Surfaces and Interfaces
·
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
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电子工程
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DOI
高影响因子
ChemElectroChem
·
2022
·Vol. 9
·期 11
·e202200423
·
IF 4.782
Wei-Qing Li,Lei Jin,Jia-Qiang Yang,Zhao-Yun Wang,Dongping Zhan,Fang-Zu Yang,Zhong-Qun Tian
Graphical Copper Electronic Electroplating : A novel copper electroplating bath in weak alkalinity and containing citrate (Cit) and ethylenediamine (En) in the through-hole thickening of printed circuit board (PCB) was presented. The selective adsorption of Cit−Cu and En−Cu coordination ions at different sites was driven by respective overpotential in TH of PCB for conformal copper electroplating. In this work, an electronic copper electroplating bath with low copper ion concentration and preeminent throwing power in through hole (TH) thickening of the printed circuit board (PCB) was successfully developed. Based upon the weak alkaline bath containing the composite complexants of citrate (Cit) and ethylenediamine (En), their synergistic effects on the preeminent bath throwing power were carefully investigated and theoretically proved. The UV-vis spectroscopy results illustrated that En exhibited a stronger coordination ability with Cu (II) ion than citrate, and the stoichiometric coordination ratio between En and Cu (II) ion was 2 : 1. The linear sweep voltammetry (LSV) results showed that the electro-reduction peak potential of Cit−Cu coordination ion was −0.55 V (vs. Hg/HgO), whereas that of En−Cu ion was at a more negative potential of −0.82 V. The in situ Fourier transform infrared (FTIR) spectroscopy revealed that the adsorptions of the Cit−Cu and En−Cu coordination ions were potential dependent on the copper electrode. The Cit−Cu coordination ion was easily adsorbed at the interior sites of through holes with lower over-potential to promote the growth of copper coating. Moreover, the En−Cu coordination ion adsorbed preferably on the surface and the edge of through hole for its higher electro-reduction overpotential, to hinder the germinating of copper nuclear. The cross-section observation of optical microscope proved that the throwing power of novel copper electroplating bath behaved surpassingly, up to 105.8 %.
研究领域:
材料科学
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电子工程
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DOI
高影响因子
JOURNAL OF COLLOID AND INTERFACE SCIENCE
·
2024
·
IF 9.4
Yicai Wu,Zijie Mao,Xianxian Qin,Kun Jiang,Xian-Yin Ma,Tian-Wen Jiang,Wen-Bin Cai
Triblock Pluronics of polyoxyethylene (PEO) and polyoxypropylene (PPO) are identified as competent suppressors for copper (Cu) electroplating in advanced electronics manufacturing. However, the specific interfacial roles of PEO and PPO blocks in Pluronic suppressors, are not yet fully understood, which is crucial for the rational design of effective suppressors. Herein, the influences of composition and block arrangement of such Pluronics on the inhibition against Cu plating are systematically investigated. The decrease in Cu deposition mass with increasing PPO content suggests that the PPO blocks are the main contributor to the inhibition strength of Pluronics, as demonstrated by the positive correlation between electrodeposited Cu mass and hydrophilic-lipophilic balance (HLB) value. Comparative analysis of normal and reverse Pluronic pairs with similar compositions indicates that an adequately long PEO block is indispensable to maintain the inhibition stability of Pluronics. Moreover, electrochemical attenuated total reflection surface-enhanced infrared absorption spectroscopy (ATR-SEIRAS) offers direct evidence that the PEO block, rather than the PPO block, compactly adsorbs on the chloridion (Cl − ) adlayer covered Cu surface. This work highlights the importance of balancing the PPO-dominated inhibition strength and the PEO-dominated inhibition stability in the design of practical copolymer suppressors, for which the HLB may serve a valuable indicator, together with the PEO block length.
研究领域:
材料科学
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电化学
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DOI
PubMed
高影响因子
ACS Omega
·
2024
·
IF 3.7
Lanfeng Guo,Renlong Liu,Zhaobo He,Shaoping Li,Tong Tan,Changyuan Tao
The copper connectivity technique is essential for achieving electrical interconnection in wafer level packaging (WLP), system in packaging (SiP), and 3D packaging. The essential processing material for copper connectivity is a copper sulfate electroplating solution in which organic additives play a crucial role in the regularity of copper electrodeposition. In this study, electrochemical tests, X-ray diffraction, 3D profiling, and scanning electron microscopy were used to investigate the leveling effect and mechanism of polyquaternary ammonium urea-containing polymer (PUB2) in the process of copper electrodeposition on-chip copper connections. PUB2 has excellent polarization ability on the target surface, remains unaffected by the sulfur additive SPS and poly(ethylene glycol), and displays a strong ability to regulate the copper deposition rate of through-holes and surface wiring. The waviness of the wafer surface wiring was reduced from 130 to approximately 70 nm after optimizing the PUB2 concentration, and the surface roughness was reduced from 10 to approximately 7 nm. The coating was dispersed evenly, and the rate of through-hole filling was improved by 57%. This study not only examined PUB2 leveling performance and mechanisms but also devised a research method and system for electroplating additives to facilitate the development and application of new electroplating additives.
研究领域:
材料科学
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电子工程
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电化学
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产品关联
DOI
PubMed
高影响因子
ELECTROCHIMICA ACTA
·
2022
·
IF 7.336
Zhao-Yun Wang,Lei Jin,Guang Li,Jia-Qiang Yang,Wei-Qing Li,DongPing Zhan,Yan-Xia Jiang,Fang-Zu Yang,Shi-Gang Sun
An organic additive, gentian violet (GVT), is explored for the first time as a novel leveler with excellent property in through-holes (THs) metallization of Cu electronic plating in acidic medium for printed circuit board (PCB) applications. Studies of galvanostatic measurements with a platinum rotation disk electrode and density functional theory calculations demonstrate that the GVT behaves the fundamental leveler's characteristics of mass transfer adsorption, and displays a strong inhibition effect on electro-reduction of cupric ions at high rotating rate. Although the adsorption ability of GVT on Cu surface is weaker than that of commercial leveler Janus Green B (JGB), the potential difference of cupric ion reduction between low and high rotating rates is larger in case of GVT than that of JGB at same current density. Cyclic voltammetry measurements indicate that the Cu amounts of cathodic deposition and that of anodic stripping tend to the same at both low and high rotating rates when GVT, Cl − , polyethylene glycol (PEG) and bis-(sodium sulfopropyl)-disulfide (SPS) coexist in the solution, demonstrating excellent synergistic action of these additives and super leveling effect. In situ FTIR spectroscopic analysis combined with cyclic voltammetry measurements illustrate that the GVT adsorbs on Cu surface and thus affects the electro-reduction of cupric ions, which reveals the very complicated synergistic actions of these additives, i.e., the adsorption ability of GVT can be slightly enhanced by Cl − , while it has been greatly enhanced in the presence of PEG which nevertheless decreases slightly the inhibition effect of PEG on electro-reduction of cupric ions; the SPS plays an antagonistic effect with GVT due to their competitive adsorption. Based on the characterization of GVT as a novel leveler, we developed a GVT-based formula of THs metallization of Cu electronic plating, and demonstrated an excellent efficiency of a throwing power of 97.6% at 10 mA·cm −2 in a real PCB THs metallization of Cu electronic plating.
研究领域:
材料科学
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电化学
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表面工程
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DOI
高影响因子
JOURNAL OF MATERIALS SCIENCE-MATERIALS IN ELECTRONICS
·
2023
·Vol. 34
·期 3
·1-10
·
IF 2.8
Chen Junye,Lu Guanbin,Zhang Yuan,Cheng Yuanrong,Xiao Fei
Additives are essential for damascene copper electroplating to achieve defect-free deposition in nanoscale interconnect on chips. A hybrid additive named 1000EQ with capabilities of both suppressor and leveler has been synthesized and analyzed. The additive contains polyether segment and nitrogen cation which are typical functional groups of suppressor and leveler, respectively. Electrochemical measurements reveal that 1000EQ has strong inhibition toward copper deposition and is more resistant to the desorption of accelerator than traditional suppressor polyethylene glycol (PEG, Mw = 10,000). 1000EQ and bis-(sodium sulfopropyl)-disulfide (SPS) were used as additives to achieve a defect-free filling of features with 70 nm in width and an aspect ratio above 3. The ratio of copper film thickness over dense and sparse patterned area is close to 1 and the root mean square roughness (Rq) of the film is 9.4 nm, acting as a solid proof of its hybrid characteristic. The resistivity of the copper film is 1.80 ± 0.02 µΩ cm. The characterizations establish that 1000EQ is a promising candidate which can serve as both suppressor and leveler for damascene copper electrodeposition and is able to simplify the bath used in copper electrodeposition process.
研究领域:
材料科学
·
电化学
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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
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DOI
高影响因子
JOURNAL OF ELECTROANALYTICAL CHEMISTRY
·
2024
·
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
·
电化学工程
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产品关联
DOI
高影响因子
Materials Today Communications
·
2021
·
IF 3.383
Weidong Han,Xin Qian,Hongbo Ma,Xuefei Wang,Yonggang Zhang
The nickel electroplating followed by a further copper electroplating process was conducted on high modulus carbon fibers (HMCFs), and the HMCFs were oxidized in nitric acid prior to the Ni-plating process. Effect of the electroplating process on the microstructure and mechanical properties of HMCFs was investigated. Uniform nickel particles were observed on the surfaces of Ni-plated HMCFs and fiber diameter increased from 5.0 μm to 6.1 μm. With a further Cu-electroplating process, the fiber diameter continued increasing to 7.5 μm. The Ni-plating process resulted in increased surface roughness, whereas the surface RMS and Ra values dropped significantly after the Cu-plating process. Owing to the Ni-plating treatment, the relative content of carbon element on fiber surfaces decreased from 96.54 % to 36.74 %. After a further Cu-plating process, the relative content of Cu element on HMCF surfaces was as high as 54.01 %. The electroplating process resulted in decreased tensile modulus from 415.71 GPa to 407.71 GPa. By contrast, the tensile strength of electroplated HMCFs increased by 1.1 % due to the reduction of fiber defects and stress concentration. Results also showed that both the Ni-plating and Cu-plating process could lead to significant decreases in the values of electrical resistance and resistivity.
研究领域:
材料科学
·
表面工程
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DOI
高影响因子
ACS Applied Nano Materials
·
2021
·
IF 5.097
Zhiqiang Lai,Tao Zhao,Pengli Zhu,Jing Xiang,Dan Liu,Xianwen Liang,Rong Sun
The metallization of flexible polymer surface is a necessary process to realize the electrical interconnection of insulating substrates, which is of great significance for the fabrication of flexible wearable electronics. Herein, a method for the fabrication of a metal/polymer composite is presented on the basis of a silver nanowire (AgNW) conductive composite by direct copper electroplating. A precoating was first coated on the polyethylene terephthalate (PET) substrate to form the interspace structures on the surface. AgNWs could just be embedded into these interspace structures by the means of coating to obtain excellent adhesion. Furthermore, these interspace structures were filled with deposited copper atoms, thus contributing to a strong interlock between the plated copper layer and the substrate. The obtained Cu/PET composites were subjected to morphological and mechanical characterizations to analyze the peeling strength, crystalline structure, and surface morphology of the plated copper layer. Experimental results show that the plated copper layer is dense and consistent with a maximum peel strength of 11 N cm–1. In addition, large scale of the Cu/PET (20 cm × 30 cm) composite with a thickness of 21 μm was fabricated by this method, and copper patterns were further fabricated using a conventional etching process. The fabricated copper patterns exhibit an outstanding electrical stability after 3000 times of a bending fatigue test, proving the excellent flexibility of the Cu/PET composite. In conclusion, this approach provides an insight into the design of metal/polymer composites addressing a significant potential application in flexible printed circuit, electrode, and antenna for wearable electronics.
研究领域:
材料科学
·
电子工程
✓ 已验证
DOI
高影响因子
CHEMICAL PHYSICS LETTERS
·
2023
·
IF 2.8
Huijuan Shi,Yunzhi Tang,Yuhui Tan,Zhen Sun
Due to the decomposition, condensation, and invalidation of organic additives in acid copper plating solution, it is hard to identify the effective concentration of additives, which causes difficulties in the prediction and grasping of the electroplating effect. To solve this problem, this paper established the linear relationship between absorbency and the concentration of organic additives based on the principle of ultraviolet spectrophotometry and the luminescence mechanism of the chromogenic agent and three organic additives after eliminating the interference of copper and hydrogen ions in the plating solution. The concentrations of polyethylene glycol (PEG), bis-(sodium sulfopropyl)-disulfide(SPS), and gelatin in the solution were analyzed quantitatively according to Law of Lambert-Beer. According to the results, the linear relationship between PEG’s mass concentration and absorbency can be described as y = 0.01057 + 0.01372x, with a linear correlation of 0.9982, a relative error of about 0.56%-3.7%, and a minimum detection limit of 1 mg/L. The method adopted for detecting the SPS content records a relative error of around 0.817%-4.202% with the minimum detection limit of 2 μmol/L. The linear relationship between gelatin concentration and absorbancy is expressed as y = 0.02165x + 0.00932, in which the linear correlation r = 0.9906.
研究领域:
化学工程
·
分析化学
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产品关联
DOI
高影响因子
COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS
·
2023
·
IF 5.2
Lei Jin,An-Ni Zheng,Mei Wang,Jia-Qiang Yang,Zhao-Yun Wang,Fang-Zu Yang,De-Yin Wu,Dongping Zhan
In this work, we develop a novel safranine (SA)-based acidic sulfate copper electronic plating process for through-hole copper void-free filling for high-quality electronics interconnection, and both the molecule actions and synergistic effects of safranine (SA) are carefully explored. Cyclic voltammetry experiments at rotating rates of 200 r/min and 1200 r/min demonstrate that SA itself can accelerate the electro-reduction of copper ion , heighten the inhibiting effect of polyethylene glycol (PEG) and acceleration effect of bis-(3-sulfopropyl) disulfide (SPS). The addition of SA to the virgin make-up solution (VMS) containing PEG and SPS makes the relative electric charge (∆ Q ) between the low and high rotating rates be increased from 1.27 ± 0.04–22.53% ± 0.05, indicating the higher copper electronic plating amount at the center than that at the mouth of through-hole. In situ Fourier transform infrared spectroscopy together with theoretical calculations further illustrate that the molecule SA is adsorbed on the copper surface through the N atom in the aromatic ring , PEG and SPS can heighten the adsorption of SA on the Cu surface, and both PEG and SPS both synergistically influence with SA to achieve the void-free copper filling of through-hole.
研究领域:
材料科学
·
电化学
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产品关联
DOI
高影响因子
危险品化学品经营许可证（带存储）