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SEM images of plated copper films obtained from electrodeposition with or without TPM-based levelers. The electroplating solution is composed of 0.88 mol/L CuSO4.5H2O, 0.54 mol/L H2SO4, 200 ppm PEG, 2 ppm SPS and 40 ppm Cl -. (a) leveler free, (b) 1 ppm TPM-1, (c) 0.5 ppm TPM-2, (d) 4 ppm TPM-3, (e) 0.5 ppm TPM-4, (f) 20 ppm TPM-5.
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Leveler is one of the most important additives for super-conformal copper electroplating, which has been widely applied in the fabrication of nanoscale (or microscale) interconnect features in integrated circuits (ICs) and printed circuit boards (PCBs). Because the structure-property relationship of the leveler is not clear, the development of nove...
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Context 1
... structural influences of the TPM-based levelers on the surface morphology of the copper depositions were characterized with SEM. As shown in Figure 8, in the presence of PEG and SPS, the surface morphology of the copper film electroplated without leveler is already flat and uniform. When TPM-based levelers have been added into the electroplating solution, the grain sizes of the copper depositions become smaller (Figures 8b -8f). ...
Context 2
... shown in Figure 8, in the presence of PEG and SPS, the surface morphology of the copper film electroplated without leveler is already flat and uniform. When TPM-based levelers have been added into the electroplating solution, the grain sizes of the copper depositions become smaller (Figures 8b -8f). The addition of TPM-based levelers in the electroplating solution can improve the surface morphologies of the copper depositions. ...
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... In the current acidic plating solution system, the main components include one inorganic additive and three organic additives: chloride ions, accelerators, inhibitors, and leveling agents. 20 The concurrent presence of various additives in the electroplating solution system enables improved filling of microvias, ensuring better coating quality and achieving interlayer interconnection. Additionally, additives can enhance current efficiency, simultaneously regulate the deposition rate of copper in high and low current density areas, refine grains, and improve crystal orientation. ...
Acid copper electroplating stands as a core technology in advanced packaging processes, facilitating the realization of metal interconnects, bumps, vias, and substrate wiring between transistors. The deposition quality of copper interconnect materials has a crucial impact on the final performance of chips, directly influencing their yield, reliability, and stability. In this intricate process, additives play a pivotal role in regulating the deposition quality and behavior of metal copper. This mini-review comprehensively summarizes the recent research progress in the field of electroplating copper additives for advanced packaging, both domestically and internationally, delving into the types and mechanisms of various additive molecules, including accelerators, inhibitors, and leveling agents. Through in-depth research on these additives, we gain a profound understanding of their specific roles in the electroplating process and the intricate interaction mechanisms among them, providing theoretical support for optimizing the electroplating process. Furthermore, this mini-review also delves into a thorough analysis of the current issues and challenges facing acid copper electroplating, exploring the key factors that constrain the further development of electroplating copper technology. Based on this analysis, we propose several potential solutions and research directions, offering crucial references for the development and application of electroplating copper additives in advanced packaging. In conclusion, this mini-review aims to provide a comprehensive perspective and profound understanding of the development and application of electroplating copper additives through a review and analysis of recent research progress, ultimately aiming to promote the further advancement of advanced packaging technology.
... Also, inhibitors (such as polyethylene glycol) will chelate with the cuprous ions to form a passivation film that inhibits the reactions [15][16][17]. The main types of surfactants are levelers and brighteners [18][19][20][21], which also play an essential role in copper plating, such as reducing the uneven surface of plated parts and increasing the surface gloss of plated parts. On the other hand, stress relievers are a specific type of additive that primarily aims to reduce internal and external stresses on the surface of the plated parts and the plated layer [22]. ...
In the processing technology of printed circuit boards, the common electroless copper plating technology of ethylenediaminetetraacetic acid disodium (EDTA-2Na) has the problems of large surface stress, uneven crystal particles, and large surface roughness of the copper plating layer. To remedy the above shortcomings and meet the current requirements for copper interconnects in printed circuit boards (PCBs), the present study has investigated a chemical copper plating system that combines a high deposition rate with low stress. An electroless copper plating was then performed on a polyacrylonitrile-butadiene-styrene (ABS) plastic resin plate with 2,6-diaminopyridine (2,6-DAP), 2,2-bipyridine, sodium hydroxyethyl sulfonate (SHES) and NiSO4·6H2O as supplementary additives. By using scanning electron microscopy (SEM), electrochemical, atomic force microscopy (AFM), and X-ray diffraction (XRD) analyses, it has been shown that the average surface roughness Ra became reduced from 202 nm to 76.1 nm when using additives in the chemical copper plating process. Also, the internal stresses of the deposited copper layer on the (220) and (311) planes of a crystalline copper layer decreased from − 70.48 and − 53.03 to − 27.31 and − 27.16 MPa, respectively. The composite additive improved the quality of the copper layer of the EDTA-2Na-based chemical copper plating system, increasing the practical range of industrial applications and facilitating the subsequent application of higher-precision processing.
... It is also well known that an additive in a electrolytic bath induce the transformation from a preferential crystal orientation of (220) to a random crystal orientation that containing (111) and (200) textures. Some additives, such as thiourea and SPS, contain sulfur atoms in the molecules [22]. These sulfur atoms in a boundary of polycrystalline metallic materials will cause a brittle fracture under stress [23]. ...
Nanocrystalline thick copper films with the thickness of ~250 µm were electrochemically synthesized from an acidic aqueous solution containing polyethylene glycol (PEG) with the average molecular weight of 3,000 to investigate the preferential crystal orientation and mechanical properties such as microhardness and tensile strength. By addition of PEG to the electrolytic bath, the cathode potential was shifted to a less noble direction during the electrodeposition and the average crystallite size of electrodeposited copper thick films was decreased. The copper thick films electrodeposited from the solution without PEG exhibited a preferentially orientation in (220) texture while that obtained from the solution containing PEG was composed of nanocrystals with random crystal orientation that containing (111) and (200) textures. The micro-Vickers hardness, tensile strength, and elongation of the electrodeposited copper thick films reached up to 133 HV, 234 MPa, and 13.1%, respectively. These improvements in mechanical properties can be explained by the grain refinement effect and the random crystal orientation effect.
... 论文作者课题组亦长期从事电子电镀铜用整平剂的研 究工作. 针对整平剂分子构效关系不清及作用机理不 明的研究现状, 论文作者课题组通过有目的性地设计 并合成一系列具有含氮基团规律分布的整平剂分子 (如图4所示), 探索其构效关系, 并取得一定成果 [29,43] . ...
... 图 4 具有不同含氮基团及对阴离子的整平剂分子 [43] (网络版彩图) 铜工艺被开发出来 [44] . 大马士革电镀铜工艺与传统电 镀工艺不同之处在于, 普通电镀工艺涂覆了整个表面, 而大马士革电镀铜技术只会将铜沉积到特定的微孔和 槽中. ...
... Molecular structures of TPM-based levelers[43] (color online). 进行图案化. ...
A series of quaternary ammonium salts base on quinacridone aromatic ring were synthesized using 2,9-quinacridone as the parent material, and their leveling performance were evaluated using constant-current chronoamperometry addition curves. Additionally, the adsorption abilities of the leveler molecules on copper surfaces were investigated through quantum chemical calculations and molecular dynamics simulations, and their specific adsorption sites on the copper surface were investigated by XPS, then the effect of concentration on the leveling performance was probed by through-hole plating, and the copper surface was characterized by XRD and SEM. Among four quinacridone aryl quaternary ammonium salts, DCQA-C8-MI exhibits optimal leveling effects, serving as an excellent leveler with outstanding performance. This study expands the application scope of quinacridone aromatic heterocyclic quaternary ammonium salts and offers insights for exploring efficient organic additives for copper electrodeposition.
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