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

Authors

  • Yuki Kawaguchi Yuki Kawaguchi Faculty of Chemistry, Materials and Bioengineering, Kansai University
  • Ryuichi Ryuichi Faculty of Chemistry, Materials and Bioengineering, Kansai University
  • Hideya Kawasaki Faculty of Chemistry, Materials and Bioengineering, Kansai University

DOI:

https://doi.org/10.6000/2369-3355.2016.03.02.2

Keywords:

Metal-organic decomposition ink, Electrical conductivity, Sintering.

Abstract

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—10-5Ω 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.

References

[1] Wunscher S, Abbel R, Perelaer J, Schubert US. Progress of alternative sintering approaches of inkjet-printed metal inks and their application for manufacturing of flexible electronic devices. J Mater Chem C 2014; 2: 10232-10261.
http://dx.doi.org/10.1039/C4TC01820F
[2] Abhinav KV, Rao RVK, Karthika P, Singh SP. Copper conductive inks: synthesis and utilization in flexible electronics. RSC Adv 2015; 5: 63985-64030.
http://dx.doi.org/10.1039/C5RA08205F
[3] Woo K, Bae C, Jeong Y, Kim D, Moon J. Inkjet-printed Cu source/drain electrodes for solution-deposited thin film transistors. J Mater Chem 2010; 20: 3877-3882.
http://dx.doi.org/10.1039/c000162g
[4] Jeong S, Lee SH, Jo Y, Lee SS, Seo Y, Ahn BW, Kim G, Jang G-E, Park J-U, Ryua B-H, Choi Y. Air-stable, surface-oxide free Cu nanoparticles for highly conductive Cu ink and their application to printed graphene transistors. J Mater Chem C 2013; 1: 2704-2710.
http://dx.doi.org/10.1039/c3tc00904a
[5] Lee B, Kim Y, Yang S, Jeong I, Moon J. A low-cure-temperature copper nano ink for highly conductive printed electrodes. Curr Appl Phys 2009; 9: e157-e160.
http://dx.doi.org/10.1016/j.cap.2009.03.008
[6] Lee YI, Lee KJ, Goo YS, Kim NW, Byun Y, Kim JD, Yoo B, Choa YH. Effect of Complex Agent on Characteristics of Copper Conductive Pattern Formed by Ink-jet Printing. Jpn J Appl Phys 2010; 49: 086501.
http://dx.doi.org/10.1143/JJAP.49.086501
[7] Kim SJ, Lee J, Choi YH, Yeon DH, Byun Y. Effect of copper concentration in printable copper inks on film fabrication. Thin Solid Films 2012; 520: 2731-2734.
http://dx.doi.org/10.1016/j.tsf.2011.11.056
[8] Yabuki A, Tanaka S. Electrically conductive copper film prepared at low temperature by thermal decomposition of copper amine complexes with various amines. Mater Res Bull 2012; 47: 4107-4111.
http://dx.doi.org/10.1016/j.materresbull.2012.08.052

[9] Araki T, Sugahara T, Jiu J, Nagao S, Nogi M, Koga H, Uchida H, Shinozaki K, Suganuma K. Cu Salt Ink Formulation for Printed Electronics using Photonic Sintering. Langmuir 2013; 35: 11192-11197.
http://dx.doi.org/10.1021/la402026r
[10] Shin DH, Woo S, Yem H, Cha M, Cho S, Kang M, Jeong S, Kim Y, Kang K, Piao, Y. A Self-Reducible and Alcohol-Soluble Copper-Based Metal–Organic Decomposition Ink for Printed Electronics. ACS Appl Mater Interfaces 2014; 6: 3312-3319.
http://dx.doi.org/10.1021/am4036306
[11] Choi YH, Hong SH. Effect of the Amine Concentration on Phase Evolution and Densification in Printed Films Using Cu(II) Complex Ink. Langmuir 2015; 31: 8101-8110.
http://dx.doi.org/10.1021/acs.langmuir.5b01207
[12] Farraj Y, Grouchko M, Magdass S. Self-reduction of a copper complex MOD ink for inkjet printing conductive patterns on plastics. Chem Commun 2015; 51: 1587-1590.
http://dx.doi.org/10.1039/C4CC08749F
[13] Deng D, Qi T, Cheng Y, Jin Y, Xiao F. Copper carboxylate with different carbon chain lengths as metal–organic decomposition ink. J Mater Sci Mater Electron 2014; 25: 390-397.
http://dx.doi.org/10.1007/s10854-013-1599-y
[14] Adner D, Wolf FM, Möckel S, Perelaer J, Schubert US, Lang H. Copper(II) ethylene glycol carboxylates as precursors for inkjet printing of conductive copper patterns. Thin Solid Films 2014; 565: 143-148.
http://dx.doi.org/10.1016/j.tsf.2014.06.054
[15] Yonezawa T, Tsukamoto H, Yong Y, Nguyen MT, Matsubara M. Low temperature sintering process of copper fine particles under nitrogen gas flow with Cu2+-alkanolamine metallacycle compounds for electrically conductive layer formation. RSC Adv 2016; 6: 12048-12052.
http://dx.doi.org/10.1039/C5RA25058G
[16] Hokita Y, Kanzaki M, Sugiyama T, Arakawa R, Kawasaki H. High-Concentration Synthesis of Sub-10-nm Copper Nanoparticles for Application to Conductive Nanoinks. ACS Appl Mater Interfaces 2015; 7: 19382-19389.
http://dx.doi.org/10.1021/acsami.5b05542
[17] Lin Z, Han D, Li S. Study on thermal decomposition of copper(II) acetatemonohydrate in air. J Therm Anal Calorim 2012; 107: 471-475.
http://dx.doi.org/10.1007/s10973-011-1454-4

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Published

2016-10-14

How to Cite

Yuki Kawaguchi, Y. K., Ryuichi, R., & Kawasaki, H. (2016). Formate-Free Metal-Organic Decomposition Inks of Copper Particles and Self-Reductive Copper Complex for the Fabrication of Conductive Copper Films. Journal of Coating Science and Technology, 3(2), 56–61. https://doi.org/10.6000/2369-3355.2016.03.02.2

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