Air-stable, surface-oxide free Cu nanoparticles for highly conductive Cu ink and their application to printed graphene transistors

Jeong, Sunho; Lee, Su Hyeon; Jo, Yejin; Lee, Su Yeon; Seo, Yeong Hui; Ahn, Byeong Wan; Kim, Gyeomuk; Jang, Gun–Eik; Park, Jang Ung; Ryu, Beyong Hwan; Choi, Youngmin

doi:10.1039/c3tc00904a

Cited by 138 publications

(104 citation statements)

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“…In a previous study, we demonstrated that oleic acid was capable of acting as a primary surface capping molecule that could stabilize the surface atoms of Cu nanoparticle. 12,25 We believe that oleic acid-involved chemical stabilization is also valid for 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 12 conventional thermal sintering, the efficient role of a low melting-point phase as a flux has been demonstrated widely for various ceramics, for enhancing densification rates, achieving accelerated grain growth, or producing specific grain boundary properties. [26][27][28][29][30] The requisites for a flux phase applicable to Cu nanoparticles are as follows: the possibility of a facile wetchemical synthesis reaction, spatially uniform distribution inside particulate films, interfacial compatibility at a heterogeneous junction between the flux and Cu phase, a low melting point, an electrically conductive nature, and earth-abundance/cost-effectiveness of elements.…”

Section: Resultsmentioning

confidence: 98%

“…Cu nanoparticles were synthesized via chemical reduction of Cu ions in octylamine in an inert atmosphere, as described in our previous study. 12,25 Briefly, 10.4 g of Cu acetate and 25.1 g of oleic acid were added to a three-neck round-bottomed flask containing 73.6 mL of oleylamine. The oleic acid was incorporated as a surface capping molecule and phenylhydrazine was used as a reducing agent.…”

Section: Introductionmentioning

confidence: 99%

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Newly Designed Cu/Cu₁₀Sn₃ Core/Shell Nanoparticles for Liquid Phase-Photonic Sintered Copper Electrodes: Large-Area, Low-Cost Transparent Flexible Electronics

Kim

et al. 2016

Chem. Mater.

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The conductive nanomaterials applicable to unconventional printing techniques have attracted the tremendous attention, and in particular, cost-effective copper-based electrode materials have been recognized a viable candidate to replace the expensive silver counterpart. In this study, we synthesize newly-designed Cu core/Cu 10 Sn 3 shell nanoparticles, as an additive material for overcoming the critical drawbacks in Cu nanoparticle-based electrodes, in combination with a large-area processable, continuous photonic sintering process in a time scale of 10 -3 sec. By virtue of a low melting-point nature of Cu 10 Sn 3 phase, the facile electrode fabrication process is easily triggered, evolving the resistivities of 27.8 and 12.2 µΩ·cm under energy dose conditions of 0.97 and 1.1 J/cm 2 , respectively, at which highly conductive electrodes are not obtainable from phase-pure Cu nanoparticles. The mixture suspension of Cu and Cu/Cu 10 Sn 3 nanoparticles enables for roll-to-roll processable, highly uniform Cu-based electrodes (with a sheet resistance and a standard deviation of 1.21 and 0.29 Ω/square, respectively) even on vulnerable polyethylene naphthalate (PEN) substrate, while the electrodes derived from Cu 10 Sn 3 phase-free Cu nanoparticles suffer from non-uniform characteristics and even a partially insulating nature.The practical applicability of Cu/Cu 10 Sn 3 core/shell nanoparticles is demonstrated with the fabrication of a touch screen panel and an antenna for wireless power transmission.

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Section: Resultsmentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Newly Designed Cu/Cu₁₀Sn₃ Core/Shell Nanoparticles for Liquid Phase-Photonic Sintered Copper Electrodes: Large-Area, Low-Cost Transparent Flexible Electronics

Kim

et al. 2016

Chem. Mater.

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“…Based on the effect of particle size on the sintering temperature, a variety of Cu nanoparticle inks have been developed to achieve conductive Cu wirings . However, unlike Ag and Au nanoparticles, Cu nanoparticles are easily oxidized during the preparation and storage stages under an air atmosphere and form a stable but undesirable surface oxide layer .…”

Section: Introductionmentioning

confidence: 99%

Highly Densified Cu Wirings Fabricated from Air‐Stable Cu Complex Ink with High Conductivity, Enhanced Oxidation Resistance, and Flexibility

Yang

Zhang

et al. 2018

Adv Materials Inter

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The microstructure of printed Cu wirings fabricated from air‐stable Cu complex inks is greatly modified by low‐temperature curing followed by intense pulsed light densification enhancement treatment. The resulting almost full densification of printed Cu wirings enables them to possess a high electrical conductivity of 50% bulk Cu. The dense structure also largely prevents the permeation of oxygen and water into the inner side of the Cu wirings, thereby improving their oxidation resistance and maintaining a stable resistance (R/R0 < 1.5) even after 1000 h aging at 85 °C‐85% RH. In addition, the dense and robust structure can improve the resistance to crack generation and propagation in Cu wirings during the bending, so as to improve their flexibility. The relative resistance of Cu wirings can be kept below 1.2 after 1000 bending cycles. All the results indicate that these highly densified Cu wirings fabricated from air‐stable Cu complex inks can be used to replace the noble metallic Au and Ag wirings for practical application in flexible electronics.

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“…A major challenge for copper-based inks is the very rapid oxidation rate in air, during storage and sintering (essential for obtaining conductive percolation paths). To avoid the oxidation of copper in the sintering process, a reducing gas, such as hydrogen, is typically introduced to supress the oxidation during the sintering process, and the reduction temperature should be higher than 230 ºC when hydrogen is used in order to achive the enhanced reducing aibility [3,4].…”

Section: Introduction *mentioning

confidence: 99%

Formate-Free Metal-Organic Decomposition Inks of Copper Particles and Self-Reductive Copper Complex for the Fabrication of Conductive Copper Films

Kawaguchi

Ryuichi

Kawasaki

2016

J. Coat. Sci. Technol.

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Metal-organic decomposition (MOD) inks have been developed for printed electronics applications. Cu-based MOD inks prevent the oxidation of the metal during storage, as the Cu is already present in an oxidized form (i.e. a salt). However, usually hazardous formates such as Cu (II) formate have to be used as the copper salt in order to ensure thermal decomposition and self-reduction of the metal salt at moderate temperatures (less than 150 °C). In this study, a formate-free hybrid ink containing copper particles and a Cu/1-amino-2-propanol (AmIP)/acetate complex was developed for the fabrication of conductive copper films on flexible polymer substrates at low sintering temperatures. A hybrid ink with a weight ratio of 3:1copper particles to MOD ink produced a conductive copper film with close-packed copper particles and a low resistance of 7.3×10⁻ 5 Ω cm after sintering at a temperature of 180 °C for 60 min under a N2 gas flow. Good oxidation resistance of the copper films was observed after exposure to air at 23 °C for two months. Figure 7: FE-SEM images of a Cu film (prepared from a hybrid MOD ink with a weight ratio of 3:1, copper particles:MOD ink) on a polyimide film after sintering at (a)150 °C and (b) 200 °C for 60 min under N2 flow.

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Air-stable, surface-oxide free Cu nanoparticles for highly conductive Cu ink and their application to printed graphene transistors

Cited by 138 publications

References 48 publications

Newly Designed Cu/Cu₁₀Sn₃ Core/Shell Nanoparticles for Liquid Phase-Photonic Sintered Copper Electrodes: Large-Area, Low-Cost Transparent Flexible Electronics

Newly Designed Cu/Cu₁₀Sn₃ Core/Shell Nanoparticles for Liquid Phase-Photonic Sintered Copper Electrodes: Large-Area, Low-Cost Transparent Flexible Electronics

Highly Densified Cu Wirings Fabricated from Air‐Stable Cu Complex Ink with High Conductivity, Enhanced Oxidation Resistance, and Flexibility

Formate-Free Metal-Organic Decomposition Inks of Copper Particles and Self-Reductive Copper Complex for the Fabrication of Conductive Copper Films

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Air-stable, surface-oxide free Cu nanoparticles for highly conductive Cu ink and their application to printed graphene transistors

Cited by 138 publications

References 48 publications

Newly Designed Cu/Cu10Sn3 Core/Shell Nanoparticles for Liquid Phase-Photonic Sintered Copper Electrodes: Large-Area, Low-Cost Transparent Flexible Electronics

Newly Designed Cu/Cu10Sn3 Core/Shell Nanoparticles for Liquid Phase-Photonic Sintered Copper Electrodes: Large-Area, Low-Cost Transparent Flexible Electronics

Highly Densified Cu Wirings Fabricated from Air‐Stable Cu Complex Ink with High Conductivity, Enhanced Oxidation Resistance, and Flexibility

Formate-Free Metal-Organic Decomposition Inks of Copper Particles and Self-Reductive Copper Complex for the Fabrication of Conductive Copper Films

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Newly Designed Cu/Cu₁₀Sn₃ Core/Shell Nanoparticles for Liquid Phase-Photonic Sintered Copper Electrodes: Large-Area, Low-Cost Transparent Flexible Electronics

Newly Designed Cu/Cu₁₀Sn₃ Core/Shell Nanoparticles for Liquid Phase-Photonic Sintered Copper Electrodes: Large-Area, Low-Cost Transparent Flexible Electronics