Indium electrodeposition from indium(<scp>iii</scp>) methanesulfonate in DMSO

Monnens, Wouter; Deferm, Clio; Binnemans, Koen; Fransaer, Jan

doi:10.1039/d0cp03277h

Cited by 10 publications

(3 citation statements)

References 29 publications

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“…Non-aqueous solutions have drawn much attention to the electrodeposition of indium. Monnens et al reported indium electrodeposition from DMSO, 1,2-dimethoxyethane and poly(ethylene glycol), respectively [7,8]. It was shown that the reduction of In(III) to both In(I) and In(0) occurred and micron-and nano-sized metallic indium were formed.…”

Section: Introductionmentioning

confidence: 99%

Electrodeposition of Indium from an Ionic Liquid Investigated by In Situ Electrochemical XPS

Liu

Cheng

Höfft

et al. 2021

Metals

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The electrochemical behavior and electrodeposition of indium in an electrolyte composed of 0.1 mol/L InCl3 in 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)amide ([Py1,4]TFSI) on a gold electrode were investigated. The cyclic voltammogram revealed several reduction and oxidation peaks, indicating a complex electrochemical behavior. In the cathodic regime, with the formation of an In-Au alloy, the reduction of In(III) to In(I) and of In(I) to In(0) takes place. In situ electrochemical X-ray photoelectron spectroscopy (XPS) was employed to investigate the reduction process by monitoring the oxidation states of the components during the cathodic polarization of 0.1 mol/L InCl3/[Py1,4]TFSI on a gold working electrode under ultra-high vacuum (UHV) conditions. The core electron binding energies of the IL components (C 1s, O 1s, F 1s, N 1s, and S 2p) shift almost linearly to more negative values as a function of the applied cell voltage. At −2.0 V versus Pt-quasi reference, In(I) was identified as the intermediate species during the reduction process. In the anodic regime, a strong increase in the pressure in the XPS chamber was recorded at a cell voltage of more than −0.5 V versus Pt quasi reference, which indicated, in addition to the oxidation reactions of In species, that the oxidation of Cl− occurs. Ex situ XPS and XRD results revealed the formation of metallic In and of an In-Au alloy.

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Section: Introductionmentioning

confidence: 99%

Electrodeposition of Indium from an Ionic Liquid Investigated by In Situ Electrochemical XPS

Liu

Cheng

Höfft

et al. 2021

Metals

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“…However, these electrolytes can support the formation of intermediate monovalent species, both for indium and gallium, which are typically unstable and undergo a disproportionation reaction. [27][28][29][30][31][32] Ideally, the formation of these monovalent species should be avoided as it complicates the overall process.…”

Section: Introductionmentioning

confidence: 99%

Scalable Electrodeposition of Liquid Metal from an Acetonitrile‐Based Electrolyte for Highly Integrated Stretchable Electronics

Monnens,

Zhang,

Zhou

et al. 2023

Advanced Materials

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The advancement of highly integrated stretchable electronics requires the development of scalable sub‐micrometer conductor patterning. Eutectic gallium indium (EGaIn) is an attractive conductor for stretchable electronics, as its liquid metallic character grants it high electrical conductivity upon deformation. However, its high surface tension makes its patterning with sub‐micrometer resolution challenging. In this work, this limitation is overcome by way of the electrodeposition of EGaIn. A non‐aqueous acetonitrile‐based electrolyte that exhibits high electrochemical stability and chemical orthogonality is used. The electrodeposited material leads to low‐resistance lines that remain stable upon (repeated) stretching to a 100% strain. Because electrodeposition benefits from the resolution of mature nanofabrication methods used to pattern the base metal, the proposed “bottom‐up” approach achieves a record‐high density integration of EGaIn regular lines of 300 nm half‐pitch on an elastomer substrate by plating on a gold seed layer prepatterned by nanoimprinting. Moreover, vertical integration is enabled by filling high‐aspect‐ratio vias. This capability is conceptualized by the fabrication of an omnidirectionally stretchable 3D electronic circuit, and demonstrates a soft‐electronic analog of the stablished damascene process used to fabricate microchip interconnects. Overall, this work proposes a simple route to address the challenge of metallization in highly integrated (3D) stretchable electronics.

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“…It is demonstrated that indium(I) is more stable than a methanesulfonate-based DMSO electrolyte that was previously investigated by us, indicating that chlorides (as well as DMSO) play a major role in stabilizing the monovalent species. 17 In circumstances where there is an abundance of indium metal and indium(III), the comproportionation (reverse of reaction (1)) even occurs, favoring the formation of indium(I) species. Interestingly, this has not been observed in chloridecontaining aqueous environments.…”

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confidence: 99%

The Electrochemical Behavior of Indium in DMSO-Based Electrolytes Containing Indium(III) Chloride and Indium(I) Chloride: An Interplay Between the Disproportionation and the Comproportionation Reaction, and the Occurrence of Oscillations

Monnens,

Binnemans,

Fransaer

2024

J. Electrochem. Soc.

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The electrochemistry of indium was investigated using electrolytes composed of (1) indium(III) chloride (InCl3) in dimethyl sulfoxide (DMSO) and (2) indium(I) chloride (InCl) in DMSO, with tetraethylammonium chloride (TEACl) used as a conducting background electrolyte. Cyclic voltammograms (CVs) in combination with quartz crystal microbalance (QCM) and rotating ring disk electrode (RRDE) tools revealed that indium(I) species play a prominent role during reduction. Both a disproportionation reaction and a comproportionation reaction were observed involving indium metal, indium(I), and indium(III) species, with the occurrence of either reaction depending on their relative concentrations. An equilibrium can exist between indium(I), indium(III), and indium(0). The equilibrium constant for the disproportionation reaction was determined to be 6.98 × 102 M–2. For both electrolyte (1) and (2), the reduction of indium(I) to indium metal, of indium(III) to indium(I), and of indium(III) to indium metal was identified by the CVs. Stripping of indium metal led to the formation of indium(I), which could be further oxidized to indium(III). Electrochemical oscillations were observed during the reduction of indium(III) to indium(I) (followed by the reduction of indium(I) to indium(0)). These oscillations occurred at –1.5 V vs Ag+/Ag and only appear on an indium (covered) electrode surface. It was postulated that these oscillations are due to the negative resistance that originates from the chloride-catalyzed reduction of indium(III) to indium(I), due to chloride removal from the indium surface.

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Indium electrodeposition from indium(iii) methanesulfonate in DMSO

Abstract: The electrochemical investigation and electrodeposition of indium in a mixture of indium(iii) methanesulfonate and DMSO.

Cited by 10 publications

References 29 publications

Electrodeposition of Indium from an Ionic Liquid Investigated by In Situ Electrochemical XPS

Electrodeposition of Indium from an Ionic Liquid Investigated by In Situ Electrochemical XPS

Scalable Electrodeposition of Liquid Metal from an Acetonitrile‐Based Electrolyte for Highly Integrated Stretchable Electronics

The Electrochemical Behavior of Indium in DMSO-Based Electrolytes Containing Indium(III) Chloride and Indium(I) Chloride: An Interplay Between the Disproportionation and the Comproportionation Reaction, and the Occurrence of Oscillations

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