Precursor (Metal-organic decomposition (MOD)) inks are used to fabricate 2D and 3D printed conductive structures directly onto a substrate. By formulating a nanoalloy structure containing multiple metals, the opportunity to modify chemical and physical properties exists. In this paper, a copper-nickel bimetallic nanoalloy film was fabricated by mixing copper and nickel precursor inks and sintering them in vacuum. The individual elemental inks were formulated and characterized using SEM, EDS, and XRD. During thermal processing, elemental copper forms first and is followed by the formation of bimetallic copper-nickel alloy. The encapsulation of the underlying copper by the nickel-rich alloy provides excellent oxidation resistance. No change in film resistance was observed after the film was exposed to an oxygen plasma. Nanoalloy films printed using reactive metallic inks have a variety of important applications involving local control of alloy composition. Examples include facile formation of layered nanostructures, and electrical conductivity with oxidative stability.
Kahn, B.E. (2015) Patterning Processes for Flexible Electronics. Proceedings of the IEEE, 103, 497-517. https://doi.org/10.1109/JPROC.2015.2401553
Jung, M., Kim, J., Noh, J., Lim, N., Lim, C., Lee, G., Kim, J., Kang, H., Jung, K. and Leonard, A.D. (2010) All-Printed and Roll-to-Roll-Printable 13.56-MHz-Operated 1-Bit RF Tag on Plastic Foils. IEEE Transactions on Electron Devices, 57, 571-580. https://doi.org/10.1109/TED.2009.2039541
Sangoi, R., Smith, C.G., Seymour, M.D., Venkataraman, J.N., Clark, D.M., Kleper, M.L. and Kahn, B.E. (2005) Printing Radio Frequency Identification (RFID) Tag Antennas Using Inks Containing Silver Dispersions. Journal of Dispersion Science and Technology, 25, 513-521. https://doi.org/10.1081/DIS-200025721
Montoya, T.P. and Kirshchenmann, K.J. (2007) Antennas with Discrete Resistive Loading Built by Direct-Write Fabrication. 2007 IEEE Antennas and Propagation Society International Symposium, Honolulu, HI, 9-15 June 2007, 4080-4083. https://doi.org/10.1109/APS.2007.4396437
Yang, L., Rida, A., Vyas, R. and Tentzeris, M.M. (2007) RFID Tag and RF Structures on a Paper Substrate Using Inkjet-Printing Technology. IEEE Transactions on Microwave Theory and Techniques, 55, 2894-2901. https://doi.org/10.1109/TMTT.2007.909886
Vaillancourt, J., Zhang, H., Vasinajindakaw, P., Xia, H., Lu, X., Han, X., Janzen, D.C., Shih, W.-S., Jones, C.S. and Stroder, M. (2008) All Ink-Jet-Printed Carbon Nanotube Thin-Film Transistor on a Polyimide Substrate with an Ultrahigh Operating Frequency of Over 5 GHz. Applied Physics Letters, 93, Article ID: 243301. https://doi.org/10.1063/1.3043682
Noguchi, Y., Sekitani, T. and Someya, T. (2007) Printed Shadow Masks for Organic Transistors. Applied Physics Letters, 91, Article ID: 133502. https://doi.org/10.1063/1.2790495
Jabbour, G.E., Radspinner, R. and Peyghambarian, N. (2001) Screen Printing for the Fabrication of Organic Light-Emitting Devices. IEEE Journal of Selected Topics in Quantum Electronics, 7, 769-773. https://doi.org/10.1109/2944.979337
Jo, J., Yu, J.-S., Lee, T.-M. and Kim, D.-S. (2009) Fabrication of Printed Organic Thin-Film Transistors Using Roll Printing. Japanese Journal of Applied Physics, 48, Article ID: 04C181. https://doi.org/10.1143/JJAP.48.04C181
Kopola, P., Tuomikoski, M., Suhonen, R. and Maaninen, A. (2009) Gravure Printed Organic Light Emitting Diodes for Lighting Applications. Thin Solid Films, 517, 5757-5762. https://doi.org/10.1016/j.tsf.2009.03.209
Liu, R., Ding, H., Lin, J., Shen, F., Cui, Z. and Zhang, T. (2012) Fabrication of Platinum-Decorated Single-Walled Carbon Nanotube Based Hydrogen Sensors by Aerosol Jet Printing. Nanotechnology, 23, Article ID: 505301. https://doi.org/10.1088/0957-4484/23/50/505301
Wei, L.-J. and Oxley, C.H. (2016) Carbon Based Resistive Strain Gauge Sensor Fabricated on Titanium Using Micro-Dispensing Direct Write Technology. Sensors and Actuators A: Physical, 247, 389-392. https://doi.org/10.1016/j.sna.2016.06.025
Khan, S., Lorenzelli, L. and Dahiya, R. (2014) Screen Printed Flexible Pressure Sensors Skin. 25th Annual SEMI Advanced Semiconductor Manufacturing Conference (ASMC 2014), Saratoga Springs, NY, 19-21 May 2014, 219-224. https://doi.org/10.1109/ASMC.2014.6847002
Shi, C., Shan, X., Tarapata, G., Jachowicz, R., Weremczuk, J. and Hui, H. (2011) Fabrication of Wireless Sensors on Flexible Film Using Screen Printing and via Filling. Microsystem Technologies, 17, 661-667. https://doi.org/10.1007/s00542-010-1161-2
Deng, D., Jin, Y., Cheng, Y., Qi, T. and Xiao, F. (2013) Copper Nanoparticles: Aqueous Phase Synthesis and Conductive Films Fabrication at Low Sintering Temperature. ACS Applied Materials & Interfaces, 5, 3839-3846. https://doi.org/10.1021/am400480k
Joo, S.-J., Park, S.-H., Moon, C.-J. and Kim, H.-S. (2015) A Highly Reliable Copper Nanowire/Nanoparticle Ink Pattern with High Conductivity on Flexible Substrate Prepared via a Flash Light-Sintering Technique. ACS Applied Materials & Interfaces, 7, 5674-5684. https://doi.org/10.1021/am506765p
Joo, S.-J., Hwang, H.-J. and Kim, H.-S. (2014) Highly Conductive Copper Nano/Microparticles Ink via Flash Light Sintering for Printed Electronics. Nanotechnology, 25, Article ID: 265601. https://doi.org/10.1088/0957-4484/25/26/265601
Ohlund, T., Schuppert, A.K., Hummelgard, M., Backstrom, J., Nilsson, H.-E. and Olin, H. (2015) Inkjet Fabrication of Copper Patterns for Flexible Electronics: Using Paper with Active Precoatings. ACS Applied Materials & Interfaces, 7, 18273-18282. https://doi.org/10.1021/acsami.5b03061
Kim, H.-S., Dhage, S.R., Shim, D.-E. and Hahn, H.T. (2009) Intense Pulsed Light Sintering of Copper Nanoink for Printed Electronics. Applied Physics A: Materials Science & Processing, 97, 791-798. https://doi.org/10.1007/s00339-009-5360-6
Lee, Y., Choi, J.-R., Lee, K.-J., Stott, N.E. and Kim, D. (2008) Large-Scale Synthesis of Copper Nanoparticles by Chemically Controlled Reduction for Applications of Inkjet-Printed Electronics. Nanotechnology, 19, Article ID: 415604. https://doi.org/10.1088/0957-4484/19/41/415604
Li, Y., Wu, Y. and Ong, B.S. (2005) Facile Synthesis of Silver Nanoparticles Useful for Fabrication of High-Conductivity Elements for Printed Electronics. Journal of the American Chemical Society, 127, 3266-3267. https://doi.org/10.1021/ja043425k
Lee, H.-H., Chou, K.-S. and Huang, K.-C. (2005) Inkjet Printing of Nanosized Silver Colloids. Nanotechnology, 16, 2436. https://doi.org/10.1088/0957-4484/16/10/074
Zhang, Z., Zhang, X., Xin, Z., Deng, M., Wen, Y. and Song, Y. (2011) Synthesis of Monodisperse Silver Nanoparticles for Ink-Jet Printed Flexible Electronics. Nanotechnology, 22, Article ID: 425601. https://doi.org/10.1088/0957-4484/22/42/425601
Chen, C.-N., Chen, C.-P., Dong, T.-Y., Chang, T.-C., Chen, M.-C., Chen, H.-T. and Chen, I. (2012) Using Nanoparticles as Direct-Injection Printing Ink to Fabricate Conductive Silver Features on a Transparent Flexible PET Substrate at Room Temperature. Acta Materialia, 60, 5914-5924. https://doi.org/10.1016/j.actamat.2012.07.034
Zope, K.R., Cormier, D. and Williams, S. (2018) Reactive Silver Oxalate Ink Composition with Enhanced Curing Conditions for Flexible Substrates. ACS Applied Materials & Interfaces, 10, 3830-3834. https://doi.org/10.1021/acsami.7b19161
Jeong, S., Song, H.C., Lee, W.W., Choi, Y., Lee, S.S. and Ryu, B.-H. (2010) Combined Role of Well-Dispersed Aqueous Ag Ink and the Molecular Adhesive Layer in Inkjet Printing the Narrow and Highly Conductive Ag Features on a Glass Substrate. The Journal of Physical Chemistry C, 114, 22277-22283. https://doi.org/10.1021/jp106994t
Calvo, F. (2013) Nanoalloys: From Fundamentals to Emergent Applications. Elsevier, Massachusetts.
Peng, Z. and Yang, H. (2008) Ag-Pt Alloy Nanoparticles with the Compositions in the Miscibility Gap. Journal of Solid State Chemistry, 181, 1546-1551. https://doi.org/10.1016/j.jssc.2008.03.013
Andrews, M.P. and O’Brien, S.C. (1992) Gas-Phase “Molecular Alloys” of bulk Immiscible Elements: Iron-Silver (FexAgy). The Journal of Physical Chemistry, 96, 8233-8241. https://doi.org/10.1021/j100200a007
Chatterjee, J., Bettge, M., Haik, Y. and Chen, C.J. (2005) Synthesis and Characterization of Polymer Encapsulated Cu-Ni Magnetic Nanoparticles for Hyperthermia Applications. Journal of Magnetism and Magnetic Materials, 293, 303-309. https://doi.org/10.1016/j.jmmm.2005.02.024
Kline, T.L., Xu, Y.-H., Jing, Y. and Wang, J.-P. (2009) Biocompatible High-Moment FeCo-Au Magnetic Nanoparticles for Magnetic Hyperthermia Treatment Optimization. Journal of Magnetism and Magnetic Materials, 321, 1525-1528. https://doi.org/10.1016/j.jmmm.2009.02.079
W, Q.-W., Y, J.-L., R, J.-F., H, M.M. and Y, C.-H. (1990) Structure and Catalytic Properties of Cu-Ni Bimetallic Catalysts for Hydrogenation. Catalysis Letters, 4, 63-74. https://doi.org/10.1007/BF00764872
He, J., Ichinose, I., Kunitake, T., Nakao, A., Shiraishi, Y. and Toshima, N. (2003) Facile Fabrication of Ag-Pd Bimetallic Nanoparticles in Ultrathin TiO2-Gel Films: Nanoparticle Morphology and Catalytic Activity. Journal of the American Chemical Society, 125, 11034-11040. https://doi.org/10.1021/ja035970b
Alloyeau, D., Mottet, C. and Ricolleau, C. (2012) Nanoalloys: Synthesis, Structure and Properties. Springer Science & Business Media, Berlin/Heidelberg, Germany. https://doi.org/10.1007/978-1-4471-4014-6
Ferrer, D., Torres-Castro, A., Gao, X., Sepulveda-Guzman, S., Ortiz-Mendez, U. and Jose-Yacaman, M. (2007) Three-Layer Core/Shell Structure in Au-Pd Bimetallic Nanoparticles. Nano Letters, 7, 1701-1705. https://doi.org/10.1021/nl070694a
Yamauchi, T., Tsukahara, Y., Sakata, T., Mori, H., Yanagida, T., Kawai, T. and Wada, Y. (2010) Magnetic Cu-Ni (Core-Shell) Nanoparticles in a One-Pot Reaction under Microwave Irradiation. Nanoscale, 2, 515-523. https://doi.org/10.1039/b9nr00302a
Choi, E., Lee, S. and Piao, Y. (2015) Asolventless Mix-Bake-Wash Approach to the Facile Controlled Synthesis of Core-Shell and Alloy Ag-Cu Bimetallic Nanoparticles. CrystEngComm, 17, 5940-5946. https://doi.org/10.1039/C5CE00670H
Badawy, W.A., Ismail, K.M. and Fathi, A.M. (2005) Effect of Ni Content on the Corrosion Behavior of Cu-Ni Alloys in Neutral Chloride Solutions. Electrochimica Acta, 50, 3603-3608. https://doi.org/10.1016/j.electacta.2004.12.030
Kim, H., Lu, C., Worrell, W., Vohs, J. and Gorte, R. (2002) Cu-Ni Cermet Anodes for Direct Oxidation of Methane in Solid-Oxide Fuel Cells. Journal of the Electrochemical Society, 149, A247-A250. https://doi.org/10.1149/1.1445170
Qiu, R., Zhang, X.L., Qiao, R., Li, Y., Kim, Y.I. and Kang, Y.S. (2007) CuNi Dendritic Material: Synthesis, Mechanism Discussion, and Application as Glucose Sensor. Chemistry of Materials, 19, 4174-4180. https://doi.org/10.1021/cm070638a
Hashemizadeh, S.A. and Biglari, M. (2018) Cu: Ni Bimetallic Nanoparticles: Facile Synthesis, Characterization and Its Application in Photodegradation of Organic dyes. Journal of Materials Science: Materials in Electronics, 29, 13025-13031. https://doi.org/10.1007/s10854-018-9424-2
Kuznetsov, A.A., Leontiev, V.G., Brukvin, V.A., Vorozhtsov, G.N., Kogan, B.Y., Shlyakhtin, O.A., Yunin, A.M., Tsybin, O.I. and Kuznetsov, O.A. (2007) Local Radiofrequency-Induced Hyperthermia Using CuNi Nanoparticles with Therapeutically Suitable Curie Temperature. Journal of Magnetism and Magnetic Materials, 311, 197-203. https://doi.org/10.1016/j.jmmm.2006.11.199
Songping, W., Li, J., Jing, N., Zhenou, Z. and Song, L. (2007) Preparation of Ultra Fine Copper-Nickel Bimetallic Powders for Conductive Thick Film. Intermetallics, 15, 1316-1321. https://doi.org/10.1016/j.intermet.2007.04.001
Ahmed, J., Ramanujachary, K.V., Lofland, S.E., Furiato, A., Gupta, G., Shivaprasad, S. and Ganguli, A.K. (2008) Bimetallic Cu-Ni Nanoparticles of Varying Composition (CuNi3, CuNi, Cu3Ni). Colloids and Surfaces A: Physicochemical and Engineering Aspects, 331, 206-212. https://doi.org/10.1016/j.colsurfa.2008.08.007
Feng, J. and Zhang, C.-P. (2006) Preparation of Cu-Ni Alloy Nanocrystallites in Water-in-Oil Microemulsions. Journal of Colloid and Interface Science, 293, 414-420. https://doi.org/10.1016/j.jcis.2005.06.071
Souilah, S., Alleg, S., Bououdina, M., Sunol, J. and Hlil, E. (2017) Magnetic and Structural Properties of the Nanostructured Cu50Ni50 Powders. Journal of Superconductivity and Novel Magnetism, 30, 1927-1935. https://doi.org/10.1007/s10948-017-4001-0
Bonet, F., Grugeon, S., Dupont, L., Urbina, R.H., Guery, C. and Tarascon, J. (2003) Synthesis and Characterization of Bimetallic Ni-Cu Particles. Journal of Solid State Chemistry, 172, 111-115. https://doi.org/10.1016/S0022-4596(02)00163-9
Chen, L., Xu, H., Cui, H., Zhou, H., Wan, H. and Chen, J. (2017) Preparation of Cu-Ni Bimetallic Nanoparticles Surface-Capped with Dodecanethiol and Their Tribological Properties as Lubricant Additive. Particuology, 34, 89-96. https://doi.org/10.1016/j.partic.2016.12.006
Jung, C.-H., Lee, H.-G., Kim, C.-J. and Bhaduri, S. (2003) Synthesis of Cu-Ni Alloy Powder Directly from Metal Salts Solution. Journal of Nanoparticle Research, 5, 383-388. https://doi.org/10.1023/A:1025510910814
Pál, E., Kun, R., Schulze, C., Zollmer, V., Lehmhus, D., Baumer, M. and Busse, M. (2012) Composition-Dependent Sintering Behaviour of Chemically Synthesised CuNi Nanoparticles and Their Application in Aerosol Printing for Preparation of Conductive Microstructures. Colloid and Polymer Science, 290, 941-952. https://doi.org/10.1007/s00396-012-2612-3
Pál, E., Zollmer, V., Lehmhus, D. and Busse, M. (2011) Synthesis of Cu0.55Ni0.44Mn0.01 Alloy Nanoparticles by Solution Combustion Method and Their Application in Aerosol Printing. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 384, 661-667. https://doi.org/10.1016/j.colsurfa.2011.05.038
Ginley, D.S., Curtis, C.J., Miedaner, A., Van Hest, M.F.A.M. and Kaydanova, T. (2014) Metal Inks. US Patent No. 8641931 B2.
Farraj, Y., Grouchko, M. and Magdassi, S. (2015) Self-Reduction of a Copper Complex MOD Ink for Inkjet Printing Conductive Patterns on Plastics. Chemical Communications, 51, 1587-1590. https://doi.org/10.1039/C4CC08749F
Shevchenko, E.V., Talapin, D.V., Schnablegger, H., Kornowski, A., Festin, O., Svedlindh, P., Haase, M. and Weller, H. (2003) Study of Nucleation and Growth in the Organometallic Synthesis of Magnetic Alloy Nanocrystals: The Role of Nucleation Rate in Size Control of CoPt3 Nanocrystals. Journal of the American Chemical Society, 125, 9090-9101. https://doi.org/10.1021/ja029937l
Gupta, S. (1998) Peak Decomposition Using Pearson Type VII Function. Journal of Applied Crystallography, 31, 474-476. https://doi.org/10.1107/S0021889897011047
Cullity, B.D. (1978) Elements of X-Ray Diffraction. Addison-Wesley Publishing Company, Inc., Massachusetts.