Development of high copper concentration, low operating temperature, and environmentally friendly electroless copper plating using a copper ‐ glycerin complex solution

Huang, Jui Hsien; Shih, Po-Ta; Renganathan, Vengudusamy; Gräfner, Simon Johannes; Chen, Y.A.; Huang, Cheng‐Chieh; Kao, Chin-Li; Lin, Yung Sheng; Hung, Yun-Ching; Kao, C. R.

doi:10.1016/j.electacta.2022.140710

Cited by 14 publications

(8 citation statements)

References 25 publications

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“…The glycerin concentration was determined by a spectrophotometer based on the reaction of glycerin and Cu(OH) 2 to form a blue complex. 25,26 The byproduct P has similar reaction paths as the reactant M. The first path is also a ring-closing reaction similar to Reaction I to form W. Thus, the conversion of P to W (Reaction IV) is also a consecutive reaction including a second-order reaction and a first-order intramolecular Williamson reaction. The other path is similar to Reaction VI that P will react with OH À to form Q (Reaction VII) following the mechanism of intermolecular S N 2 reaction.…”

Section: Methodsmentioning

confidence: 99%

“…In addition to conductivity meter, spectrophotometer and gas chromatography (GC) are also used to determine the content of organic substance in the experiments. The glycerin concentration was determined by a spectrophotometer based on the reaction of glycerin and Cu(OH) 2 to form a blue complex 25,26 . Figure 4 depicts a great linear relationship about the complex concentration and the absorbance.…”

Section: Methodsmentioning

confidence: 99%

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Mechanism and kinetics investigation of reaction network: 1,3‐Dichloro‐2‐propanol with alkali to prepare epichlorohydrin

Zhang,

Zhu

et al. 2023

AIChE Journal

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Dehydrochlorination of 1,3‐dichloropropanol with alkali is a key step to industrially produce epichlorohydrin. But there are many side reactions involved in the synthesis process. In this work, a complete mechanism and kinetics investigation of the related reaction network was constructed. Density functional theory simulation method was first used to simulate the possible reactions so as to confirm the reaction mechanism and simplify the reaction network. Based on the simulation results, the complex reaction network was simplified into a three‐step consecutive reaction. The kinetic parameters of the three consecutive steps, including the order of the reaction, the pre‐exponential factor, and activation energy, were experimentally determined by conductance and other methods. All the experimental results are basically consistent with the simulation. The obtained kinetics data provide a basis for epichlorohydrin synthesis process optimization.

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Mechanism and kinetics investigation of reaction network: 1,3‐Dichloro‐2‐propanol with alkali to prepare epichlorohydrin

Zhang,

Zhu

et al. 2023

AIChE Journal

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“…An additional simplification from the experimental to the numerical model concerns the movement of the interface and the contact angle for the hydrophobic behavior of the pillar surfaces. In the experiment, hydrophobic behavior is observed, possibly due to surface roughness caused by the fabrication method or the characteristic electroless Cu-plated deposition layer, [36][37][38] as well as enhanced surface tension, which forces the bubble to form a rounded shape and thereby avoid contact forces. [39] In the numerical model, a frictional force F fr is applied as a Navier slip condition to address the moving interface on the solid walls.…”

Section: Affiliation Among Analytical Numerical and Experimental Studiesmentioning

confidence: 99%

Dislodgement of Hydrogen Bubbles in Microchannels with Embedded Pillars: An Analytical, Experimental, and Numerical Study

Gräfner,

Huang,

et al. 2024

Advanced Materials

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Microchannels with integrated pillars have enhanced the production capabilities and performance of various applications due to their high surface‐to‐volume ratio. However, emerging gas bubbles can become trapped, potentially limiting the functionality or efficiency of the device when scaled down to the low‐micrometer scale. Understanding the conditions required to dislodge these bubbles is thus critical for optimizing microfluidic devices with complex physical behaviors. This study presents an analytical model that outlines the dislodgment conditions and driving forces for such gas–liquid flows. These terms are derived from the gas–liquid interface properties, geometry, and processing parameters. As the density of the pillar arrangement is scaled down, the resistance to bubble dislodgment typically increases. Nevertheless, the bubble is compelled to dislodge at lower pressure loads when critical volumes are reached. This newly discovered effect is particularly noticeable in densely packed arrays and can be explained by the interplay of increased surface tension, geometrical restrictions, and volume‐preserving forces. The analytical terms and effects are validated through novel experimental and numerical methods tailored for microchannels in the low‐micrometer scale, showing strong agreement.This article is protected by copyright. All rights reserved

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“…Huang et al developed a copper-glycerin complex solution with a high copper concentration, specifically for use in electroless plating [13]. This solution had a significantly higher plating rate than commercially available electroless Cu plating solutions and a Cu concentration that was more than four times higher than that of conventional solutions.…”

Section: Developed a New Technique Called Microfluidic Electroless In...mentioning

confidence: 99%

“…A previous patent presented a high copper concentration copper-quadrol complex solution with a Cu concentration of 0.2 M, which is over five times that of conventional electroless copper plating solutions [18]. Nonetheless, a high Cu concentration poses difficulties such as selfdecomposition and a short decomposition time, making it difficult to use in the process [13]. As a result, the concentrations of copper sulfate, formaldehyde, and surfactant were kept constant in this study, whereas the concentrations of quadrol, cytosine, temperature, and pH were varied to optimize the solution.…”

Section: Developed a New Technique Called Microfluidic Electroless In...mentioning

confidence: 99%

A High Copper Concentration Copper-Quadrol Complex Electroless Solution for Chip Bonding Applications

Huang,

Shih,

Renganathan

et al. 2024

Materials

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This article presents a novel bonding method for chip packaging applications in the semiconductor industry, with a focus on downsizing high-density and 3D-stacked interconnections to improve efficiency and performance. Microfluidic electroless interconnections have been identified as a potential solution for bonding pillar joints at low temperatures and pressures. However, the complex and time-consuming nature of their production process hinders their suitability for mass production. To overcome these challenges, we propose a tailored plating solution using an enhanced copper concentration and plating rate. By eliminating the need for fluid motion and reducing the process time, this method can be used for mass production. The Taguchi approach is first used to optimize the copper–quadrol complex solution with the plating rate and decomposition time. This solution exhibits a copper concentration that is over five times higher than that of conventional solutions, a plating rate of 22.2 μm/h, and a decomposition time of 8 min on a Cu layer substrate. This technique enables Cu pillars to be successfully bonded within 7 min at 35 °C. Planarizing the pillar surface yields a high bonding percentage of 99%. Mechanical shear testing shows a significant fracture strength of 76 MPa.

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Development of high copper concentration, low operating temperature, and environmentally friendly electroless copper plating using a copper ‐ glycerin complex solution

Cited by 14 publications

References 25 publications

Mechanism and kinetics investigation of reaction network: 1,3‐Dichloro‐2‐propanol with alkali to prepare epichlorohydrin

Mechanism and kinetics investigation of reaction network: 1,3‐Dichloro‐2‐propanol with alkali to prepare epichlorohydrin

Dislodgement of Hydrogen Bubbles in Microchannels with Embedded Pillars: An Analytical, Experimental, and Numerical Study

A High Copper Concentration Copper-Quadrol Complex Electroless Solution for Chip Bonding Applications

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