印制电路板通孔电镀铜添加剂的研究

在2.0 A/dm2、24°C和空气搅拌条件下,采用由60 g/L Cu SO4·5H2O、200 g/L H2SO4、60 mg/L Cl-和4种添加剂组成的酸性镀铜液对印制线路板通孔进行电镀铜。以PCB通孔孔口、孔中心铜层厚度和镀液的深镀能力为指标,通过正交试验对添加剂聚二硫二丙烷磺酸钠(SPS)、聚乙二醇(PEG-10000)、季铵盐类化合物(MX-86)和嵌段聚醚类化合物(SQ-5)的用量进行优化,得到添加剂的最优组合为:SPS 20 mg/L,SQ-5 0.5 g/L,PEG-10000 0.2 g/L,MX-86 20 mg/L。采用该配方对深径比为8∶1的通孔电镀时,深镀能力在90%以上,铜层的延展性和可靠性均能满足印制线路板的工业应用要求。     

高深径比通孔电镀铜的添加剂优化

以75 g/L CuSO4·5H2O、230 g/L硫酸和0.1 g/L十二烷基苯磺酸钠(SDBS)组成的溶液作为基础镀液,并以Cl-、聚乙二醇(PEG-10000)、聚二硫二丙烷磺酸钠(SPS)及2,2′-二硫代二吡啶(2-PDS)作为添加剂,在温度(23±2)℃、电流密度1.8 A/dm2和空气搅拌的条件下对印制电路板(PCB)上深径比为10∶1的通孔电镀铜。以深镀能力作为评价指标,通过正交试验对添加剂用量进行优化,得到较优的组合为:SPS 5 mg/L,PEG 250 mg/L,Cl- 60 mg/L,2-PDS 2 mg/L。采用该组合添加剂电镀通孔时,深镀能力高达112.9%,镀层均匀、细致、平整,抗热冲击性能良好,符合PCB生产对可靠性的要求。     

添加剂对高电流密度下通孔电镀铜的影响

通过测量25°C的计时电位曲线研究了聚二硫二丙烷磺酸钠(SPS)、二甲基甲酰胺基丙烷磺酸钠(TPS)、N,N-二甲基二硫代甲酰胺丙烷磺酸钠(DPS)、3-巯基-1-丙烷磺酸钠(MPS)、噻唑啉基二硫代丙烷磺酸钠(SH110)和醇硫基丙烷磺酸钠(HP)这6种常用添加剂对高电流密度(3.0 A/dm2)下通孔电镀铜的影响。基础镀液为70 g/L硫酸+200 g/L五水合硫酸铜+60 mg/L氯离子,抑制剂为200 mg/L聚乙二醇(PEG-10000),整平剂为1 mg/L健那绿(JGB)。结果表明,镀液中单独加入抑制剂时镀液的分散能力没有提高,而MPS的去极化能力过强,能抵消抑制剂和整平剂的作用。采用100 mg/L PEG-10000+1 mg/L TPS+1 mg/L JGB作为添加剂时,镀液的分散能力为82%,所得通孔镀铜层热应力情况较好。     

加速剂对铝基覆铜板通孔电镀铜的影响

在由70 g/L硫酸铜、200 g/L浓硫酸、60 mg/L盐酸、200 mg/L聚乙二醇(PEG6000)和1 mg/L健那绿B(JGB)组成的基础镀液中分别添加聚二硫二丙烷磺酸钠(SPS)、3-巯基-1-丙磺酸钠(MPS)和N,N-二甲基二硫代甲酰胺丙烷磺酸钠(DPS)作为加速剂。通过计时电位曲线测试和热冲击试验,研究了不同加速剂对通孔电镀铜的影响。结果表明,镀液中添加2.5 mg/L SPS或9 mg/L DPS作为加速剂时,镀液的深镀能力显著提高,所得Cu镀层的抗热冲击性能合格。     

骨胶和聚二硫二丙烷磺酸钠对厚电解铜箔性能的影响

研究了骨胶和聚二硫二丙烷磺酸钠(SPS)对厚电解铜箔光泽、表面粗糙度、抗拉强度、延伸率等的影响.结果表明,随骨胶质量浓度增大,厚电解铜箔的表面粗糙度先减小后增大,当骨胶质量浓度为4 mg/L时,表面粗糙度(Rz)最低,为10.1μm.电解液中骨胶过量时,加入SPS可有效降低铜箔的表面粗糙度,得到平滑、均匀而细致的厚电解铜箔.     

整平剂对铝基覆铜板通孔电镀铜的影响

在由100 g/L CuSO₄·5H₂O、200 g/L浓硫酸、60 mg/L Cl^-、200 mg/L聚乙二醇(PEG-6000)和10 mg/L聚二硫二丙烷磺酸钠(SPS)组成的镀液中加十六烷基三甲基溴化铵(CTAB)、聚乙烯吡咯烷酮(PVP)或2-巯基-5-甲基-1,3,4-噻二唑(MMTD)作为整平剂。通过计时电位曲线测试和热冲击试验,研究了不同整平剂对通孔电镀铜的影响。结果表明,镀液中添加2～4 mg/L CTAB或MMTD时都能够在一定程度上抑制铜电沉积,镀液的深镀能力均符合≥80%的要求。但只有采用4 mg/L MMTD作为整平剂时所得电镀铜层的抗热冲击性能合格。     

新型酸铜电镀加速剂MA的应用研究

酸性电镀铜是重要的电子互连制造技术之一。为解决其工业生产过程中,聚二硫二丙烷磺酸钠（SPS）和3-巯基-1-丙烷磺酸钠（MPS）稳定性欠佳,导致镀液老化,使添加剂监控失效、镀液均镀能力下降和镀层结瘤等问题,通过电化学实验、定量分析实验和电镀实验,研究了巯基丙烷磺酸络二铜（MA）作为电子互连中酸铜电镀加速剂的特性。结果表明,MA能够直接替代原配方中的SPS和MPS,作为酸铜加速剂使用,且工作浓度更低,具有更宽的CVS分析线性区间,能够提供更准确的定量分析结果,在微通孔保型电镀中表现出良好的均镀能力,并能实现微盲孔的超级填充,不改变铜镀层的金相织构等,展现出广阔的应用前景。     

自配酸铜光亮剂的经验及配方

阐述了自配酸铜光亮剂的好处。指出最简单的M(2巯基苯并咪唑)–N(乙撑硫脲)–SP(聚二硫二丙烷磺酸钠)–P(聚乙二醇)体系所存在的问题及改进方法。给出了一种二液型酸铜光亮剂的配方。总结了可能导致自配酸铜光亮剂失败的原因。     

整平剂对酸性电镀硬铜的影响

研究了噻唑啉基二硫代丙烷磺酸钠(SH110)、十六烷基三甲基溴化铵(CTMAB)、聚乙烯亚胺烷基盐(PN)以及四氢噻唑硫酮(H1)4种整平剂对酸性电镀铜层表面形貌和显微硬度的影响。基础镀液组成为:Cu SO4·5H2O 220 g/L,H2SO4 55 g/L,Cl-60 mg/L,聚二硫二丙烷磺酸钠(SPS)3 mg/L,聚乙二醇(PEG6000)100 mg/L。在一定范围内,整平剂的质量浓度越高,镀层表面越光滑、平整,显微硬度越高。选择2 g/L H1作为整平剂时,所得镀层的显微硬度可长时间(14 d以上)满足电子雕刻的要求(180~220 HV)。H1与其他3种整平剂之间的协同作用的强度顺序为:H1+SH110H1+CTMABH1+PN。     

挠性板通孔电镀配方与工艺优化研究

为解决使用传统电镀液配方进行挠性板通孔电镀时出现的均镀能力(TP)差等问题,本文基于加速剂聚二硫二丙烷磺酸钠(SPS)、N,N-二甲基二硫代甲酰胺丙烷磺酸钠(DPS)的电化学性能测试,研究了整平剂对挠性板通孔电镀效果的影响,并对无整平剂的镀液体系中挠性板通孔电镀的影响因素进行了分析讨论。结果表明,SPS具有持续性的加速作用,是典型的加速剂,而DPS在高浓度条件下呈现出抑制效果,具有加速-整平双重特性;无整平剂体系下挠性板通孔的电镀效果(TP≥200%)明显要比有整平剂体系下的电镀效果(TP≈100%)要好,但是无整平剂条件下所得的铜镀层质量差;通过在无整平剂体系中加入DPS,利用DPS的微整平性能能够有效改善镀层质量。提高镀液中的铜离子浓度,降低酸的浓度、采用小电流密度、短时间电镀以及低气流量有利于提高通孔电镀的均镀能力。     

Design and achievement of a complete bottom-up electroless copper filling for sub-micrometer trenches

The bottom-up filling of electroless copper usually depends on inhibiting the Cu deposition at the surface or accelerating the Cu deposition in the bottom of trenches to achieve a relative high deposition rate of electroless copper in the bottom of trenches. In this paper, a complete bottom-up filling of electroless copper, in which the deposition rates of the electroless copper were not only inhibited at the surface of the substrate, but also were accelerated in the bottom of the trenched, was designed and achieved in the plating bath with an addition of bis (3-sulfopropyl) disulfide (SPS) and polyethylene glycol (PEG). The cross-sectional SEM observation of trenches indicated that all trenches with different widths ranging from 100 to 290 nm were filled completely by electroless copper, and no void was found. This was attributed to three factors, the electroless Cu deposition was accelerated markedly by an addition SPS only; but it was suppressed sharply by a combination addition SPS and PEG-4000; the large molecular weight and lower diffusion coefficient of PEG-4000 resulted in concentration gradient of PEG-4000 in the trenches. The effects of PEG-4000 and SPS on the polarization behaviors of the electroless copper plating bath were investigated by the linear sweep voltammetry method and mixed potential theory.     

去屑香波中吡啶硫酮锌的沉积机理研究

通过测试去屑香波的絮胶形态、皮肤上吡啶硫酮锌(ZPT)的沉积量及漂白头发的梳理性,对比不同阳离子聚合物和硅油粒径大小对ZPT的覆盖均匀程度和沉积量的作用效果。研究发现:体系中由于同时存在小粒径硅油(SPS)和ZPT的过度积聚,大部分阳离子聚合物不适用于SPS去屑香波中,而改性瓜儿胶由于其特殊的表面处理,不会形成过度絮胶,适用于SPS去屑香波,保证ZPT有效沉积并提供优越调理性;而含大粒径硅油(LPS)的去屑香波中ZPT有效沉积与阳离子聚合物的电荷密度和分子量成正比。     

高产量、高分子量透明质酸发酵条件优化

研究了搅拌转速、初糖浓度及通气量对兽疫链球菌Streptococcus zooepidemicus WSH24发酵生产透明质酸的影响. 研究结果表明,搅拌转速对透明质酸产量及分子量影响很大,搅拌转速为200 r/min时透明质酸产量达到5.3 g/L,平均分子量达到1.88×106 Da,产率系数为0.13 g/g;初始葡萄糖浓度为65.8 g/L时有利于透明质酸的生产,产量达5.9 g/L,平均分子量达1.90×106 Da,产率系数为0.17 g/g;通气量对透明质酸的发酵也有较大影响,通气量为1.2 L/(min·L)时透明质酸的产量及分子量均高于0.5 L/(min·L)时的发酵结果.     

Enhancement of filling performance of a copper plating formula at low chloride concentration

In this work, microvia filling was performed by copper electroplating using two plating formulas with and without a leveler at a low concentration of chloride. The base plating solution contained CuSO₄, H₂SO₄, polyethylene glycol (PEG), bis (3-sulfopropyl) disulfide (SPS) and Cl⁻. When the Cl⁻ concentration was lower than 30 ppm, the plating formula without a leveler became dead for bottom-up filling, resulting in conformal deposition. The addition of 1 ppm Alcian Blue, used as a leveler, could effectively recover the filling performance of the plating formula with low chloride concentration. Electrochemical analyses revealed possible mechanisms. The results demonstrate that the usage of Alcian Blue can widen the operation window of chloride concentration, since it can assist PEG in competing with SPS in adsorption at low chloride concentration.     

Environmental usefulness of PLA/PEG blends for controlled-release systems of soil-applied herbicides

Blends consisting of biodegradable polylactide (PLA) and poly(ethylene glycol) (PEG) were investigated for their usefulness as an environmentally friendly herbicide formulation with prolonged activity. The aim of this study was to evaluate the release rate of selected soil-applied herbicides from the PLA/PEG blend containing PEG of various molecular weights and to assess the phytotoxicity of the PEGs according to OECD 208 guidelines. The release rate of immobilized herbicides was correlated with degradation of the blends used. The progress of PLA/PEG blend degradation in water, soil, and activated sludge was estimated by sample weight loss, changes in blend composition, and microscopic observations of the blend surfaces during the experiment. The proposed formulation of the immobilized herbicide in a blend consisting of slowly biodegradable PLA and water-soluble PEG provides the possibility to release the herbicides for a relatively long time, for approximately six months, which is a demand of weed management. The effect of PEGs on plant growth and development was dependent on both their concentration and molecular weight. With a higher concentration in soil and a higher molecular weight of PEG, a more harmful effect on plants was noticed. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47856.     

PEG、PPG改性PLA材料的性能研究

采用熔融共混法用聚乙二醇(PEG)对生物可降解材料聚乳酸(PLA)进行改性,研究了PEG的相对分子质量对共混体系热性能和力学性能的影响,对比了相同相对分子质量的PEG和聚丙二醇(PPG)由分子结构差异对共混体系性能的影响。结果表明,PEG的相对分子质量为2 000时,改性效果最好;相同相对分子质量的PEG改性效果优于PPG。     

PEG/（NH4）2SO4双水相萃取分离茶氨酸的研究

采用聚乙二醇(PEG)/(NH4)2SO4双水相体系萃取分离生产茶多酚所得废液中的茶氨酸,考察了PEG分子量与含量、硫酸铵含量、pH、温度、加盐(KCl、KBr、KI)、茶氨酸含量对双水相及萃取分离茶氨酸的影响。结果表明,PEG/(NH4)2SO4双水相萃取分离茶氨酸的适宜条件是:PEG平均分子量为4 000,质量分数为10%,硫酸铵质量分数为15%,pH约为6,30℃。在此条件下,茶氨酸的分配系数K1=0.16,蛋白质的分配系数K2=0.28,糖类的分配系数K3=9.8,茶氨酸在下相的萃取率为89.5%,可以将茶多酚废液中的茶氨酸与糖类及其他有颜色的杂质分开。     

椰油丙基酰胺甜菜碱/聚乙二醇水溶液的分相研究

Phase separation behavior of cocamidopropyl betaine/water/polyethylene glycol (PEG) system was studied. The effects of concentration and molecular weight of PEG on the phase separation behavior were investigated. Clouding occurred when the con-centration of PEG was large enough in the betaine aqueous solution, and the concentration of PEG at cloud point decreased with the increase of PEG molecular weight for a constant betaine concentration. The bottom phase was the PEG-rich phase, and the upper phase was the betaine-rich phase. The volumetric ratio of PEG-rich phase to betaine-rich phase, at the same difference between the PEG concentration and the one at the cloud point, Ccp (0.1 g•ml－1), decreased as the PEG molecular weight increased and approached 1 for higher PEG molecular weight (about 20000), which was similar to the typical aqueous two-phase system. This volumetric ratio depended on the initial PEG concentration, but independent of PEG molecular weight. The concentration ratio of betaine to PEG in both phases depended on the Ccp, independent of PEG molecular weight.