Effectiveness of Ligand Denticity-Dependent Oxidation Protection in Copper MOD Inks

Marchal, Wouter; Mattelaer, Felix; Hecke, Kristof Van; Briois, Valérie; Longo, Alessandro; Reenaers, Dieter; Elen, Ken; Detavernier, Christophe; Deferme, Wim; Bael, Marlies K. Van; Hardy, An

doi:10.1021/acs.langmuir.9b02281

Cited by 10 publications

(11 citation statements)

References 54 publications

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“…Evidence for the advantageous properties of bidendate ligands have been reported with ethylenediamine ligands yielding uniform particle films with less oxides, an indication that these ligands improve the stability of intermediates. 23,52 These films could be sintered in air to yield films with resistivity values as low as 1.8 × 10 −5 Ω•cm and were demonstrated as flexible conductors for LED lights. 23 Opportunities may exist to balance these two opposing effects by using mixtures of ligands 2,7,9 or by adding conductive fillers, 53,54 as has been reported previously.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Mechanistic Insight into Bis(amino) Copper Formate Thermochemistry for Conductive Molecular Ink Design

Shin

Lacelle

et al. 2020

ACS Appl. Mater. Interfaces

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Increasing attention has been given to amine−copper formate complexes for their use as low-cost printable conductive inks. The structure of amine ligands coordinated to copper centers has been reported to dictate the properties of copper molecular inks, such as stability and printability, thereby influencing the copper reduction pathway during the thermolysis. Yet, the underlying mechanism by which formate is oxidized when complexed with amine ligands is still not fully understood. Here, we propose a mechanistic pathway of copper formate dehydrogenation and decarboxylation and examine the critical role that amine ligands play in their thermal decomposition by employing first-principles electronic structure computations and experimental analyses of thermolysis reactions. Based on the computational characterization of the relevant reaction pathways for a number of primary and secondary amines as well as pyridine ligand complexes, we are the first to show that the hydrogen bonds formed between the amine ligand and formate are the key factors governing the activation energy, providing a design principle for the synthesis of organic ligands that can tune the height of the reaction barriers of the dehydrogenation and decarboxylation reactions. The calculations, confirmed by NMR studies, show that the reduction of Cu(II) to Cu(I) occurs in concert with the release of H 2 via the dimerization of Cu(II) hydride. This result suggests that the monomeric elimination of H 2 is not favorable for the Cu(II) to Cu(I) reduction and thus identifies dimeric amino copper formate as an important intermediate for copper reduction whose thermodynamic stabilities are also dictated by the nature of the amine ligands.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Mechanistic Insight into Bis(amino) Copper Formate Thermochemistry for Conductive Molecular Ink Design

Shin

Lacelle

et al. 2020

ACS Appl. Mater. Interfaces

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“…When a 1:1 stoichiometry was used, no reaction occurred whilst 1:3 and greater would yield the previously reported CuL 2 compound. [34,35] Interestingly, a 1:2 stoichiometry yielded a tetrameric type-II cube-like copper alkoxide (4), [24,41] with the Scheme 1. Synthetic routes to compounds 1-4.…”

Section: Synthesismentioning

confidence: 99%

“…Previous DFT calculations had indicated that two copper bound formate ligands would be required to provide a sufficiently reducing environment for the complete conversion to metallic copper. [22][23][24][25] Boiling point of the alkanolamine has been previously demonstrated to alter the degradation profile of copper(II) formate based inks; in the TGA-MS, the lower boiling point additives (b.p. 1-aminopropan-2-ol: 150 °C) are released first, as expected, likely playing a role in the TGA profile of inks I 1-3 .…”

Section: Printing Optimisation and Device Fabricationmentioning

confidence: 99%

“…TGA-mass spectrometry (MS) detected CO 2 as the first by-product leading to the conclusion that the two formate ligands are responsible for the reduction of the copper. [22][23][24][25] Marchal et al used in situ Xray absorption spectroscopy confirming the Cu(I) presence during reduction, [23] following this work with a study showing that bidentate ligands aided in oxidation prevention. [24] A chemical explanation to this lowering effect upon coordination with alkanolamines remains unclear, highlighting the urgent need to ascertain the link between molecular structure and precursor properties [26] to make more informed decisions about ligand choice.…”

Section: Introductionmentioning

confidence: 96%

“…[22][23][24][25] Marchal et al used in situ Xray absorption spectroscopy confirming the Cu(I) presence during reduction, [23] following this work with a study showing that bidentate ligands aided in oxidation prevention. [24] A chemical explanation to this lowering effect upon coordination with alkanolamines remains unclear, highlighting the urgent need to ascertain the link between molecular structure and precursor properties [26] to make more informed decisions about ligand choice. [27][28][29] There are few literature reports that attempt to establish this link [30] though Paquet et al [31,32] have recently reported the isolation of a range of MOD complexes synthesized by the reaction of copper(II) formate with various pyridines and primary and secondary amines.…”

Section: Introductionmentioning

confidence: 96%

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Unraveling the Steric Link to Copper Precursor Decomposition: A Multi‐Faceted Study for the Printing of Flexible Electronics

et al. 2023

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The field of printed electronics strives for lower processing temperatures to move toward flexible substrates that have vast potential: from wearable medical devices to animal tagging. Typically, ink formulations are optimized using mass screening and elimination of failures; as such, there are no comprehensive studies on the fundamental chemistry at play. Herein, findings which describe the steric link to decomposition profile: combining density functional theory, crystallography, thermal decomposition, mass spectrometry, and inkjet printing, are reported. Through the reaction of copper(II) formate with excess alkanolamines of varying steric bulk, tris-co-ordinated copper precursor ions: "[CuL 3 ]," each with a formate counter-ion (1-3) are isolated and their thermal decomposition mass spectrometry profiles are collected to assess their suitability for use in inks (I 1-3 ). Spin coating and inkjet printing of I 1,2 provides an easily up-scalable method toward the deposition of highly conductive copper device interconnects (𝝆 = 4.7-5.3 × 10 −7 𝛀 m; ≈30% bulk) onto paper and polyimide substrates and forms functioning circuits that can power light-emitting diodes. The connection among ligand bulk, coordination number, and improved decomposition profile supports fundamental understanding which will direct future design.

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Precursor Design Strategies for the Low‐Temperature Synthesis of Functional Oxides: It's All in the Chemistry

Marchal

Sloovere

Daenen

et al. 2020

Chemistry A European J

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Solution‐based (multi)metal oxide synthesis has been carried out employing a large diversity of precursor routes. The selection of an appropriate synthesis strategy is frequently dictated by the resulting material properties, although this choice should also be based on green chemistry principles, atom economy considerations and energy efficiency. In order to limit the required energy budget to convert the chemical precursor to the target oxide material, various approaches were recently reported. This Review summarizes some frequently encountered low‐temperature routes, critically assessing their application window and advantages. More specifically, auto‐combustion synthesis, UV‐assisted decomposition routes, sol–gel network adjustments and precursor complex design concepts are discussed. It is expected that this toolbox of low‐temperature strategies may assist further progress in the field, stimulating novel applications, such as flexible electronics or organic–oxide hybrid materials, which are very sensitive to the temperature requirements.

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Effectiveness of Ligand Denticity-Dependent Oxidation Protection in Copper MOD Inks

Cited by 10 publications

References 54 publications

Mechanistic Insight into Bis(amino) Copper Formate Thermochemistry for Conductive Molecular Ink Design

Mechanistic Insight into Bis(amino) Copper Formate Thermochemistry for Conductive Molecular Ink Design

Unraveling the Steric Link to Copper Precursor Decomposition: A Multi‐Faceted Study for the Printing of Flexible Electronics

Precursor Design Strategies for the Low‐Temperature Synthesis of Functional Oxides: It's All in the Chemistry

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