544-19-4Relevant articles and documents
Understanding the Importance of Cu(I) Intermediates in Self-Reducing Molecular Inks for Flexible Electronics
Marchal, Wouter,Longo, Alessandro,Briois, Valérie,Van Hecke, Kristof,Elen, Ken,Van Bael, Marlies K.,Hardy, An
, p. 15205 - 15215 (2019/01/03)
Fast and scalable low-temperature deposition of microscale metallic features is of utmost importance for the development of future flexible smart applications including sensors, wireless communication, and wearables. Recently, a new class of metal-organic decomposition (MOD) copper inks was developed, consisting of self-reducing copper formate containing amine complexes. From these novel inks, copper metal features with outstanding electrical conductivity (±105 S cm-1) are deposited at a temperature of 150 °C or less, which is well below the reduction temperature of orthorhombic α-copper formate (around 225 °C). However, the underlying principle of this reaction mechanism and the relationship between the corresponding temperature shift and the amine coordination are still under debate. The current study provides a full explanation for the shift in reduction temperatures via in situ characterization. The results clearly indicate that the structural resemblance and stability of the Cu(II) starting compound and the occurring Cu(I) intermediate during the in situ reduction are the two main variables that rationalize the temperature shift. As such, the thermal compatibility of copper MOD inks with conventional plastic substrates such as polyethylene terephthalate can be explained, based on metal-organic complex properties.
New complexes of Mn(II), Co(II), Ni(II) and Cu(II) with 2,2'- or 2,4'-bipyridine and formates (Synthesis, thermal and other properties)
Czakis-Sulikowska,Radwanska-Doczekalska,Czylkowska,Markiewicz,Broniarczyk
, p. 327 - 335 (2008/10/09)
New mixed-ligand complexes with empirical formulae: Mn(2-bpy) 1.5L2?2H2O, M(2-bpy)2L 2?3H2O (M(II)=Co, Cu), Ni(2-bpy)3L 2?4H2O and M(2,4'-bpy)2L 2?2H2O (where 2-bpy=2,2'-bipyridine, 2,4'-bpy=2,4'-bipyridine; L=HCOO- ) have been obtained in pure solid-state. The complexes were characterized by chemical and elemental analysis, IR and VIS spectroscopy, conductivity (in methanol and dimethylsulfoxide). The way of metal-ligand coordination discussed. The formate and 2,4'-bpy act as monodentate ligands and 2-bpy as chelate ligand. The new complexes with ligand isomerism were identified. During heating the complexes lose water molecules in one or two steps. Thermal decomposition after dehydration is multistage and yields corresponding metal oxides as final products. A coupled TG-MS system was used to analysis principal volatile thermal decomposition (or fragmentation) products of Ni(2,4'-bpy)2(HCOO) 2?2H2O under dynamic air or argon atmosphere.
Kinetic and thermodynamic studies of the nonisothermal decomposition of anhydrous copper(II) formate in different gas atmospheres
Mohamed, Mohamed A.,Galwey, Andrew K.,Halawy, Samih A.
, p. 13 - 20 (2008/10/09)
The thermal decomposition of anhydrous (orthorhombic) copper(II) formate was studied by programmed rising-temperature methods (TG, DTG, DTA and DSC) to about 250°C in flowing gas atmospheres of nitrogen (inert), hydrogen (reducing) and air (oxidizing). The degradation reaction, anion breakdown, proceeded to completion in two distinct, but partially overlapping, rate processes and apparent Arrhenius parameters, calculated by the Ozawa nonisothermal kinetic method, agreed satisfactorily with the literature results. It was concluded that the two consecutive processes, contributing to the overall reaction, involved stepwise cation reduction: Cu2+ →Cu+→Cu0, with copper(I) formate as intermediate. This mechanism is similar to that proposed in previous studies of the decompositions of copper(II) oxalate, malonate, maleate, fumarate, mellitate and squarate. For all of these reactants, the Cu+ salt has been identified as an intermediate, exhibiting a (slightly) lower relative reactivity than the corresponding Cu2+ salt. For copper(II) formate the response curves in the three different gaseous atmospheres were generally similar, showing that neither oxidizing nor reducing conditions caused a marked change in reactivity. The temperature of reaction initiation in H2 was slightly diminished and the temperature of the second stage of reaction in O2 was raised appreciably. It is believed that electron transfer contributed to the control of reactivity and that the gases present appreciably influence the rates of the contributory reactions occurring.
