ACS Applied Materials & Interfaces
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2025
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IF 8.2
Zhao-Yun Wang,Li-Xin Yu,Yu-Qing Feng,Lei Jin,Jia-Qiang Yang,Yi Zhao,Tao Song,DongPing Zhan,Daquan Yu,Fang-Zu Yang,Shi-Gang Sun
Leveler is the key additive for achieving microvia void-free filling in the high-density integration of electronic components for miniaturization, lightweighting, and intelligent development of electronic devices. Traditional organic levelers are mostly quaternary ammonium salts and nitrogen-containing heterocyclic compounds. In this study, thiosemicarbazide (TA) and 1-phenyl 2-thiourea (PTA), which are the thioamino compounds with different substituents of amino and phenyl, are used for the first time as levelers for microvia filling in an acidic copper sulfate bath of Cu electroplating (Cu-EP). The results demonstrate that only the PTA, when used as the leveler in combination with poly(ethylene glycol) (PEG) as the suppressor and bis(sodium sulfopropyl)-disulfide (SPS) as the accelerator, can achieve microvia void-free filling. Chronopotentiometric analyses reveal that both TA and PTA accelerate the reduction of cupric ions. The accelerator of SPS with TA synergistically enhances accelerating effect, while with PTA, it behaves with competitive adsorption to weaken this effect. The suppressor of PEG can cooperate with PTA to show a strong inhibiting effect on cupric ion reduction but presents competitive adsorption with TA, weakening the inhibiting effect of PEG. Under such complex interactions of these additives, it has been found that only the combination of PTA, SPS, and PEG exhibits convection-dependent adsorption behavior, which results in a more negative reduction potential of cupric ions at the mouth of the microvia than that at the bottom of the microvia, indicating a theoretical feasibility of achieving microvia void-free filling. Cyclic voltammetry experiments further demonstrate that the PTA can accelerate the reduction of cupric ions, but this acceleration effect is weakened by SPS due to competitive adsorption. PTA synergizes with PEG to greatly enhance the inhibiting effect on cupric ions reduction. According to electrochemical properties and interactions of the additives, the essence of the PTA-based acidic Cu sulfate bath for achieving microvia void-free filling is elucidated through electroplating simulations. When the three additives coexist, the adsorption coverage of PTA–PEG gradually decreases from the mouth to the bottom. As PTA–PEG exhibits a synergistic inhibition effect, such a gradient significantly inhibits Cu deposition at the mouth; simultaneously, the adsorption coverage of SPS, which behaves with an accelerating effect, gradually increases from the mouth to the bottom, facilitating the reduction of cupric ions at the bottom. The dual gradient effects enable the microvia void-free filling.
研究领域:
材料科学
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电化学
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电子器件
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表面工程
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DOI
PubMed
高影响因子
NEW JOURNAL OF CHEMISTRY
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2025
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IF 2.5
Mingjie Li,Xuesong Peng,Jie Jiang,Yaqiang Li,Fan Meng,Youzheng Wu,Maozhong An,Ruopeng Li,Penghui Ren,Peixia Yang
The void-free blind microvia copper electroplating process is a key technology in HDI PCB manufacturing. This work systematically studied the influence of the Acid Blue 1 (AB1) leveler on blind microvia filling. AB1 exhibits excellent suppression during electroplating, with its effect strengthening as the AB1 concentration increases. Chronopotentiometry was used to study the interaction among AB1, SPS, and PEG. There is a synergistic suppressing interaction between the new leveler AB1 and suppressor PEG, while there is competition between AB1 and accelerator SPS. During electrodeposition, AB1 can adsorb on the copper substrate to reduce active sites and suppress copper electrodeposition, based on theoretical studies and in situ infrared spectroscopy. At the optimized electroplating process, void-free microvia filling is achieved with 20 mg L−1 AB1 and successive electroplating confirms the stability of AB1. Based on diffusion differences among additives and the competition between AB1 and SPS, a gradient competitive adsorption superfilling mechanism was proposed to illustrate the filling process of the AB1–SPS–PEG system. AB1 is beneficial to improving flatness and lowering surface roughness of the copper layer, which is conducive to reducing signal losses during high-frequency transmission. Additionally, AB1 can modulate the preferential formation of Cu(111) and Cu(200) and facilitate grain refinement.
研究领域:
材料科学
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电化学工程
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DOI
高影响因子
Journal of the Taiwan Institute of Chemical Engineers
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2019
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IF 3.834
Jie Yang,Jiangdong Dai,Lulu Wang,Wenna Ge,Atian Xie,Jinsong He,Yongsheng Yan
The problem of tetracycline (TC) antibiotic pollution in aquatic environment has attracted wide attention and research. It is still meaningful to develop high-efficiency separation materials and investigate their adsorption behavior and mechanism. In this research, porous carbons were prepared using the renewable willow branches as carbon source, via pre-carbonization and alkali activation. The activation temperature and alkali usage played important roles in the pore structure, which was mainly microporous. The WBAC-850-4 obtained at 850 °C and alkali/biochar ratio of 4:1 exhibited the largest specific surface area (3342 m 2 /g) and total pore volume (1.912 cm 3 /g), displaying the ultrahigh TC adsorption capacity of 1300 mg/g at 298 K. which was higher than that of the reported TC-adsorbents. WBAC-850-4 kept high adsorption ability with a minor impact in the broad pH range of 3.0–8.0. Thermodynamic analysis implied the physisorption dominated the spontaneous adsorption process. The structure-activity relationship between the TC adsorption capacity and porosity properties was established for the first time. Notably, the adsorption capacity of TC had a positive linear correlation with specific surface area, total pore volume, micropore surface area and micropore pore volume, and the correlation coefficient were higher than 0.97. It was first revealed that micropore filling was the main mechanism for porous carbons to bind TC, which meaningfully provided new insight for designing advanced TC-adsorbents in future.
研究领域:
环境科学
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材料科学
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DOI
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
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2024
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IF 4.1
Tao Song,Zhao-Yun Wang,Jia-Qiang Yang,Yi Zhao,Fang-Zu Yang,Dongping Zhan
A phosphorus-containing new compound of tributyl(hexyl)phosphonium chloride (TBHP), but not the commonly used nitrogen-containing heterocycles and quaternary ammonium salts, is successfully applied for the superconformal copper filling of microvia in acid sulfate electroplating bath for the application of electronic industry. The molecular interaction mechanisms of TBHP combined with suppressor (polyethylene glycol, PEG) and accelerator (bis-(sodium sulfopropyl)-disulfide, SPS) are investigated in detail. Galvanostatic measurements at platinum rotation disk electrode indicate that the leveler of TBHP among with the suppressor and accelerator behaves the key characters of inhibition and convection-dependent adsorption during copper ions electroreduction for the bottom-up filling of microvia. Cyclic voltammetry measurements and in-situ FTIR spectroscopy further reveal that TBHP synergistically interacts with the suppressor to inhibit copper ions electroreduction at the mouth of microvia; while TBHP competes for adsorption with the accelerator, behaving as TBHP gradually replaced by the accelerator at the bottom. Based on the sufficient theoretical supports, the practical copper electroplating is conducted for the verification of microvia void free filling. In the developed novel copper plating formula containing TBHP, PEG and SPS, the void free filling is successfully achieved and the filling percentage (FP) is high in 95.5%.
研究领域:
材料科学
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电化学工程
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DOI
高影响因子
Nanomaterials
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2022
·Vol. 12
·期 7
·1063
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IF 5.719
Guannan Yang,Shaogen Luo,Tao Lai,Haiqi Lai,Bo Luo,Zebo Li,Yu Zhang,Chengqiang Cui
In this work, we developed an eco-friendly and facile microvia filling method by using printing and sintering of Cu-Ag core-shell nano-microparticles (Cu@Ag NMPs). Through a chemical reduction reaction in a modified silver ammonia solution with L-His complexing agent, Cu@Ag NMPs with compact and uniform Ag shells, excellent sphericity and oxidation resistance were synthesized. The as-synthesized Cu@Ag NMPs show superior microvia filling properties to Cu nanoparticles (NPs), Ag NPs, and Cu NMPs. By developing a dense refill method, the porosity of the sintered particles within the microvias was significantly reduced from ~30% to ~10%, and the electrical conductivity is increased about twenty-fold. Combing the Cu@Ag NMPs and the dense refill method, the microvias could obtain resistivities as low as 7.0 and 6.3 μΩ·cm under the sintering temperatures of 220 °C and 260 °C, respectively. The material and method in this study possess great potentials in advanced electronic applications.Keywords:Cu-Ag core-shell nano-microparticles;microvias;vertical interconnection;blind hole filling;sintering
研究领域:
材料科学
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电子工程
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DOI
PubMed
高影响因子
International Journal of Smart and Nano Materials
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2022
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IF 4
Guannan Yang,Shaogen Luo,Bo Luo,Yan Zuo,Shiwo Ta,Tingyu Lin,Zhaohui Zhao,Yu Zhang,Chengqiang Cui
Conductive fillers made from metal nanoparticles offer many advantages for the fabrication of a variety of electronic devices, but when they have a porous structure, their poor conductivity limits their adoption in many applications. In this study, an Ag-coated Cu micro-nanoparticle paste is used to achieve compact filling of blind vias on flexible copper clad polyimide laminates through a multistep filling and sintering technique. The filled blind vias achieve a resistivity as low as 6.2 μΩ·cm, which is comparable that of electroplated blind vias. Higher sintering pressure and temperature promote the filling performance, while the conductivity deteriorates at a via depth/diameter ratio greater than 1:1. Finite element simulations reveal a stress inhomogeneity in vias with large depth/diameter ratios, which is the key to understanding the evolution of the conductive properties of a paste-filled via. This study provides an effective method for high-performance microvia filling as well as insights into the mechanism that influences its performance.
研究领域:
先进电子封装
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材料科学
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微电子学
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纳米技术
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DOI
高影响因子
ENVIRONMENTAL RESEARCH
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2025
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IF 7.7
Yao Fang,Yuanjun Tang,Guoneng Li,Jun Dong,Chao Ye,Zhongming Bu,Wenwen Guo
The efficient removal of fluoroquinolone antibiotics from water is critical for water pollution control. In this study, a novel self-nitrogen doped porous biochar (KBC) was synthesized using waste peanut meal as a precursor, combined with high-temperature pyrolysis (900 °C) and an activating agent (C 2 H 2 K 2 O 5 ) at an optimal mass ratio of 1:2. The KBC exhibited excellent adsorption capacity for levofloxacin (LEV) with the maximum capacity of 717.87 mg g −1 (at 0.15 g L −1 ). The adsorbents demonstrated rapid adsorption kinetics, achieving 83.36 % of total adsorption within 2 h, and exhibited pH-dependent adsorption behavior, with optimal performance at pH = 9. Thermodynamic studies indicated that the adsorption process was spontaneous and endothermic. The adsorption isotherm followed the Langmuir model, suggesting monolayer chemisorption as the dominant mechanism. Additionally, the pseudo-second-order kinetic model further confirmed the involvement of chemical interactions. Material characterization and density functional theory (DFT) simulations were employed to reveal the underlying adsorption mechanisms: (1) micropore filling-dominated physical adsorption (BET surface area = 2119.96 m 2 g −1 ); (2) hydrogen bonding and π-π electron donor-acceptor interactions between oxygen-containing functional groups on the KBC surface and LEV molecules; (3) DFT calculations revealed that the adsorption energy of anionic LEV (−321.72 kJ mol −1 ) was significantly higher than that of neutral and cationic forms, consistent with the experimental pH-dependent trend; and (4) DFT-optimized configurations demonstrated strong interactions between LEV and the biochar with a bond distance of 2.0 Å, providing atomic-level evidence for adsorption stability. These findings offer practical insights into the valorization of agricultural waste and advanced strategies for water remediation.
研究领域:
环境科学
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材料科学
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化学工程
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水污染控制
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吸附技术
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计算化学
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产品关联
DOI
PubMed
高影响因子
危险品化学品经营许可证（带存储）