Arrays of Plasmonic Nanoparticles Assembled on Patterns of Polymer Brushes Fabricated by Soft Lithography

Abstract

This work employed end-grafted poly ethylene glycol PEG and hydroxyl-terminated poly 2-vinylpyridine P2VP polymer chains for selective immobilization and patterning of plasmonic nanoparticles NPs . A soft lithographic method which called micromolding in capillaries MIMIC used in this study. The polymers are deposited the capillary flow by the channels which formed by an elastomeric mold and substrate. The localized coatings are referred as polymer brushes and show great promise in the assembly of NPs due to the tunable interaction between the polymer chains and particles. The results show that the width of patterns defined by the channels is smaller than 1.5 µm with a length of around 0.5 cm. Also, the heights of the patterns are ~3.5 nm for P2VP and ~10 nm for PEG. The fabricated structures exhibited high levels of plasmonic activity and surface enhanced Raman scattering due to the immobilized Au NPs. The patterning polymer brushes and plasmonic NPS over large areas by a low-cost process show great promise for a variety of applications that range from molecular sensors to biotechnology

Keywords

• Soft-lithography, Polymer brushes, Nanoparticles, Plasmonics.

References

1. 1. Sugnaux C, Mallorqui AD, Herriman J, Klok HA, Morral, AFI. Polymer Brush Guided Formation of Conformal, Plasmonic Nanoparticle-Based Electrodes for Microwire Solar Cells. Adv Funct Mater 25 (2015) 3958-3965.
2. 2. Ipekci HH, Arkaz HH, Onses MS, Hancer, M. Superhydrophobic coatings with improved mechanical robustness based on polymer brushes. Surf Coat Tech 299 (2016) 162-168.
3. 3. Mansky P, Liu Y, Huang E, Russell TP, Hawker, CJ. Controlling polymer-surface interactions with random copolymer brushes. Science 275 (1997) 1458-1460.
4. 4. Thode CJ, Cook PL, Jiang YM, Onses MS, Ji SX, Himpsel FJ, Nealey, PF. In situ metallization of patterned polymer brushes created by molecular transfer print and fill. Nanotechnology 24 (2013).
5. 5. Kroning A, Furchner A, Aulich D, Bittrich E, Rauch S, Uhlmann P, Eichhorn KJ, Seeber M, Luzinov I, Kilbey SM, Lokitz BS, Minko S, Hinrichs, K. In Situ Infrared Ellipsometry for Protein Adsorption Studies on Ultrathin Smart Polymer Brushes in Aqueous Environment. Acs Appl Mater Inter 7 (2015) 12430-12439.
6. 6. Yu K, Lo JCY, Mei Y, Haney EF, Siren E, Kalathottukaren MT, Hancock REW, Lange D, Kizhakkedathu, JN. Toward Infection-Resistant Surfaces: Achieving High Antimicrobial Peptide Potency by Modulating the Functionality of Polymer Brush and Peptide. Acs Appl Mater Inter 7 (2015) 28591- 28605.
7. 7. Onses MS, Liu CC, Thode CJ, Nealey, PF. Highly Selective Immobilization of Au Nanoparticles onto Isolated and Dense Nanopatterns of Poly(2-viinyl pyridine) Brushes down to Single-Particle Resolution. Langmuir 28 (2012) 7299- 7307.
8. 8. Nguyen M, Kanaev A, Sun XN, Lacaze E, Lau-Truong S, Lamouri A, Aubard J, Felidj N, Mangeney, C. Tunable Electromagnetic Coupling in Plasmonic Nanostructures Mediated by Thermoresponsive Polymer Brushes. Langmuir 31 (2015) 12830-12837.

9. 9. Christau S, Genzer J, Klitzing, RV. Polymer Brush/Metal Nanoparticle Hybrids for Optical Sensor Applications: from Self-Assembly to Tailored Functions and Nanoengineering. Zeitschrift Fur Physikalische Chemie-International Journal of Research in Physical Chemistry & Chemical Physics 229 (2015) 1089-1117.
10. 10. Lu XM, Rycenga M, Skrabalak SE, Wiley B, Xia, YN. Chemical Synthesis of Novel Plasmonic Nanoparticles. Annu Rev Phys Chem 60 (2009) 167-192.
11. 11. Onses MS, Nealey, PF. Tunable Assembly of Gold Nanoparticles on Nanopatterned Poly(ethylene glycol) Brushes. Small 9 (2013) 4168-4174.
12. 12. Tokareva I, Minko S, Fendler JH, Hutter, E. Nanosensors based on responsive polymer brushes and gold nanoparticle enhanced transmission surface plasmon resonance spectroscopy. J Am Chem Soc 126 (2004) 15950-15951.
13. 13. Romo-Herrera JM, Alvarez-Puebla RA, Liz-Marzan, LM. Controlled assembly of plasmonic colloidal nanoparticle clusters. Nanoscale 3 (2011) 1304-1315.
14. 14. Liu Y, Xie SW, Xiao X, Li SH, Gao FH, Zhang ZY, Du, JL. Fabricating metal nanoparticle arrays at specified and localized regions of microfluidic chip for LSPR sensing. Microelectron Eng 151 (2016) 7-11.
15. 15. Wang GP, Chen XC, Liu S, Wong CP, Chu, S. Mechanical Chameleon through Dynamic Real Time-Plasmonic Tuning. Acs Nano 10 (2016) 1788-1794.
16. 16. Liu N, Tang ML, Hentschel M, Giessen H, Alivisatos, AP. Nanoantenna-enhanced gas sensing in a single tailored nanofocus. Nat Mater 10 (2011) 631-636.
17. 17. Kim BH, Onses MS, Lim JB, Nam S, Oh N, Kim H, Yu KJ, Lee JW, Kim JH, Kang SK, Lee CH, Lee J, Shin JH, Kim NH, Leal C, Shim M, Rogers, JA. High-Resolution Patterns of Quantum Dots Formed by Electrohydrodynamic Jet Printing for Light-Emitting Diodes. Nano Lett 15 (2015) 969-973.
18. 18. Zhu M, Baffou G, Meyerbroker N, Polleux, J. Micropatterning Thermoplasmonic Gold Nanoarrays To Manipulate Cell Adhesion. Acs Nano 6 (2012) 7227-7233.
19. 19. Kim SO , Solak HH, Stoykovich MP, Ferrier NJ, Pablo JJ, Nealey, PF. Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates. Nature 424 (2003) 411-414.
20. 20. Poelma JE, Fors BP, Meyers GF, Kramer JW, Hawker, CJ. Fabrication of Complex Three-Dimensional Polymer Brush Nanostructures through Light-Mediated Living Radical Polymerization. Angew Chem Int Edit 52 (2013) 6844- 6848.
21. 21. Chen CJ, Zhou XC, Xie Z, Gao TT, Zheng, ZJ. Construction of 3D Polymer Brushes by Dip-Pen Nanodisplacement Lithography: Understanding the Molecular Displacement for Ultrafine and High-Speed Patterning. Small 11 (2015) 613-621.
22. 22. Onses MS, Ramirez-Hernandez A, Hur SM, Sutanto E, Williamson L, Alleyne AG, Nealey PF, Pablo JJ, Rogers, JA. Block Copolymer Assembly on Nanoscale Patterns of Polymer Brushes Formed by Electrohydrodynamic Jet Printing. Acs Nano 8 (2014) 6606-6613.
23. 23. Parry AV, Straub AJ, Villar-Alvarez EM, Phuengphol T, Nicoll JE, Lim X, WK, Jordan LM, Moore KL, Taboada P, Yeates, SG. Sub-Micron Patterning of Polymer Brushes: An Unexpected Discovery from Inkjet Printing of Polyelectrolyte Macroinitiators. J Am Chem Soc (2016).
24. 24. Onses MS. Fabrication of Nanopatterned Poly(ethylene glycol) Brushes by Molecular Transfer Printing from Poly(styrene-block-methyl methacrylate) Films to Generate Arrays of Au Nanoparticles. Langmuir. 31 (2015) 1225-1230.
25. 25. Li YF, Zhang JH, Fang LP, Jiang LM, Liu WD, Wang TQ, Cui LY, Sun HC, Yang, B. Polymer brush nanopatterns with controllable features for protein pattern applications. J Mater Chem 22 (2012) 25116-25122.
26. 26. Weibel DB, DiLuzio WR, Whitesides, GM. Microfabrication meets microbiology. Nat Rev Microbiol 5 (2007) 209-218.
27. 27. Singh A, Kulkarni SK, Khan-Malek, C. Patterning of SiO2 nanoparticle-PMMA polymer composite microstructures based on soft lithographic techniques. Microelectron Eng 88 (2011) 939-944.
28. 28. Zhou F, Zheng ZJ, Yu B, Liu WM, Huck, WTS. Multicomponent polymer brushes. J Am Chem Soc 128 (2006) 16253-16258.
29. 29. Chen T, Jordan R, Zauscher, S. Dynamic Microcontact Printing for Patterning Polymer-Brush Microstructures. Small 7 (2011) 2148-2152.
30. 30. Roling O, De Bruycker K, Vonhoren B, Stricker L, Korsgen M, Arlinghaus HF, Ravoo BJ, Du Prez, FE. Rewritable Polymer Brush Micropatterns Grafted by Triazolinedione Click Chemistry. Angew Chem Int Edit 54 (2015) 13126-13129.
31. 31. Diamanti S, Arifuzzaman S, Elsen A, Genzer J, Vaia, RA. Reactive patterning via post-functionalization of polymer brushes utilizing disuccinimidyl carbonate activation to couple primary amines. Polymer 49 (2008) 3770-3779.
32. 32. Chen T, Jordan R, Zauscher, S. Extending microcontact printing for patterning complex polymer brush microstructures. Polymer 52 (2011) 2461-2467.
33. 33. Felts JR, Onses MS, Rogers JA, King, WP. Nanometer Scale Alignment of Block-Copolymer Domains by Means of a Scanning Probe Tip. Adv Mater 26 (2014) 2999-3002.
34. 34. Liu XY, Biswas S, Jarrett JW, Poutrina E, Urbas A, Knappenberger KL, Vaia RA, Nealey, PF. Deterministic Construction of Plasmonic Heterostructures in WellOrganized Arrays for Nanophotonic Materials. Adv Mater 27 (2015) 7314-+.
35. 35. Onses MS, Wan L, Liu XY, Kiremitler NB, Yilmaz H, Nealey, PF. Self-Assembled Nanoparticle Arrays on Chemical Nanopatterns Prepared Using Block Copolymer Lithography. Acs Macro Lett 4 (2015) 1356-1361.
36. 36. Vonhoren B, Langer M, Abt D, Barner-Kowollik C, Ravoo, BJ. Fast and Simple Preparation of Patterned Surfaces with Hydrophilic Polymer Brushes by Micromolding in Capillaries. Langmuir 31 (2015) 13625-13631.
37. 37. Kim E, Xia YN, Whitesides, GM. Micromolding in capillaries: Applications in materials science. J Am Chem Soc 118 (1996) 5722-5731.
38. 38. Lee JN, Park C, Whitesides, GM. Solvent compatibility of poly(dimethylsiloxane)-based microfluidic devices. Anal Chem 75 (2003) 6544-6554.
39. 39. Yunker PJ, Still T, Lohr MA, Yodh, AG. Suppression of the coffee-ring effect by shape-dependent capillary interactions. Nature 476 (2011) 308-311.
40. 40. Xia YN, Whitesides, GM. Soft lithography. Angew Chem Int Edit 37 (1998) 550-575.
41. 41. Yilmaz H, Pekdemir S, Ipekci HH, Kiremitler NB, Hancer M, Onses, MS. Ambient, rapid and facile deposition of polymer brushes forimmobilization of plasmonic nanoparticles. Appl Surf Sci 385 (2016) 299-307.
42. 42. Shalabaeva V, La Rocca R, Miele E, Dipalo M, Messina GC, Perrone M, Maidecchi G, Gentile F, De Angelis, F. Plasmonic microholes for SERS study of biomolecules in liquid. Microelectron Eng 158 (2016) 59-63.