随着第五代移动通信技术(5th Generation Mobile Communication Technology，5G)的到来，全球超低轮廓(HVLP)铜箔的需求量持续增长。为了获得性能良好并适用于高频高速电路用铜箔，需要调和低轮廓和高抗剥离性能之间的矛盾。目前我国仅有几家公司拥有相关技术，但是产品稳定性等方面与国外先进企业相比还存在较大差距，产品成熟度也不高。添加剂是影响铜箔质量的关键因素，因此寻求更佳电解添加剂复配技术以改善电解工艺条件，是取代进口铜箔的重要途经。本文模拟企业后处理的工艺参数，探索不同添加剂体系及其作用机制，从而获得性能优异的5G通讯用铜箔的添加剂配方。

本文的主要研究内容及结论如下：

采用“低铜高酸”基础电解液(Cu²⁺浓度：10 g/L、浓H₂SO₄浓度：110 g/L)，研究溶液中引入单一聚二硫二丙烷磺酸钠(SPS)、羟乙基纤维素(HEC)、明胶和苯基二硫丙烷磺酸钠(BSP)四种有机添加剂对铜箔粗化层组织及性能的影响，并研究其对铜电沉积过程电化学行为的影响。结果表明，SPS可促进铜沉积，细化粗化层铜颗粒，使铜箔剥离强度提高至0.49 N/mm；HEC会抑制铜箔活性点位的铜沉积，但其提高剥离强度的效果较差；明胶可提高铜形核密度，在提高剥离强度(0.48 N/mm)的同时也降低了表面粗糙度(1.58 μm)。此外，通过对比单一添加剂性能，BSP提高铜箔剥离强度的效果较明显，在浓度为20 mg/L时达到最大值0.52 N/mm。

将四种添加剂以促进剂和抑制剂进行二元复配，组成SPS与HEC(称为SH)、SPS与明胶(称为SG)、BSP与HEC(称为BH)及BSP与明胶(称为BG)组合，研究不同添加剂组合对铜箔粗化层形貌及性能的影响，同时分析双组分添加剂对铜电沉积行为的影响。结果表明，SH和SG添加剂体系均具有去极化作用，但相比单一SPS作用减弱，可知SPS和HEC或明胶存在拮抗作用，抑制剂的加入降低了SPS的促进作用；其中SG改善铜箔剥离强度和整平性的效果最优；而从BSP双组份复合体系结果可知明胶或HEC的加入增强了添加剂体系的去极化作用，说明明胶或HEC与BSP存在协同作用。

研究了新型添加剂噻唑啉基二硫代丙烷磺酸钠(SH110)对铜箔粗化层组织及性能的影响，并研究了铜电沉积行为。结果表明，SH110可在溶液中分解出促进剂(MPS)和抑制剂片段(H1)，二者协同使其发挥出与复合添加剂相同的效果。引入SH110后，铜箔的粗糙度最低可至1.6 μm，剥离强度也在SH110浓度为20 mg/L时出现较明显的提升(0.55 N/mm，提升152.3%)，可达到双组份复合的效果，且浓度较二元添加剂更易调控。

通过正交实验探索新的多组份添加剂配方，研究了SPS+HEC+明胶(SHG)、BSP+HEC+明胶(BHG)及BSP+SPS+HEC+明胶(BSHG)组合对铜箔粗化层形貌及性能的影响。获得了最佳配方为BSHG-5(30 mg/L BSP，60 mg/LSPS，3 mg/LHEC，40 mg/L 明胶)，此复合添加剂体系下沉积的粗化层铜颗粒均匀细小，且剥离强度最大(0.70 N/mm)，该体系中 BSP对剥离强度影响较大，而SPS对粗糙度数值影响较大。

With the arrival of the 5th Generation Mobile Communication Technology (5G), the global demand for very low profile (HVLP) copper foil continues to grow. It is vital to resolve the conflict between low profile and strong peel resistance in order to produce copper foil that performs well and is appropriate for high frequency and high speed circuits. Only a few Chinese businesses currently possess the necessary technology, but when compared to overseas sophisticated businesses, there is still a huge gap in terms of product stability, and the maturity of the products is low. Additives are a key factor affecting the quality of copper foil, so seeking better electrolytic additive compounding technology to improve electrolytic process conditions is an important way to replace imported copper foil. In order to improve the company's operations and get additive formulations that can efficiently produce copper foils for 5G communications, this experiment replicates the post-treatment method used by the company and investigates alternative additive systems and their modes of action.

The main research contents and conclusions of this paper are as follows:

"Low copper and high acid" was used as the basic electrolyte. The effects of four organic additives, including 3,3'-Dithiobis-1-propanesulfonic acid disodium salt (SPS), hydroxyethyl cellulose (HEC), gelatin, and phenyl disulfide propane sodium (BSP), on the microstructure and properties of the coarsened layer of copper foil were studied, as well as their effects on the electrochemical behavior of copper electrodeposition. The findings demonstrate that the addition of SPS accelerates copper deposition, refines the copper particles of the coarsened layer, and boosts the peel strength to 0.49 N/mm. The HEC prevents copper from depositing at copper foil's active sites; however, it has a minimal impact on peel strength. Gelatin increases the copper nucleation density and improves the peel strength (0.48 N/mm) while also reducing the surface roughness (1.58 μm). By comparing the performance of single additives, BSP was the most effective in improving the peel strength of copper foil, reaching a maximum value of 0.52 N/mm at a concentration of 20 mg/L.

The four additives were binary compounded with promoters and inhibitors, namely SPS and HEC (SH), SPS and gelatin (SG), BSP and HEC (BH), and BSP and gelatin (BG), to investigate their effects on the morphology and properties of copper foil coarsened layer. The effects of the two-component composite additive on copper electrodeposition behavior were also analyzed. The results show that SH and SG additive systems have depolarization effects, but the effect is weaker than that of single SPS. which indicates that there is an antagonistic effect of both SPS and HEC or gelatin, and the addition of inhibitor reduces the promoting effect of SPS. Among them, SG has the best effect in improving the peel strength and leveling of copper foil. In the BSP two-component composite system, the addition of gelatin or HEC enhanced the depolarizing effect of the additive system from the electrochemical test results, indicating that there was a synergistic effect of gelatin or HEC with BSP.

The effect of sodium thiazoline dithiopropane sulfonate (SH110) on the microstructure and properties of the coarsened layer of copper foil was studied, and the copper electrodeposition behavior was investigated. The results indicate that SH110 can be decomposed into accelerator (MPS) and inhibitor fragment (H1) in solution. The synergy of the two enables it to play the same effect as the composite additive. After introducing SH110, the roughness of copper foil can be as low as 1.6 μm, an improvement of 19.4%, and the peel strength also increased significantly (0.55 N/mm, increased by 152.3%) at a SH110 concentration of 20 mg/L. It can achieve a dual component composite effect, and the concentration is easier to control than binary additives.

Exploring new multi-component additive formulations through orthogonal experiments, the effects of SPS+HEC+gelatin (SHG), BSP+HEC+gelatin (BHG), and the combination of BSP+SPS+HEC+gelatin (BSHG) on the morphology and properties of the coarsened layer of copper foil were studied. The optimal formula was obtained as BSHG-5 (30 mg/L BSP, 60 mg/L SPS, 3 mg/L HEC, 40 mg/L gelatin) had the most uniform and fine copper particles and the largest peel strength (0.70 N/mm), and the influence of BSP on the peel strength was greater in this system, while the roughness value was more influenced by SPS.

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