Formate-Free Metal-Organic Decomposition Inks of Copper Particles and Self-Reductive Copper Complex for the Fabrication of Conductive Copper Films
DOI:
https://doi.org/10.6000/2369-3355.2016.03.02.2Keywords:
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
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
Downloads
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
Issue
Section
Articles
License
Policy for Journals/Articles with Open Access
Authors who publish with this journal agree to the following terms:
- Authors retain copyright and grant the journal right of first publication with the work simultaneously licensed under a Creative Commons Attribution License that allows others to share the work with an acknowledgement of the work's authorship and initial publication in this journal.
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work
Policy for Journals / Manuscript with Paid Access
Authors who publish with this journal agree to the following terms:
- Publisher retain copyright .
- Authors are permitted and encouraged to post links to their work online (e.g., in institutional repositories or on their website) prior to and during the submission process, as it can lead to productive exchanges, as well as earlier and greater citation of published work .
