Density functional theory study on the oxidation mechanisms of aldehydes as reductants for electroless Cu deposition process

Shimada, Takuya; Sakata, Koichi; Homma, Takayuki; Nakai, Hiromi; Osaka, Tetsuya

doi:10.1016/j.electacta.2005.04.051

Cited by 22 publications

(12 citation statements)

References 21 publications

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“…36,37 Ethanol and acetaldehyde, on the other hand, are adsorbed with the oxygen towards the surface. [38][39][40][41] This indicates that for the breaking of the C-O bond the carbon atom needs to be coordinated to the surface. However, this does not explain why ethylene glycol cannot be reduced since it is known to also adsorb with the carbon atoms to the surface.…”

Section: The C 2 Pathway: Route To Ethylenementioning

confidence: 99%

A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes

et al. 2011

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We have investigated the reaction mechanism of the electrochemical reduction of carbon dioxide to hydrocarbons on copper electrodes. This reaction occurs via two pathways: a C 1 pathway leading to methane, and a C 2 pathway leading to ethylene. To identify possible intermediates in the reduction of carbon dioxide we have studied the reduction of small C 1 and C 2 organic molecules containing oxygen. We followed the formation and consumption of intermediates during the reaction as a function of potential, using online mass spectrometry. For the C 1 pathway we show that it is very likely that CHO ads is the key intermediate towards the breaking of the C-O bond and, therefore, the formation of methane. For the C 2 pathway we suggest that the first step is the formation of a CO dimer, followed by the formation of a surface-bonded enediol or enediolate, or the formation of an oxametallacycle. Both the enediol(ate) and the oxametallacycle would explain the selectivity of the C 2 pathway towards ethylene. This new mechanism is significantly different from existing mechanisms but it is the most consistent with the available experimental data. ExperimentalAll experiments were carried out in an electrochemical cell using a three-electrode assembly at room temperature. The cell and

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Section: The C 2 Pathway: Route To Ethylenementioning

confidence: 99%

A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes

et al. 2011

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“…For elements H, O, C, and P, 6-311G(d,p) basis sets are used in this work. The LANL2DZ basis sets were adopted by Hay and Wadt for modeling Sn atoms − and by Homma et al − and Bozzini et al for studying electroless and electrodeposition processes. Thus, we utilize these basis sets for Sn and Au.…”

Section: Experimental Sectionmentioning

confidence: 99%

AuSn20 Eutectic Electrodeposition through Alternative Complexing of Pyrophosphoric Acid: Insights from Electrochemical and DFT Methods

et al. 2013

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Eutectic AuSn20 solder is an important material for electronic packaging technology due to its superior mechanical and thermal conductive properties. In this work, AuSn20 alloy films are prepared via the electrodeposition method for the first time. The electrodeposition is cost-effective with improved control over the alloy content when compared to traditional powdered metallurgy methods. Pyrophosphoric acid was found to be an effective complexing agent to minimize the difference of the deposition potentials between Au and Sn, making the codeposition of AuSn alloys possible. Importantly, electrochemical characterization was combined with density functional theory (DFT) calculations to provide insight into the mechanism of the alloy codeposition when pyrophosphoric acid was used as the complexing agent. In particular, natural bond orbital (NBO) charge distribution and the lowest unoccupied molecular orbital (LUMO) characteristics of [P2O7]4–-Sn(II) and [P2O7]4–-Au(I) complexes are calculated, suggesting that [P2O7]4– is able to coordinate more strongly with Sn(II) than Au(I). As a result, it can thus shift the deposition potentials of Au(I) and Sn(II) much closer. As the DFT predicted, the role of pyrophosphoric acid as a complexing agent has been experimentally verified, making codeposition of Au and Sn realistic. The structures of the obtained AuSn20 films are determined using scanning electron microscopy (SEM) and energy dispersive X-ray spectrometry (EDX) and found to be consistent with AuSn/Au5Sn eutectic as predicted by the Au–Sn phase diagram. Additionally, the measured melting point is in good agreement with the theoretically determined one. Relevant tests demonstrated in this work indicate that the newly developed electrodeposited AuSn20 alloy coatings are suitable for microelectronic soldering applications.

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“…The dehydrogenation step has also been demonstrated to be significant in case of other reductants such as dimethylamine borane (DMAB) and aldehydes; [11][12][13] thus, for elucidating its origin, further investigation on the interaction of the orbitals for hypophosphite ion and metal surfaces was conducted. 19,20 Figure 5 schematically shows the results obtained for the case with Pd and Cu surfaces.…”

Section: Theoretical Analysis On the Reaction Mechanism Ofmentioning

confidence: 99%

“…[11][12][13] For determining the optimal adsorption configuration of hypophosphite ion at the metal surface, two alternative cases were assumed, as schematically shown in Fig. 2, in which hypophosphite ion was adsorbed onto the metal surface from the O and H sides, respectively.…”

Section: Theoretical Analysis On the Reaction Mechanism Ofmentioning

confidence: 99%

Electrochemical Processes for the Fabrication of Functional Micro–nano Structures and Devices: Mechanistic Understanding and Process Development

Homma

2015

Electrochemistry

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Electrochemical approaches for the fabrication of functional micro-nano structures and devices were comprehensively described primarily on the basis of the results obtained from previous studies conducted by the author's group with the aim of demonstrating the potential for achieving further precise controllability. First, a theoretical study was conducted for investigating the processes, mainly focusing upon electroless deposition to present an approach for analyzing its reaction mechanism from the molecular level. These approaches could be powerful tools for elucidating the overall process and could contribute toward achieving the precise design of processes. Second, some experimental approaches for achieving the precise control of micro-nano fabrication of functional structures, such as maskless and electroless fabrication of metal nano-patterns, lateral enhanced electrodeposition to form ultrathin layers, as well as the nanostructures for various devices by through-mask electrochemical deposition, were introduced to demonstrate high capability of the processes for nanoscale fabrication in various applications.

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Density functional theory study on the oxidation mechanisms of aldehydes as reductants for electroless Cu deposition process

Cited by 22 publications

References 21 publications

A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes

A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes

AuSn20 Eutectic Electrodeposition through Alternative Complexing of Pyrophosphoric Acid: Insights from Electrochemical and DFT Methods

Electrochemical Processes for the Fabrication of Functional Micro–nano Structures and Devices: Mechanistic Understanding and Process Development

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Density functional theory study on the oxidation mechanisms of aldehydes as reductants for electroless Cu deposition process

Cited by 22 publications

References 21 publications

A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes

A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes

AuSn20 Eutectic Electrodeposition through Alternative Complexing of Pyrophosphoric Acid: Insights from Electrochemical and DFT Methods

Electrochemical Processes for the Fabrication of Functional Micro&ndash;nano Structures and Devices: Mechanistic Understanding and Process Development

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Electrochemical Processes for the Fabrication of Functional Micro–nano Structures and Devices: Mechanistic Understanding and Process Development