Self-reduction of a copper complex MOD ink for inkjet printing conductive patterns on plastics

Farraj, Yousef; Grouchko, Michael; Magdassi, Shlomo

doi:10.1039/c4cc08749f

Cited by 157 publications

(143 citation statements)

References 31 publications

(4 reference statements)

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“…16−18 However, the band was believed to be due to adsorbed or atmospheric CO 2 traces because it was observed from the start (100°C) with no decomposition of the carboxyl group and it disappeared gradually at an elevated temperature with the decomposition and volatilization of the carboxyl group. Furthermore, the intensity of the bands at 1590 cm 18 The growth of Cu in 1:1 and 1:3 inks can be speculated from the decrease in a whole range of transmittance intensities in the time-resolved in situ FTIR spectra during the thermal heating, because a metallic Cu reflects the IR light. As shown in Figure 4, the IR transmittance of 1:1 ink started to decrease dramatically after ∼4 min of heating and stopped after ∼5.7 min of heating, while that of 1:3 ink dropped mainly from ∼5 to ∼6.7 min of heating, indicating the significant growth of Cu nuclei in both inks.…”

Section: Resultsmentioning

confidence: 98%

Effect of the Amine Concentration on Phase Evolution and Densification in Printed Films Using Cu(II) Complex Ink

Choi

Hong

2015

Langmuir

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The nucleation and growth behavior of Cu nanoparticles during thermal heating of Cu(II) complex inks for printed Cu metallization were investigated, particularly focusing on the effects of the amine concentration on the microstructure evolution and electrical conductivity. Herein, the dual effects of hexylamine as a reducing agent dissociating the carboxyl group from the precursor and a capping agent hindering the subsequent growth of Cu nuclei were confirmed. On the basis of such dual effects of amine, the sufficient complexation of the Cu(II) precursor with a high amine concentration in the ink led to the single-route growth of Cu nanoparticles during thermal heating, which resulted in the dense film with a narrow particle size distribution exhibiting a high electrical conductivity. The electrical conductivity of the film could be further enhanced by a reducing atmosphere with formic acid. Significantly, the understanding of the ink chemistry and the nucleation and growth kinetics in the metal ion complex or metal-organic decomposition (MOD) ink can provide the design rules for the formulation of the solution-type inks to control the microstructure of printed metallization.

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Section: Resultsmentioning

confidence: 98%

Effect of the Amine Concentration on Phase Evolution and Densification in Printed Films Using Cu(II) Complex Ink

Choi

Hong

2015

Langmuir

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“…32 These organic copper complexes can decompose at temperatures as low as 100 C. 32,33 Moreover, with a low sintering temperature, one can also print the copper MOD ink on plastic sheets to make exible conductive patterns. 28 These frontier studies have shown great feasibility of copper MOD ink formulation for conductive copper thin lms. However, although those copper complexes can decompose into metals at low temperatures, the copper MOD inks are regularly found to have strong dewetting 29 or surface morphological problems 32 during the thermal calcination process.…”

Section: -29mentioning

confidence: 99%

Stabilization of the thermal decomposition process of self-reducible copper ion ink for direct printed conductive patterns

et al. 2017

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In this study, a thermally triggered self-reducible copper ink is developed to print conductive patterns on flexible substrates. Inks containing only copper formate (CuF) and monoisopropanol amine (MIPA) generated large bubbles in the CuF decomposing process, and thus the surface morphologies of prepared thin films were largely disturbed. With the addition of octylamine (OA), the bubbling disturbance was relieved due to the lower surface tension and the film uniformity was greatly improved. A low resistivity of 2 Â 10 À7 U m (8.5% of bulk copper) can be reached by heating the ink at 140 C for 5 minutes under a nitrogen environment. XRD results showed the synthesized copper films were comprised of pure metallic copper crystalline. The copper films were composed of closely packed spherical grains of 50 to 500 nm in diameter. After the addition of 1 wt% polyvinylpyrrolidone (PVP) in the ink, the synthesized copper thin films showed great adhesion on glass substrates, and sustained the same conductivity after repeated tape tests.The ink can also be printed on flexible substrates, such as polyethylene terephthalate (PET) or polyimide (PI) thin films, to create highly-conductive tracks with a strong mechanical stability. Finally, various conductive patterns were printed on flexible substrates to show the great potential of this ink for various printed electronic applications. IntroductionThe recent advancements in printing technology have provided a new fabrication method for exible and light-weight electronic devices at low costs. To fabricate these so-called printed electronic devices, inks containing conductive materials are printed on plastic sheets to produce exible microelectronic circuits. As the most essential part in every circuit, electrically conductive interconnects from metal inks have been widely used in these printed devices. To reduce the manufacturing cost, copper has recently attracted wide attention for printed conductive features because of its low price, and high electric conductivity. The most commonly used copper inks are nanoparticle suspensions. 1-7 The printed patterns can yield a low resistivity down to 2.2 times of that for bulk copper 2 aer sintering at 200 C for an hour. However, most plastic substrates might melt or deform at this high temperature. Alternatively, electroless plating approach offers a low-temperature synthetic route for copper thin lm fabrication on plastic surfaces. 8-11Solutions containing active agents are rst printed with microcontact 12-14 or inkjet printing 15-20 methods to produce patterns on plastic substrates. Copper metal are then deposited selectively on the printed patterns in a subsequent electroless plating bath. 12,13,15,16,19 Although electroless plating methods can produce highly conductive copper thin lms on exible substrates at low temperatures, the method needs two processing steps and the plating uid might contaminate or modify the plastic surfaces other than the patterned area. Thus, copper inks that can directly print on selected area with l...

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“…In the printing technique, an ink or paste containing active materials is printed and then sintered to form conductive patterns or films. This makes the method cost-effective, highly efficient in terms of material usage, scalable and simple in terms of processing, and flexible for use on various types of substrates123. Many examples have been reported for using metallic inks in printed electronics, such as light-emitting diodes (LEDs)4, circuits5, flexible displays6, and radio frequency identification (RFID) tags7.…”

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confidence: 99%

“…One type is a suspension or dispersion of fine copper particles or nanoparticles1415161718192021. The other type is the copper-based metal-organic decomposition (MOD) ink, which is composed of a copper salt, amine/amino hydroxyl ligands and other organic components22425262728. Copper-based MOD ink, which has merits such as simplicity and scalability, has been studied for achieving high electrical conductivity at a low sintering temperature.…”

mentioning

confidence: 99%

“…Copper-based MOD ink, which has merits such as simplicity and scalability, has been studied for achieving high electrical conductivity at a low sintering temperature. Some additives, such as diethylene n-butanol2, glycolmethylether2, 1-methyl-2-pyrrolidinone25, octylamine26, and ethyl cellulose25, are generally required in the copper-based MOD inks for improving the uniformity of the prepared inks, increase conductivity and reliability of copper films after sintering, and for preventing liquid film dewetting or unwanted pinholes during the sintering process. However, these organic additives do not have good electrical conductivity and prevent contact between copper particles to some extent, thus decreasing the conductivity of the sintered copper films.…”

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confidence: 99%

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Effect of decomposition and organic residues on resistivity of copper films fabricated via low-temperature sintering of complex particle mixed dispersions

Yong

Nguyen

Tsukamoto

et al. 2017

Sci Rep

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Mixtures of a copper complex and copper fine particles as copper-based metal-organic decomposition (MOD) dispersions have been demonstrated to be effective for low-temperature sintering of conductive copper film. However, the copper particle size effect on decomposition process of the dispersion during heating and the effect of organic residues on the resistivity have not been studied. In this study, the decomposition process of dispersions containing mixtures of a copper complex and copper particles with various sizes was studied. The effect of organic residues on the resistivity was also studied using thermogravimetric analysis. In addition, the choice of copper salts in the copper complex was also discussed. In this work, a low-resistivity sintered copper film (7 × 10−6 Ω·m) at a temperature as low as 100 °C was achieved without using any reductive gas.

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Self-reduction of a copper complex MOD ink for inkjet printing conductive patterns on plastics

Cited by 157 publications

References 31 publications

Effect of the Amine Concentration on Phase Evolution and Densification in Printed Films Using Cu(II) Complex Ink

Effect of the Amine Concentration on Phase Evolution and Densification in Printed Films Using Cu(II) Complex Ink

Stabilization of the thermal decomposition process of self-reducible copper ion ink for direct printed conductive patterns

Effect of decomposition and organic residues on resistivity of copper films fabricated via low-temperature sintering of complex particle mixed dispersions

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