(MSA-)的EHOMO能量值為-1.53 e V,ΔEHOMO-LUMO為6.837 e V,根據(jù)前線軌道理論,說明MSA-與金屬表面吸附作用強(qiáng)于硫酸,其靜電勢分布顯示MSA-傾向于在金屬表面垂直吸附;結(jié)構(gòu)優(yōu)化結(jié)果證實(shí)甲磺酸錫體系中有Sn[MSA]+、Sn[MSA]3-和Sn[MSA]2~(2+)三種絡(luò)合構(gòu)型存在;循環(huán)伏安曲線(CV)表明甲磺酸基礎(chǔ)鍍液的陰極極化度大于硫酸體系,但這種弱陰極極化不能抑制錫枝晶的生長。選擇對苯二酚作為甲磺酸鍍錫液穩(wěn)定劑,其酚醌結(jié)構(gòu)轉(zhuǎn)換實(shí)現(xiàn)電化學(xué)可逆循環(huán),能夠長期穩(wěn)定鍍液。通過鐵離子對錫離子氧化水解的影響研究發(fā)現(xiàn),Sn~(2+)的氧化水解遵循先氧化生成Sn~(4+)再水解形成沉淀的路徑,Fe~(3+)不能與Sn~(2+)共存,直接將Sn~(2+)氧化成Sn~(4+),Fe~(2+)在5~15 g/L時(shí),具有減緩Sn~(2+)氧化水解速度的作用,Fe~(2+)為10 g/L時(shí),其減緩作用最強(qiáng)。為了從甲磺酸體系中獲得有用鍍層,本文通過添加劑的界面作用實(shí)現(xiàn)對鍍錫陰極過程的控制,優(yōu)選出不同抑制能力的添加劑控制Sn~(2+)的放電過程,獲得亞光到全光亮的錫鍍層外觀。首先,基于亞光鍍錫添加劑一般特征,根據(jù)分子物化特性和前線軌道理輪,從聚醚中設(shè)計(jì)優(yōu)選出環(huán)氧乙烷環(huán)氧丙烷嵌段聚合物EPE4600,其分子量為4600,EO占40 wt%,作為甲磺酸鍍錫陰極抑制劑,獲得了亞光錫鍍層。靜態(tài)下Hull cell測試顯示EPE4600濃度為0.8~1.6 g/L,[Sn~(2+)]為15 g/L時(shí),EPE4600允許鍍液最大電流密度為8.0 A/dm2(市售高速鍍錫TPG7添加劑為3.0 A/dm2),結(jié)合EPE4600濁點(diǎn)為79℃,綜合表明該鍍液允許在寬電流密度和寬溫度區(qū)間工作,符合高速電鍍要求。通過旋轉(zhuǎn)圓盤電極(Pt-RDE)在不同調(diào)制動(dòng)力學(xué)條件下EPE4600在鍍液中的伏安特性和計(jì)時(shí)電位曲線說明EPE4600在陰極表面吸附并生成一層阻擋膜,該膜層阻礙Sn~(2+)擴(kuò)散傳遞,是提高鍍液陰極極化度和抑制錫枝晶生長的本質(zhì),據(jù)此建立了EPE4600吸附阻機(jī)理擋模型。密度泛函理論(DFT)計(jì)算和MD共同佐證了EPE4600在甲磺酸體系中,EPE4600分子中PO嵌段部分與界面具有較強(qiáng)的吸附活性,與MSA-存在協(xié)同吸附作用。通過暫態(tài)電流曲線研究EPE4600在甲磺酸-硫酸混合體系中錫成核行為,發(fā)現(xiàn)甲磺酸體系中,錫的成核符合擴(kuò)散控制下的三維連續(xù)成核模型,硫酸的引入,錫初始沉核模型傾向于瞬時(shí)成核轉(zhuǎn)變。計(jì)算了的錫初始成核活性位點(diǎn)(N0)和生長速率(A),臨界吉布斯成核自由能(ΔGcrit)和臨界成核尺寸(Ncrit),結(jié)果顯示甲磺酸體系中錫在電極表面活性位點(diǎn)是硫酸及其混酸體系的5~10倍,Ncrit為0~1.5說明電極表面活性位點(diǎn)上有部分基底原子參與成核,錫與基底原子有很強(qiáng)的結(jié)合能。錫的初始沉積形貌印證了電化學(xué)的成核特征。將EPE4600用于高速電鍍制備0.7 g/m2低錫量鍍層,結(jié)果顯示鍍層均勻性和致密性優(yōu)良,可用于低錫量高速鋼板電鍍錫,節(jié)約錫資源。為了實(shí)現(xiàn)對甲磺酸體系鍍錫陰極過程的進(jìn)一步抑制,獲得光亮外觀鍍層。優(yōu)選出糠叉丙酮、芐叉丙酮和戊二醛為光亮劑,NP-10和NS-665為復(fù)合載體的光亮劑組合。開發(fā)了光亮錫HIT-2添加劑配方,實(shí)現(xiàn)了無甲醛光亮鍍錫工藝,靜態(tài)下鍍液最大光亮電流密度范圍為0~5.1 A/dm2,得到(112)晶面強(qiáng)織構(gòu)的光亮錫鍍層,可用于卷對卷式的連續(xù)電鍍工藝�；贖IT-2添加劑各組分在錫電沉積過程中的電化學(xué)行為,發(fā)現(xiàn)芐叉丙酮和糠叉丙酮共同吸附抑制了Sn~(2+)的放電過程,戊二醛和丙烯酸削弱了芐叉丙酮和糠叉丙酮的吸附作用,這種反作用實(shí)現(xiàn)了光亮錫的電沉積。MD發(fā)現(xiàn)了芐叉丙酮和糠叉丙酮分子傾向于平鋪吸附,提出了添加劑分子間的界面吸附構(gòu)型。甲磺酸亞光和光亮鍍錫添加劑在通孔電鍍中,實(shí)現(xiàn)了通孔內(nèi)外選擇性鍍錫,揭示了可作為微凸點(diǎn)電鍍工藝,用于高集成度芯片互聯(lián)封裝。
[Abstract]:In recent years, with the attention and attention to environmental problems, methanesulfonic acid has gradually become a new direction for the application of tin plating because of its non-toxic and complete biodegradation characteristics. At present, the additives for electroless tin plating on the domestic market are almost monopolized by foreign brands, which are extremely unfavorable for the development of electroplating tin industry in China. Therefore, the development has independent knowledge. The tin plating additives for property rights are of great practical significance. In this paper, the stability of the sulfonic acid bath system, the optimization of additives, the optimization of the performance of the plating solution, the initial nucleation process of tin, and the addition of the chemical measurement and molecular dynamics simulation (MD), the electrochemical measurement, the electroplating performance test and the scanning electron microscope are used in this paper. The effect of addition agent on the surface of the cathode was studied. The electronic properties and orbital information of mesylsulfonic acid molecules indicate that sulfonic acid group (-SO_3) is the active position of electrophilic and nucleophilic in the molecule. The EHOMO energy of MSA- is -1.53 e V and delta EHOMO-LUMO is 6.837 e V. According to the front line theory, the adsorption of MSA- and metal surface is stronger than sulfur. The static potential distribution of acid shows that MSA- tends to adsorb vertically on the metal surface, and the structural optimization results confirm that there are three complex configurations of Sn[MSA]+, Sn[MSA]3- and Sn[MSA]2~ (2+) in tin mesylate system, and cyclic voltammetry curve (CV) indicates that the cathodic polarity of the base plating solution is larger than the sulphuric acid system, but the weak cathode polarization can not be suppressed. The growth of tin dendrites. The conversion of phenols as a tin plating bath stabilizer, the conversion of phenol quinone structure to the electrochemical reversible cycle, can stabilize the bath for a long time. Through the effect of iron ion on the oxidation hydrolysis of tin ions, it was found that the oxidation hydrolysis of Sn~ (2+) followed the first oxidation of Sn~ (4+) to form the precipitation path, Fe~ (3+) did not. Coexistence with Sn~ (2+) can directly oxidize Sn~ (2+) into Sn~ (4+) and Fe~ (2+) in 5~15 g/L, which has the effect of slowing down the oxidation hydrolysis of Sn~ (2+). When it is 10, it has the strongest slowing down effect. In order to obtain a useful coating from the sulfonic acid system, this article passes the interface action of the additive to realize the control of the process of tin plating cathodic process. The suppressing additive controls the discharge process of Sn~ (2+) and obtains the appearance of the light to all bright tin coating. First, based on the general characteristics of the tin plating additive, the epoxy propane epoxy propane block polymer EPE4600 is designed and optimized from the molecular physicochemical properties and the front orbital wheel. The molecular weight of the polymer is 4600, and the EO is 40 wt%. The tin coating was obtained for the tin plating tin cathode inhibitor. The static Hull cell test showed that the maximum current density of EPE4600 was 8 A/dm2 (3 A/dm2) when the concentration of EPE4600 was 0.8~1.6 g/L and [Sn~ (2+)], and the nodal cloud point was 79 C. The flow density and wide temperature range work in accordance with the high speed electroplating requirements. The volt ampere characteristic and the timing potential curve of the EPE4600 in the bath under the different modulation kinetics conditions show that EPE4600 adsorbs on the surface of the cathode and generates a layer of barrier film on the surface of the cathode, which hinders the diffusion transfer of Sn~ (2+) and increases the cathode pole of the plating bath. The nature of inhibition and inhibition of the growth of tin dendrite was established. The EPE4600 adsorption resistance mechanism model was established. The density functional theory (DFT) calculation and MD co supported that EPE4600 was in the mesylate system. The PO segment in EPE4600 molecules had strong adsorption activity with the interface, and there was a synergistic adsorption with MSA-. The transient current curve was used to study EPE46. 00 in the methanesulfonic acid sulphuric acid mixing system, the nucleation of tin in a sulfonic acid system shows that the nucleation of tin conforms to the three-dimensional continuous nucleation model under the control of diffusion. The introduction of sulphuric acid, the initial nucleation model of tin is inclined to the transient nucleation transformation. The initial nucleation active site (N0) and growth rate (A) of tin are calculated, and the critical Gibbs nucleation free energy (delta G) Crit) and critical nucleation size (Ncrit) show that the surface active site of tin in the sulfonic acid system is 5~10 times of sulfuric acid and its mixed acid system. Ncrit is 0~1.5 indicating that some basal atoms are involved in the nucleation on the surface active site of the electrode, and the tin has strong binding energy to the substrate. The initial deposition morphology of tin confirms the electrochemistry. EPE4600 is used to prepare 0.7 g/m2 low tin coating for high speed electroplating. The results show that the coating has good uniformity and compactness. It can be used for electroless tin plating of high speed steel plate with low tin content and save tin resources. In order to further restrain the process of tin plating cathodic plating on methanesulfonic acid system, the bright appearance coating is obtained. The optimization of furfurone acetone, benzyl acetone is obtained. With glutaraldehyde as a brightener, NP-10 and NS-665 as the combination of brighteners, a brightening tin HIT-2 additive formula was developed to achieve a formaldehyde free tin plating process. The maximum bright current density range in the static bath was 0~5.1 A/dm2, and the bright tin coating with (112) strong textured surface was obtained, which could be used for roll to roll continuous electroplating. Based on the electrochemical behavior of HIT-2 additives in the electrodeposition of tin, it was found that the CO adsorption of benzyl acetone and furfurone acetone inhibited the discharge process of Sn~ (2+), and glutaraldehyde and acrylic acid weakened the adsorption of benzyl acetone and furfurone acetone. This reaction realized the electrodeposition of bright tin.MD and found benzyl acetone and bran. An intermolecular interface adsorption configuration between the molecules of the proproacetone molecule is put forward. The sub light and bright tin plating additives of mesylate have been used in the through hole electroplating to realize the selective tin plating inside and outside the hole. It reveals that the electroplating process can be used as a micro convex point plating process for high integration chip interconnected package.
【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)】：TQ153.13

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