(12) United States Patent (10) Patent No.: US 8,900,659 B2 Zeng Et Al
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USOO890.0659B2 (12) United States Patent (10) Patent No.: US 8,900,659 B2 Zeng et al. (45) Date of Patent: Dec. 2, 2014 (54) METAL NANOWIRES, NANOMESH, ANDA B22F I/02 (2006.01) METHOD OF FABRICATION B22F 3/00 (2006.01) B22F 9/24 (2006.01) (75) Inventors: Hua Chun Zeng, Singapore (SG); (52) U.S. Cl. Shengmao Zhang, Kaifeng (CN); Yu CPC DOIF 9/08 (2013.01); B05D3/207 (2013.01); Chang, Singapore (SG); Mei Ling Lye, B05D 5/12 (2013.01); B32B 15/14 (2013.01); Singapore (SG) B32B37/02 (2013.01); H0IB I/16 (2013.01); B22F I/0025 (2013.01); B22F I/025 (73) Assignee: National University of Signapore, (2013.01); B22F3/002 (2013.01); B22F 9/24 Singapore (SG) (2013.01) c - r - USPC ........................................ 427/217: 174/126.2 (*) Notice: Subject to any disclaimer, the term of this (58) Field of Classification Search patent is extended or adjusted under 35 CPC BOSD 3/2O7. BOSD 5/12: HO1B 1/16 U.S.C. 154(b) by 10 days. B32B 15/14: B32B 37/02: D01F 9/08 (21) Appl. No.: 13/811,259 USPC ........................................ 427/217; 174/126.2 See application file for complete search history. (22) PCT Filed: Jul.19, 2011 (56) References Cited (86). PCT No.: PCT/SG2O11AOOO257 S371 (c)(1) FOREIGN PATENT DOCUMENTS C s (2), (4) Date: Jan. 19, 2013 KR 20100079781. A 7, 2010 WO 2005.005687 A1 1, 2005 (87) PCT Pub. No.: WO2012/060776 WO 2012O60776 A1 5, 2012 PCT Pub. Date: May 10, 2012 OTHER PUBLICATIONS (65) Prior Publication Data Changet al., "Large-Scale Synthesis of High-Quality Ultralong Cop per Nanowires”. Langmuir, 21. Mar. 11, 2005, p.3746-3748.* US 2013/O118775 A1 May 16, 2013 (Continued) Related U.S. Application Data Primary Examiner — Timothy Meeks (60) Provisional application No. 61/365,423, filed on Jul. Assistant Examiner — Ann Disarro 19, 2010. (57) ABSTRACT (51) Int. Cl. B05D 700 (2006.01) The present invention relates to a method of forming copper HOIB5/00 (2006.01) nanowires with a metallic coating.9. In a ppreferred embodi DOIF 9/08 (2006.01) ment, the metallic coating is copper. Due to the metal coating, B05D3/00 2OO 6. O1 the nanowires become magnetically guidable and chemically ( .01) stable. As such, the nanowires can be used to form nanomesh. B05D 5/2 (2006.01) Further, the nanowire and nanomesh of the present invention B32B I5/4 (2006.01) can be used as transparent electrodes that are used in TV, PC, B32B 37/02 (2006.01) touch-control, and Solar industries. HOB I/I6 (2006.01) B22F I/O (2006.01) 20 Claims, 8 Drawing Sheets NaOH,Cu(NO3)3, NiNOs) EDA and hydrazine Place solution in water bath at 25-100°C for 5 minutes.- 15 hours Wash and dry Nickel-coated copper nanowires US 8,900,659 B2 Page 2 (56) References Cited Zeng, Hua Chen, et al., U.S. Provisional Patent Application entitled, Wet Synthesis of Chemically Stable Copper Nanowires for T OTHER PUBLICATIONS Ransparent Conducting Electrodes and Other Electrical Interconnect Grouchko et al., “Formation of Air-Stable Copper-Silver Core-Shell Applications, U.S. Appl. No. 61/365,423, filed Jul. 19, 2010. Nanoparticles for Inkjet Printing”, Journal of Materials Chemistry Lee, J.Y., et al., “Solution-Processed Metal Nanowire Mesh Trans 19, Mar. 17, 2009, pp. 3057-3062.* parent Electrodes', Nano letters, vol. 8, No. 2, pp. 689-692, 2008. Foreign Communication From a Related Counterpart Application— Athanassiou, E. K., et al., “Template Free, Large Scale Synthesis of International Search Report and Written Opinion, PCT/SG2011/ Cobalt Nanowires Using Magnetic Fields for Alignment.” 000257, Sep. 13, 2011. Nanotechnology, vol. 18, pp. 165606-165612, 2007. Foreign Communication From a Related Counterpart Application— International Preliminary Report on Patentability, PCT/SG2011/ 000257, Jan. 31, 2013. * cited by examiner U.S. Patent Dec. 2, 2014 Sheet 1 of 8 US 8,900,659 B2 NaOH/Cu(NO3)2, Ni(NO3) -- EDA and hydrazine Mix Place solution in water bath at 25-100 °C for 15 minutes - 15 hours Wash and dry ickel-coated copper nanowires Figure 1 U.S. Patent Dec. 2, 2014 Sheet 2 of 8 Figure 2 U.S. Patent Dec. 2, 2014 Sheet 3 of 8 US 8,900,659 B2 Figure 3 U.S. Patent Dec. 2, 2014 Sheet 4 of 8 US 8,900,659 B2 Figure 4 U.S. Patent Dec. 2, 2014 Sheet 5 of 8 US 8,900,659 B2 200 210 Nanowires + solvent 220 Substrate J Evaporation of solvent - 230 Nanomesh 220 Substrate Figure 5 U.S. Patent US 8,900,659 B2 U.S. Patent Dec. 2, 2014 Sheet 7 of 8 US 8,900,659 B2 400 2. At A. ES53.33A25A93. S. Nanowires in polymer A.K. 40 Sii SS. s 8: SiSA.S.& E.X 8.(i. 532,373,575s8. 2.SS Slicing and polishing 8: 883. 88. 25A25A1A3%SR323; ELSs S3, a $53 Thin plates of nanomesh 2S3, SSAE insidep a polymer block & 2. & 2. 3. N SS t . s 3. 5. s K 5% 420 8. 3.y . S S: iESSs S563:37.53S2,& 3.x: ... SSA SSSS. Removal of polymer 2 litty-BelAZ AXAS-STX, KNS IST A23 Akye i? If 3.22.3.2; Si. Thin plates of 3,2S3R. If 33. nanomesh 23,335. Si3. *As a 2E, A&A 430 27 ASA 7 AAAAYS Figure 7 U.S. Patent Dec. 2, 2014 Sheet 8 of 8 US 8,900,659 B2 For flexible substrates: an array of nozzle jets \ \ roller ^ ::: v. flexible Substrate , roller \ w Figure 8a For rigid substrates: an array of nozzle jets moving substrate Figure 8b US 8,900,659 B2 1. 2 METAL NANOWIRES, NANOMESH, ANDA SUMMARY OF INVENTION METHOD OF FABRICATION The present invention relates to the preparation of metal CROSS-REFERENCE TO RELATED nanowires and their method of fabrication. In particular, cop APPLICATIONS per (Cu) nanowires with metal Surface coatings are prepared under simple reaction conditions. The prepared metal nanow This application is a filing under 35 U.S.C. 371 as the ires can be used as a Substitute material for expensive indium National Stage of International Application No. PCT/ tin-oxide (ITO) in general application of transparent conduct SG2011/000257, filed Jul 19, 2011, entitled “METAL ing electrodes. NANOWIRES, NANOMESH, AND AMETHOD OF FAB 10 According to a first aspect there is provided a method of RICATION” which claims the benefit of and priority to U.S. making a plurality of metal-coated copper nanowires accord Provisional Patent Application No. 61/365,423, filed Jul. 19, ing to claim 1. 2010 and entitled “METAL NANOWIRES, NANOMESH, According to a second aspect there is provided a nanowire AND A METHOD OF FABRICATION', both of which are according to claim 23. incorporated herein by reference in their entirety for all pur 15 According to a third aspect there is provided a display poses. panel according to claim 23. FIELD OF THE INVENTION BRIEF DESCRIPTION OF THE DRAWINGS The present invention relates to metal nanowires, nano The accompanying figures, which are incorporated in and tech, and a method of fabrication. constitute a part of this specification, illustrate aspects of the invention and, together with a general description of the BACKGROUND OF THE INVENTION invention given above, and the detailed description given below, serve to explain the invention. Copper (Cu) is one of the most important metals in modern 25 FIG. 1 is a simplified block diagram of the wet synthesis technologies. In nanotechnology (e.g., nano-optoelectronic redox reaction of nickel-coated copper nanowires. industry), fabrication of one-dimensional (1D) nanomaterials FIG. 2 illustrates the as-synthesized, coated metal nanow of copper (wires/cables/rods) have received considerable ires of the present invention forming a conductive path for the attention in recent years. A number of fabrication methods flow of current where plurality of copper nanowires are have been proposed including electrochemical reactions, 30 coated with nickel. vapor depositions, soft and hard template processes, reverse FIG. 3 illustrates the SEM, TEM, and HRTEM images of micellar systems, etc. So far, effective methods for large-scale the as-prepared Cu(a)Ni nanowires. production of high quality nanostructured copper or metal FIG. 4 illustrates the XRD patterns, EDX line analysis, nanowires with precise morphological control have not been SAED pattern, and chemical mappings of the as-prepared realized. Fabrication problems may include short length, non 35 Cu(a)Ni nanowires. linear morphology, polydispersivity, poor crystallinity, low FIG. 5 illustrates the preparation of the as-synthesized yield, and/or process complexity. nanomesh on a Substrate via evaporation of Solvent. Conventionally, copper nanowires have been prepared by FIG. 6 illustrates the vertical and horizontal alignments of the synthesis of Sodium hydroxide and cupric nitrate (an two or more sequentially layered metal nanowires with the aqueous solution) in a glass reactor. The general redox reac 40 assistance of parallel external magnetic fields. tion is: FIG. 7 illustrates the preparation of thin plates of nanomesh where the as-synthesized metal nanowires are embedded inside a polymer as a nanomatrix. In “Large-Scale Synthesis of High-Quality Ultralong Cop FIG. 8 illustrates the continuous process of depositing per Nanowires.” Langmuir 2005, Volume 21, pp. 3746-3748, 45 nanowires on flexible (8a) and rigid (8b) substrates. Yu Chang, Mei Ling Lye, and Hua Chun Zeng, varying amounts of ethylenediamine (EDA) and hydrazine are added DETAILED DESCRIPTION OF THE INVENTION sequentially to the aqueous solution, followed by a thorough mixing of all of the reagents. The reactor was then placed in In the present invention, high-quality ultra-long copper a water bath with a temperature control over 25-100° C.