Electrochemical Assembly of Thiol-based Monolayer on Copper for Epoxy-Cu Adhesion Improvement

Kwok, Stephen C.T.; Ciucci, Francesco; Yuen, M.M.F.

doi:10.1016/j.electacta.2013.12.146

Cited by 9 publications

(5 citation statements)

References 21 publications

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“…Here, we demonstrate a low‐cost, single‐step hybrid‐layer (HL) solution that during deposition simultaneously reduces the native Cu‐oxide and forms a strong bond to the Cu surface. The HL, synthesized through a sol–gel process with organothiol, organosilane, and metal alkoxide precursors, resulted in not only a marked ninefold improvement in adhesion and a substantially suppressed Cu‐migration, but a more efficient Cu‐oxide reduction with a rapid and organic‐solvent‐free process step requiring only 30 s compared to the previously reported 30 min …”

Section: Introductionmentioning

confidence: 92%

“…Unlike aluminum oxide (Al 2 O 3 ) which is dense and tenacious, the native Cu‐oxide is voluminous and weak, and acts as a weak interlayer preventing sufficient adhesion . Multiprocess and multilayer solutions do exist to promote adhesion such as the use of electroless‐plating in conjunction with heat treatment to control the formation/structure of the Cu oxide, the use of hot alkaline solutions as an oxide forming agent, and the combined use of a chemical reducing pretreatment followed by an organic‐solvent‐based self‐assembly of organothiol monolayer . These processes are, however, generally expensive and not compatible with low‐vcost manufacturing.…”

Section: Introductionmentioning

confidence: 99%

“…These processes are, however, generally expensive and not compatible with low‐vcost manufacturing. In the case of self‐assembly, the process is slow and must be accelerated with an electrochemical reaction, but the time to obtain adequate adhesion remains relatively long at ≈30 min …”

Section: Introductionmentioning

confidence: 99%

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Organothiol‐Based Hybrid‐Layer Strategy for High‐Performance Copper Adhesion and Stress‐Migration via Simultaneous Oxide Reduction

Xiao

Watson

Dauskardt

2016

Adv Materials Inter

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The presence of defective native copper‐oxide (CuxO) remains a challenge for device technologies owing to its detrimental effects on the adhesion, moisture sensitivity and stress‐migration. Here we demonstrate a rapid, single‐step, and organic‐solvent‐free sol‐gel deposition process that is capable of simultaneously reducing the weak native Cu‐oxide while forming a densely connected Cu/hybrid interface. A marked 9‐fold improvement in adhesion is reported, along with a substantial decrease in the Cu stress‐migration rate during in‐situ isothermal stress‐relaxation experiments. The enhanced Cu/hybrid interface adhesion and the improved Cu stress‐migration performance were attributed to the partial reduction of the ~2 nm native Cu2O layer as demonstrated via atomic‐resolution transmission electron microscopy. The hybrid‐layer strategy we developed is expected to be effective in not only being a strong candidate for adhesion improvement to Cu, but in promoting Cu stress‐ and the related electro‐migration performance.

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Section: Introductionmentioning

confidence: 92%

Section: Introductionmentioning

confidence: 99%

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Organothiol‐Based Hybrid‐Layer Strategy for High‐Performance Copper Adhesion and Stress‐Migration via Simultaneous Oxide Reduction

Xiao

Watson

Dauskardt

2016

Adv Materials Inter

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“…SAM films of some organic molecules formed on metal substrates have been used in many devices and industrial applications (bio-sensors, heat exchangers, microelectronics, conductive circuit boards, electrical switches, and pumps are some examples) owing to their features such as high coverage, fast film-forming, low cost, few defects, and favorable efficiency. [35][36][37][38] Müller and co-worker [39] reported that SAM films can be used for corrosion protection copper as well as sensor or biosensor for biomolecules and as transistors and switches for electronic devices. For all that the metal coverage has an enormous impact on the catalytic activity regarding CO oxidation as well as methanol electrooxidation in the presence of 4,4 0 -dithiodipyridine SAM film on Au (111) electrodes.…”

Section: Introductionmentioning

confidence: 99%

The use of avocado seed self‐assembly monolayer films for the catalysis of methanol electrooxidation reaction

Şahin

2022

J Chinese Chemical Soc

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Catalysts are important equipment that limits the performance of direct methanol fuel cells (DMFC). With the use of appropriate electrocatalysts, the efficiency of DMFC can be increased. Although the platinum-based catalysts have high efficiency for this process high cost and its limited sources on the earth are the main drawbacks. On the other hand, platinum affectivity may be alternative material due to its high resistance against CO-poisoning on the electrode/solution interface. They have also a low cost. In this study, the extracts of avocado seed (AS) are prepared in ethanol solvent and their self-assembly monolayer (SAM) films were prepared on the copper specimens (Cu/AS-SAM). The AS-SAM film modified catalyst was used as anode material for electrooxidation of methanol in an alkaline solution. To increase catalytic efficiency, the surface of Cu/AS-SAM was modified by electrodeposition of Ni. The surfaces of the bare copper, the AS-SAM film, and the Ni-modified were described by SEM, AFM, and EDX-mapping measurements. Their electrocatalytic activity and stability were evaluated with 1.0 M methanol containing alkaline solution by cyclic voltammetry (CV), Tafel curves and chronoamperometry (CA) tests. The results showed that a durable and homogeneous AS-SAM film forms on the copper surface from the extracts of AS in ethanol solvent. The AS-SAM film is electroactive for the methanol electrooxidation reaction. Moreover, modification of the film by depositing with Ni enhances its activity. The AS, agriculture waste can be utilized for fabricating anode materials for methanol electrooxidation reactions.

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“…Electroassisted adsorption of organothiol molecules on active metals has been reported. 24 With this approach, high-quality SAMs are formed in much shorter periods of time on gold as well as on oxidizable metals and alloys such as nickel 25 and copper. 26 More recently, Metoki et al 27 have investigated the electrochemical formation of alkylphosphonic acids SAMs on the surface of a Ti-6Al-4V alloy.…”

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confidence: 99%

Electroassisted Auto-Assembly of Alkylphosphonic Acids Monolayers on Nitinol

Vanhooland

Devillers

Issakova

et al. 2016

J. Electrochem. Soc.

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Nitinol is a very attractive material for biomedical applications due to its shape memory and superelasticity properties. However, its high nickel content makes it a potentially toxic material because of nickel biotoxicity. Among the numerous ways explored to tune Nitinol surface properties and improve its corrosion resistance, the formation of alkylphosphonic acids self-assembled monolayers (SAMs) is a versatile and attractive approach. Recently, electroassisted adsorption of surfactant molecules on active metals has been investigated. In this paper we compare the electroassisted formation (EG) of alkylphosphonic acids (n-dodecyl-and n-octadecylphosphonic acids) SAMs to the direct adsorption method (direct adsorption CG) on Nitinol surfaces initially submitted to a hydrothermal treatment. XPS, contact angle and polarization curves measurements show that electroassisted grafting gives nearly as good results as the ones obtained by the conventional immersion method, but in a much shorter time. There is no significant impact of grafting time. Grafting potential, on the contrary, appears to influence positively the layers' density and the substrate resistance to corrosion. Alkyl chain length effects on the resulting SAMs properties have also been discussed. Electroassisted grafting is thus confirmed to be a very promising method for the grafting of phosphonic acids derivatives on oxidized metallic surfaces.

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Electrochemical Assembly of Thiol-based Monolayer on Copper for Epoxy-Cu Adhesion Improvement

Cited by 9 publications

References 21 publications

Organothiol‐Based Hybrid‐Layer Strategy for High‐Performance Copper Adhesion and Stress‐Migration via Simultaneous Oxide Reduction

Organothiol‐Based Hybrid‐Layer Strategy for High‐Performance Copper Adhesion and Stress‐Migration via Simultaneous Oxide Reduction

The use of avocado seed self‐assembly monolayer films for the catalysis of methanol electrooxidation reaction

Electroassisted Auto-Assembly of Alkylphosphonic Acids Monolayers on Nitinol

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