Copper conductive patterns through spray-pyrolysis of copper-diethanolamine complex solution

Chotipanich, Jutamart; Bakar, Suraya Hanim Abu; Arponwichanop, Amornchai; Yonezawa, Tetsu; Kheawhom, Soorathep

doi:10.1371/journal.pone.0200084

Cited by 2 publications

(1 citation statement)

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“…Many of the advantages of these inks are derived from their molecular nature, and thus molecular tailoring of the amine ligand may be used to improve the stability and printability of the ink. For instance, the basicity, degree of steric hindrance, molecular weight, and stoichiometry of amine ligands bound to copper formate have been shown to govern the copper particle sizes, film morphologies, and porosity that ultimately determine the electrical properties of the copper films. − …”

Section: Introductionmentioning

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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