Surfaces and Interfaces
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2025
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IF 6.3
Zhao-Yun Wang,Xin Zhao,An-Ni Zheng,Lei Jin,Jia-Qiang Yang,Jun-Yang Liu,DongPing Zhan,Da-Quan Yu,Fang-Zu Yang,Shi-Gang Sun
Metallization of micro through silicon via (TSV) is vital in 3-dimensional integration of chips and high-density printed circuit boards. As the diameter decreases and aspect ratio increases, realizing a uniform copper seed layer inside TSV becomes increasingly challenging by using traditional techniques of high-cost physical vapor deposition (PVD) and chemical vapor deposition (CVD). Cu electroless deposition (Cu-ELD) is a promising technique for growing a conductive seed layer on the wall of TSV, and promotes the completion of metallization of micro TSV following by Cu electroplating. In the current study, an advanced method is developed to form Cu seed layer on micro TSV by Cu-ELD catalyzed through Ag nanoparticles. The Ag nanoparticles are synthesized using gallic acid as the reducing agent (denoted as GA-Ag NPs). Ultraviolet–visible absorption spectroscopy and transmission electron microscopy are applied to study the mechanism of conformal Cu-ELD catalyzed by GA-Ag NPs, and results demonstrate that all Ag ions are reduced to spherical Ag NPs of 9.7 nm in average size. Electrochemical tests and finite element simulation illustrate that the high catalytic activity of GA-Ag NPs facilitates Cu-ELD to achieve an effective conformal deposition in TSV. The obtained continuous and uniform Cu seed layer enables the void-free filling of TSV ultimately by Cu electroplating. An in situ XRD device is designed and built up for investigation of Cu-ELD process, which reveals that the Cu layer catalyzed by GA-Ag NPs during growth is stable and exhibits a mixed crystalline structure with texture coefficient ( TC ) values of Cu (220) and Cu (311) close to and higher than 25 %.
研究领域:
材料科学
·
电子工程
✓ 已验证
产品关联
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2022
·
IF 7.336
Qing Wang,Jiaxin Liu,Zhenyu Lei,Yun Mou,Mingxiang Chen
In this work, we combined the computational simulation and experiments to explore the convection on filling characteristics of the micro through-holes (THs) with multiple aspect ratio (ARs). The micro THs with ARs 6.25:1∼1.67:1 (thickness 500 μm) were chosen as research targets. The computational model was established based on the actual state of Haring-Cell, and attention was fixed on the convection distribution in the micro THs. The interaction mechanism of additives with the changing ARs systematically explored by electrochemical measurements. The simulation results show that the convection in the micro THs center declines with the increasing AR. The convection-dependent additives formed diverse adsorption states around the micro THs with different ARs, providing two kinds of Cu filling processes, including defect-free filling and insufficient filling. The weak convection is conducive to the adsorption of the accelerator and detrimental to the adsorption of the suppressor, which accelerates the Cu electrodeposition and elevates the throwing power (TP) value to over 100% to form the defect-free filling. Strong convection is instrumental in the adsorption of the leveler so that a uniform Cu film thickness can be obtained but to create the insufficient filling. Simulation and electroplating experiments show that the AR of 3.33:1 is the cut-off point of the flow field distribution and the electroplating processes. The micro THs with AR higher than 3.33:1 can be fully filled with a uniform bright Cu surface.
研究领域:
材料科学
·
电化学
·
微制造
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2023
·
IF 4.5
Zhao-Yun Wang,Lei Jin,Jia-Qiang Yang,Wei-Qing Li,De-Yin Wu,DongPing Zhan,Fang-Zu Yang,Shi-Gang Sun
The additives in acidic copper electronic plating solution are of crucial importance in uniform thickening of through-hole (TH) for printed circuit board (PCB) fabrication. In this present study, we set up a transfer-adsorption model to forward understanding the synergistic effects of additives on TH uniform thickening based on the experimental facts of galvanostatic measurements, density functional theory calculations and chronocoulometric measurements. According to this model, during copper electronic plating, the suppressor of polyethylene glycol (PEG) adsorbs more at the mouth because of the replacement of PEG by the accelerator of bis-(sodium sulfopropyl)-disulfide (SPS) at the center of TH, the leveler of Janus Green B (JGB) adsorbs uniformly both at the mouth (where it works with PEG to weaken the adsorption of SPS) and center of TH (where it cooperates with SPS to promote the cupric ions electro-reduction), resulting in the copper layer thickness decreasing at mouth and increasing at center. Such complicated but effective synergistic effects of the three additives result in uniform thickening of TH. Copper electronic plating results further confirmed the reliability of the transfer-adsorption model in synergistic effects of copper electronic plating additives, and unveiled the interaction mechanism of additives for TH uniform thickening.
研究领域:
材料科学
·
电化学
✓ 已验证
产品关联
DOI
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2024
·
IF 4.9
Ke Li,Qifei Xia,Lei Jin,Rongbin Xu,Yi Zhong,Daquan Yu
Leveler additives for Cu electrodeposition are critical for achieving bottom-up filling in micrometer scale and high aspect ratio (AR) through-silicon vias (TSVs). This study explores a highly effective imidazolium-based leveler electroplating formulation, which successfully achieves void-free filling of TSVs with a diameter of 3 μm and a depth of 45 μm (with an ultra-high AR of 15:1). Molecular dynamics simulations reveal that the leveler, 1,2-dimethyl-3-propylimidazolium iodide (DMPII), demonstrates a strong adsorption effect on the Cu surface. Electrochemical tests show that DMPII enhances the inhibitory effect of polyethylene glycol (PEG) while simultaneously amplifying the accelerating effect of bis-(sodium sulfopropyl)-disulfide (SPS). The complex interplay among these additives ultimately leads to a significant inhibitory effect on the electrochemical reduction of Cu ions at the TSV sidewalls, while promoting deposition at the bottom of the TSV. Furthermore, minimal impurities are detected in the electroplated Cu layer. These findings suggest that this DMPII-based electroplating formulation holds significant promise for the fabrication of ultra-high AR TSVs to enable future high-density 3D integration.
研究领域:
材料科学
·
微电子工程
✓ 已验证
产品关联
DOI
高影响因子
APPLIED SURFACE SCIENCE
·
2025
·
IF 6.9
Qiao Ding,Ning Li,Bo Wu,Qing Cheng,Qi Zhao,Tong Liu,Rui Wang,Deyu Li
In this study, SO 2 was used to chemically modify the commonly used leveling agent polydimethyldiallylammonium (PD) in through-hole electroplating, resulting in a more effective leveling agent, PDS, which improved the throwing power (TP), leading to through-hole circuit boards with better metal coverage in difficult-to-reach areas. Furthermore, theoretical and experimental studies were conducted to understand how the −SO 2 structure influences the leveling ability of the leveling agent. The study demonstrates that the −SO 2 -modified additive significantly enhances the copper plating process, resulting in thicker and more uniform deposits in through-holes, which are critical for ensuring high-quality circuit boards.Additionally, this study elucidates the mechanism of action of the leveling agent on the copper surface, providing theoretical support for the development of copper plating leveling agents. The leveling ability differences between the leveling agents PD and PDS were investigated using Cyclic Voltammetry, constant current method, and Electrochemical Impedance Spectroscopy. Additionally, the optimal concentrations of the additives were determined. Quantum chemical calculations were employed to analyze the electrostatic potential, HOMO/LUMO orbitals, and differential charge density on the Cu (111) surface for both leveling agents. These theoretical analyses provided insights into the reasons behind the differing leveling abilities of the two agents.
研究领域:
材料科学
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电化学
·
理论化学
✓ 已验证
产品关联
DOI
高影响因子
VACUUM
·
2023
·
IF 4
Luobin Zhang,Jintao Wang,Sheng Zhou,Xiaojia Luo,Yufeng Li
This research is an attempt to apply the silver thick-film metallization and the soft soldering process to the ultra-high vacuum packaging of atom chips with through silicon via (TSV). During the packaging process, a vacuum environment is used to avoid oxidation of the Cu layer on the chip during heating. At the same time, tin foil is used to protect the inner wall of the glass cell to prevent the gas emitted by the solder from polluting the inner wall. In general, by the adoption of screen printing, sintered surface metallization at a constant temperature of 450–500 °C for 5 min, combined with soft soldering, the packaging of an atom chip with TSV and a silica glass cell is realized. The weld gap is less than 50 μm, the airtightness can reach 8.5 × 10 −13 Pa m 3 /s, and the vacuum degree can reach 2.18 × 10 −8 Pa. That can meet the requirements of cold atom experiment for light path and vacuum degree.
研究领域:
材料科学
·
物理学
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF INDUSTRIAL AND ENGINEERING CHEMISTRY
·
2023
·
IF 6.1
Lei Jin,Zhao-Yun Wang,Zhuan-Yun Cai,Jia-Qiang Yang,An-Ni Zheng,Fang-Zu Yang,De-Yin Wu,Dongping Zhan
In this work, we develop a novel 1-(2-Pyridylazo)-2-naphthol (PAN)-based acidic sulfate copper electronic electroplating process for compact, homogeneous and conformal copper thickening of through hole (TH). The adsorption characteristics, electrochemical properties and the interaction mechanisms of three additives (PEG, SPS and PAN) are studied in detail. Scanning electron microscope (SEM) and optical microscope (OM) reveal that PAN can make the copper coating in fine grains and high throwing power of 90.35% in TH without an overhang phenomenon. Theoretical calculations illustrate that the binding energies between additive molecules and copper surface decrease in the order: PAN > SPS > PEG . Cyclic voltammetry experiments at rotating rates of 1200 and 200 r/min prove that PAN itself can accelerate and weakly suppress copper electrodeposition at the center and mouth of TH, respectively. PAN behaves respectively the synergistic and antagonistic effects with PEG at the mouth and center of TH, and the weakly synergistic effects with SPS both at the mouth and center of TH. The addition of PAN to the virgin make-up solution (VMS) containing PEG and SPS causes decreasing the relative electric charge (Δ Q ) at high and low rotating rates from 18.52 ± 0.08% to 8.25 ± 0.05%, which satisfies the closer copper electronic electroplating rate at the center and mouth of TH. The effective and complicated synergistic effects of the additives PEG, SPS and PAN can achieve compact, homogeneous and conformal copper thickening of TH.
研究领域:
材料科学
·
电化学工程
✓ 已验证
产品关联
DOI
高影响因子
JOURNAL OF ALLOYS AND COMPOUNDS
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2019
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IF 4.175
Yanting Tian,Xiang Guo,Pingping Wu,Xu Zhang,Zhongquan Nie
Ni-based anode supports with straight open pores were well prepared using self-organization process. The scanning electron microscopy (SEM) results of YSZ ceramic skeletons showed that honeycomb-like structures with highly ordered straight pores were obtained. The regulation of solid loading and CaCl 2 concentration on the morphology of YSZ skeletons were discussed. The YSZ skeleton with solid loading of 10 wt% and CaCl 2 concentration of 1.5 mol L −1 delivered a pore size of 99 μm and a porosity of 46.9%. The solid oxide fuel cell based on Ni-YSZ anode possessed a maximum power density of 253 mW cm −2 and an ohmic resistance of 0.16 Ω cm 2 at 800 °C. The pore diameter and porosity of the ceramic supports could be adjusted to expected values by further optimization of the parameters. The self-organization method will become a feasible and valid operation to produce anode supports with appropriate morphologies.
研究领域:
材料科学
·
能源工程
✓ 已验证
DOI
高影响因子
ELECTROCHIMICA ACTA
·
2025
·
IF 5.6
Zhao-Yun Wang,Lei Jin,Jia-Qiang Yang,Yi Zhao,Tao Song,DongPing Zhan,Da-quan Yu,Fang-Zu Yang,Shi-Gang Sun
The uniform thickening of high aspect ratio (AR) through-holes (HAR-TH, AR: 10–12:1) by Cu electronic plating (Cu-EP) is essential in printed circuit boards fabrication, and is often accomplished with organic levelers and at low current densities (6–15 mA/cm 2 ). Nevertheless, the organic levelers are often unstable and the Cu-EP at low current densities presents low production efficiency. In this study, we demonstrate that inorganic compound sodium azide (SAD) can act as a novel leveler in acidic Cu-EP for achieving uniform thickening of HAR-THs (AR: 12:1) even at a high current density of 20 mA/cm 2 . The throwing power using SAD for HAR-THs (AR: 12:1) thickening reaches as high as 94.7 %. Galvanostatic measurements and cyclic voltammetry tests on Pt rotating disk electrode (Pt-RDE) reveal that the competitive adsorption among the three additives of SAD, PEG and SPS occurs only at high rotating rate, referring to a strong inhibition of cupric ions reduction at violent convection area of the HAR-THs mouth. In situ FTIR spectroscopy analyses combined with DFT theoretical calculations illustrate that the synergistic effect of SAD and PEG is manifested by the formation of a PEG-SAD co-adsorption layer. The key to achieving uniform thickening lies in the difference in competitive adsorption abilities between the PEG-SAD co-adsorbed layer and SPS at both mouth and middle part of the HAR-THs. The PEG-SAD co-adsorption layer occupies all active sites of the HAR-THs mouth, preventing SPS from adsorption and thus reducing Cu deposition rate. However, the SPS firmly occupies active sites of middle part of the HAR-THs, facilitating to maintain a consistent Cu deposition rate inside the HAR-THs, consequently achieving uniform Cu thickening of the HAR-THs.
研究领域:
材料科学
·
电化学工程
✓ 已验证
产品关联
DOI
高影响因子
MICROELECTRONIC ENGINEERING
·
2021
·
IF 2.523
Fuliang Wang,Yuhang Tian,Kang Zhou,Rui Yang,Tian Tan,Yan Wang,Wenhao Yao
Through silicon via (TSV) is a promising interconnect technology in three-dimensional (3D) integration which has large packing density, improves efficiency and consumes less energy. Since the optimization process of multi-additives system is complicated to achieve void-free TSV copper filling, the use of a single additive become a new trend. In this paper, the using of a triblock copolymer ethylene oxide (EO) - propylene oxide (PO) - ethylene oxide (EO) as a single additive in TSV copper electrodeposition was investigated. High and low concentration of EPE (0.02 g/L and 0.002 g/L) were used for the filling experiment at different current densities. It was found that low concentration EPE had stronger inhibition ability, and achieved “V shape” filling at 0.3 ASD (A/dm 2 ). However, EPE of high concentration would form micelles in electrolyte, resulting in the decrease of inhibition ability. We proposed a mechanism for the different EPE concentrations to explan the phenomenon. In addition, the effect of ultrasonic agitation on EPE filling performance was investigated. With the ultrasonic agitation , bottom-up filling can be achieved at 0.02 g/L, and filling rates can be increased at 0.002 g/L. This can be attributed to the cavitation of the ultrasound which can promote the mass transfer and clean the activated electrode.
研究领域:
材料科学
·
电子工程
✓ 已验证
DOI
高影响因子
POLYMER
·
2025
·
IF 4.5
Xiao Zhang,Xixun Shen,Runlin Wang,Zihao Zhang,Wei Huang,Qunjie Xu,Zhenni Kang,Junfeng He
At present, the hole metallization of printed Circuit Boards (PCBs) is achieved through using traditional electroless copper as a conductive seed, accompanied by an electroplating copper filling process. This method has serious environmental issues due to the carcinogenic formaldehyde and recalcitrant chelating agents in the electroless plating solution. To address this issue, a green polymer polypyrrole conductive film is proposed to replace traditional electroless copper as a conductive seed layer for the metallization of PCB. The polypyrrole film is formed via in-situ polymerization of pyrrole monomers on blind-hole walls. The cross-sectional SEM and EDS analysis confirmed that the polypyrrole film was uniformly formed on the walls of blind holes. The polypyrrole conductive layer exhibits a low sheet resistance of 1.45 kΩ/sq. Electrochemical characterizations demonstrate rapid copper electrodeposition on this conductive polymer layer. The contact angle measurements also demonstrate that the polypyrrole conductive film enhances substrate wettability, facilitating electrolyte infiltration into the vias. The filling experiment shows that dense super filling of copper in blind holes can be achieved within about 70 min. Thermal shock experiments confirm excellent adhesion of the plated copper. These results demonstrate that the polypyrrole conductive film represents a highly promising material to replace traditional electroless copper as the conductive seed layer for the metallization of PCB.
研究领域:
材料科学
·
电子封装
·
表面工程
·
高分子化学
·
环境友好技术
✓ 已验证
产品关联
DOI
高影响因子
ACS Applied Materials & Interfaces
·
2016
·
IF 7.145
Shengnan Wang,Min Chen,Limin Wu
A facile, one-step method to prepare cagelike hollow silica nanospheres with large through-holes (HSNLs) using a lysozyme-assisted O/W miniemulsion technique is presented. The tetraethoxysilane (TEOS)–xylene mixture forms oil droplets which are stabilized by the cationic surfactant cetyltrimethylammonium bromide (CTAB), cosurfactant hexadecane (HD), and protein lysozyme. HSNLs (with diameter of 300–460 nm) with large through-holes (10–30 nm) were obtained directly after ultrasonic treatment and aging. Lysozyme can not only stabilize the oil/water interface, assist the hydrolysis of TEOS, and interact with silica particles to assemble into silica-lysozyme clusters but also contribute to the formation of through-holes due to its hydrophilicity variation at different pH conditions. A possible new mechanism called the interface desorption method is proposed to explain the formation of the through-holes. To confirm the effectiveness of large through-holes in delivering large molecules, bovine serum albumin (BSA, 21 × 4 × 14 nm3) was chosen as a model guest molecule; HSNLs showed much higher loading capacity compared with common hollow mesoporous silica nanospheres (HMSNs). The release of BSA can be well controlled by wrapping HSNLs with a heat-sensitive phase change material (1-tetradecanol). Cell toxicity was also conducted with a Cell Counting Kit-8 (CCK-8) assay to roughly evaluate the feasibility of HSNLs in biomedical applications.
研究领域:
材料科学
·
生物医学工程
·
纳米技术
✓ 已验证
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）