Skip to main content
SpringerLink
Log in

General approach for fabricating nanoparticle arrays via patterned block copolymer nanoreactors

  • Research Paper
  • Published:
Journal of Nanoparticle Research Aims and scope Submit manuscript

Abstract

A general approach to fabricate nanoparticle arrays of different kinds of materials is demonstrated in this paper. It was found that the center-to-center distance of the nanoparticles or the nanoclusters can be controlled using patterned block copolymer nanoreactors by adding polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer thin film. The number of the nanoparticles formed in the P4VP nanodomains can also be adjusted by addition of polystyrene (PS) homopolymer to poly(styrene-b-4-vinylpyridine) (PS-b-P4VP) diblock copolymer. In fabrication of Au nanoparticle arrays, HAuCl4 precursor was directly loaded into P4VP nanodomains of the diblock copolymer thin film by using a methanol solvent, which is a good solvent for P4VP but non-solvent for PS. The Au nanoparticle arrays were then obtained by reducing HAuCl4 with sodium citrate dihydrate, and then in situ transferred to silicon substrate by a two-step calcination method. ZnO and Fe x O y nanoparticle arrays were also synthesized by this approach with thermal decomposition and double decomposition reactions, respectively. Additionally, the advantage of using two-step calcination method over the air plasma method was discussed.

This is a preview of subscription content, log in via an institution to check access.

Access this article

Log in via an institution

Price excludes VAT (USA)
Tax calculation will be finalised during checkout.

Instant access to the full article PDF.

Institutional subscriptions

Scheme 1
Fig. 1
Fig. 2
Fig. 3
Fig. 4
Fig. 5
Fig. 6
Fig. 7
Fig. 8

Similar content being viewed by others

References

  • Ansari IA, Hamley IW (2003) Templating the patterning of gold nanoparticles using a stained triblock copolymer film surface. J Mater Chem 13:2412–2413

    Article  CAS  Google Scholar 

  • Baek IC, Vithal M, Chang JA, Yum JH, Nazeeruddin MK, Grätzel M, Chung YC, Seok SI (2009) Facile preparation of large aspect ratio ellipsoidal anatase TiO2 nanoparticles and their application to dye-sensitized solar cell. Electrochem Commun 11:909–912

    Article  CAS  Google Scholar 

  • Bang J, Jeong U, Ryu DY, Russell TP, Hawker CJ (2009) Block copolymer nanolithography: translation of molecular level control to nanoscale patterns. Adv Mater 21:4769–4792

    Article  CAS  Google Scholar 

  • Braun CH, Richter TV, Schacher F, Müller AHE, Crossland EJW, Ludwigs S (2010) Block copolymer micellar nanoreactors for the directed synthesis of ZnO nanoparticles. Macromol Rapid Commun 31:729–734

    Article  CAS  Google Scholar 

  • Chai JA, Buriak JM (2008) Using cylindrical domains of block copolymers to self-assemble and align metallic nanowires. ACS Nano 2:489–501

    Article  CAS  Google Scholar 

  • Chai JA, Wang D, Fan XN, Buriak JM (2007) Assembly of aligned linear metallic patterns on silicon. Nat Nanotechnol 2:500–506

    Article  Google Scholar 

  • Chang SW, Chuang VP, Boles ST, Ross CA, Thompson CV (2009a) Densely packed arrays of ultra-high-aspect-ratio silicon nanowires fabricated using block-copolymer lithography and metal-assisted etching. Adv Funct Mater 19:2495–2500

    Article  CAS  Google Scholar 

  • Chang JJ, Kwon JH, Yoo SI, Park C, Sohn BH (2009b) Bimodal arrays of two types of nanoparticles by mixtures of diblock copolymer micelles. J Mater Chem 19:1621–1625

    Article  CAS  Google Scholar 

  • Fahmi AW, Stamm M (2005) Spatially correlated metallic nanostructures on self-assembled diblock copolymer templates. Langmuir 21:1062–1066

    Article  CAS  Google Scholar 

  • Fan HJ, Fuhrmann B, Scholz R, Syrowatka F, Dadgar A, Krost A, Zacharias M (2006a) Well-ordered ZnO nanowire arrays on GaN substrate fabricated via nanosphere lithography. J Cryst Growth 287:34–38

    Article  CAS  Google Scholar 

  • Fan HJ, Werner P, Zacharias M (2006b) Semiconductor nanowires: from self-organization to patterned growth. Small 2:700–717

    Article  CAS  Google Scholar 

  • Fuhrmann B, Leipner HS, Höche HR, Schubert L, Werner P, Gösele U (2005) Ordered arrays of silicon nanowires produced by nanosphere lithography and molecular beam epitaxy. Nano Lett 5:2524–2527

    Article  CAS  Google Scholar 

  • Guo LJ (2007) Nanoimprint lithography: methods and material requirements. Adv Mater 19:495–513

    Article  CAS  Google Scholar 

  • Haque SA, Koops S, Tokmoldin N, Durrant JR, Huang JS, Bradley DDC, Palomares E (2007) A multilayered polymer light-emitting diode using a nanocrystalline metal-oxide film as a charge-injection electrode. Adv Mater 19:683–687

    Article  CAS  Google Scholar 

  • Hirai T et al (2009) One-step direct-patterning template utilizing self-assembly of POSS-containing block copolymers. Adv Mater 21:4334–4338

    Article  CAS  Google Scholar 

  • Horiuchi S, Fujita T (2003) Three-dimensional nanoscale alignment of metal nanoparticles using block copolymer films as nanoreactors. Langmuir 19:2963–2973

    Article  CAS  Google Scholar 

  • Hornyak G, Kröll M, Pugin R, Sawitowski T, Schmid G, Bovin JO, Karsson G, Hofmeister H, Hopfe S (1997) Gold clusters and colloids in alumina nanotubes. Chem Eur J 3(12):1951–1956

    Article  CAS  Google Scholar 

  • Hutter E, Fendler JH (2004) Exploitation of localized surface plasmon resonance. Adv Mater 16:1685–1706

    Article  CAS  Google Scholar 

  • Hwang W et al (2008) Chem Mater 20:6041–6047

    Article  CAS  Google Scholar 

  • Jung YS, Ross CA (2009) Well-ordered thin-film nanopore arrays formed using a block-copolymer template. Small 5:1654–1659

    Article  CAS  Google Scholar 

  • Kannaiyan D, Cha MA, Jang YH, Sohn BH, Huh J, Park C, Kim DH (2009) Efficient photocatalytic hybrid Ag/TiO2 nanodot arrays integrated into nanopatterned block copolymer thin films. New J Chem 33:2431–2436

    Article  CAS  Google Scholar 

  • Kannaiyan D, Kim E, Won N, Kim KW, Jang YH, Cha M, Ryu DY, Kim S, Kim DH (2010) On the synergistic coupling properties of composite CdS/TiO2 nanoparticle arrays confined in nanopatterned hybrid thin films. J Mater Chem 20:677–682

    Article  CAS  Google Scholar 

  • Kim SO, Solak HH, Stoykovich MP, Ferrier NJ, Pablo JJ, Nealey PF (2003) Epitaxial self-assembly of block copolymers on lithographically defined nanopatterned substrates. Nature 424:411–414

    Article  CAS  Google Scholar 

  • Koh HD, Kang NG, Lee JS (2007) Fabrication of an open Au/nanoporous film by water-in-oil emulsion-induced block copolymer micelles. Langmuir 23:12817–12820

    Article  CAS  Google Scholar 

  • Lee JY, Horiuchi S (2007) Electroless nickel plating on patterned catalytic surfaces by electron beam lithography. Thin Solid Films 515:7798–7804

    Article  CAS  Google Scholar 

  • Li MQ, Ober CK (2006) Block copolymer patterns and templates. Mater Today 9:30–39

    Article  CAS  Google Scholar 

  • Li JZ, Kamata K, Iyoda T (2008) Tailored Ag nanoparticle array fabricated by block copolymer photolithography. Thin Solid Films 516:2577–2581

    Article  CAS  Google Scholar 

  • Li FH, Wang ZH, Shan CS, Song JF, Han DX, Niu L (2009a) Preparation of gold nanoparticles/functionalized multiwalled carbon nanotube nanocomposites and its glucose biosensing application. Biosens Bioelectron 24:1765–1770

    Article  CAS  Google Scholar 

  • Li GX, Nan HY, Zheng XW (2009b) The investigation of photo-induced chemiluminescence on Co2+-doped TiO2 nanoparticles and its analytical application. Analyst 134:1396–1404

    Article  CAS  Google Scholar 

  • Li WC, Park SE, Kim JS, Lee SW (2009c) Self-assembled two-dimensional array of gold nanoparticles with different size for the sensing application. Jpn J Appl Phys 48:06FF14

    Article  Google Scholar 

  • Lin ZQ, Kim DH, Wu XD (2002) A rapid route to arrays of nanostructures in thin films. Adv Mater 14:1373–1376

    Article  CAS  Google Scholar 

  • Lin Y et al (2005) Self-directed self-assembly of nanoparticle/copolymer mixtures. Nature 434:55–59

    Article  CAS  Google Scholar 

  • Lopes WA, Jaeger HM (2001) Hierarchical self-assembly of metal nanostructures on diblock copolymer scaffolds. Nature 414:735–738

    Article  CAS  Google Scholar 

  • Ma XY (2008) Memory properties of a Ge nanoring MOS device fabricated by pulsed laser deposition. Nanotechnology 19:275706

    Article  Google Scholar 

  • Mendoza C, Pietsch T, Gindy N, Fahmi A (2008) Fabrication of 3D-periodic ordered metallic nanoparticles in a block copolymer bulk matrix via oscillating shear flow. Adv Mater 20:1179–1184

    Article  CAS  Google Scholar 

  • Morin SA, La YH, Liu CC, Streifer JA, Hamers RJ, Nealey PF, Jin S (2009) Assembly of nanocrystal arrays by block-copolymer-directed nucleation. Angew Chem Int Ed 48:2135–2139

    Article  CAS  Google Scholar 

  • Nagesha DK, Plouffe BD, Phan M, Lewis LH, Sridhar S, Murthy SK (2009) Functionalization-induced improvement in magnetic properties of Fe3O4 nanoparticles for biomedical applications. J Appl Phys 105:07B317

    Article  Google Scholar 

  • Nandan B, Gowd EB, Bigall NC, Eychmüller A, Formanek P, Simon P, Stamm M (2009) Arrays of inorganic nanodots and nanowires using nanotemplates based on switchable block copolymer supramolecular assemblies. Adv Funct Mater 19:2805–2811

    Article  CAS  Google Scholar 

  • Pál E, Oszkó A, Mela P, Möller M, Dékány I (2008) Preparation of hexagonally aligned inorganic nanoparticles from diblock copolymer micellar systems. Colloids Surf A 331:213–219

    Article  Google Scholar 

  • Park SM, Craig GSW, La YH, Solak HH, Nealey PF (2007) Square arrays of vertical cylinders of PS-b-PMMA on chemically nanopatterned surfaces. Macromolecules 40:5084–5094

    Article  CAS  Google Scholar 

  • Park S, Kim B, Wang JY, Russell TP (2008) Fabrication of highly ordered silicon oxide dots and stripes from block copolymer thin films. Adv Mater 20:681–685

    Article  CAS  Google Scholar 

  • Park HJ, Kang MG, Guo LJ (2009) Large area high density sub-20 nm SiO2 nanostructures fabricated by block copolymer template for nanoimprint lithography. ACS Nano 3:2601–2608

    Article  CAS  Google Scholar 

  • Peng J, Mao C, Kim J, Kim DH (2009) From nanodot to nanowire: hybrid Au/titania nanoarrays by block copolymer templates. Macromol Rapid Commun 30:1857–1861

    Article  CAS  Google Scholar 

  • Qiao YH, Wang D, Buriak JM (2007) Block copolymer templated etching on silicon. Nano Lett 7:464–469

    Article  CAS  Google Scholar 

  • Schmid G (1994) Clusters and colloids. From theory to applications. Vch Verlagsgesellschaft, New York

    Book  Google Scholar 

  • Schmid G, Chi LF (1998) Metal clusters and colloids. Adv Mater 10:515–526

    Article  CAS  Google Scholar 

  • Seow ZLS, Wong ASW, Thavasi V, Jose R, Ramakrishna S, Ho GW (2009) Controlled synthesis and application of ZnO nanoparticles, nanorods and nanospheres in dye-sensitized solar cells. Nanotechnology 20:045604

    Article  CAS  Google Scholar 

  • Sohn BH, Seo BH (2001) Fabrication of the multilayered nanostructure of alternating polymers and gold nanoparticles with thin films of self-assembling diblock copolymers. Chem Mater 13:1752–1757

    Article  CAS  Google Scholar 

  • Son JG, Bae WK, Kang HM, Nealey PF, Char K (2009) Placement control of nanomaterial arrays on the surface-reconstructed block coplymer thin films. ACS Nano 3:3927–3934

    Article  CAS  Google Scholar 

  • Spatz JP, Roescher A, Möller M (1996) Gold nanoparticles in micellar poly(styrene)-b-poly(ethylene oxide) films—size and interparticle distance control in monoparticulate films. Adv Mater 8:337–340

    Article  CAS  Google Scholar 

  • Sutherland WS, Winefordner JD (1992) Colloid filtration: a novel substrate preparation method for surface-enhanced Raman spectroscopy. J Colloid Interface Sci 148:129–141

    Article  CAS  Google Scholar 

  • Tang CB, Lennon EM, Fredrickson GH, Kramer EJ, Hawker CJ (2008) Evolution of block copolymer lithography to highly ordered square arrays. Science 322:429–432

    Article  CAS  Google Scholar 

  • Tang CB, Hur SM, Stahl BC, Sivanandan K, Dimitriou M, Pressly E, Fredrickson GH, Kramer EJ, Hawker CJ (2010) Thin film morphology of block copolymer blends with tunable supramolecular interactions for lithographic applications. Macromolecules 43:2880–2889

    Article  CAS  Google Scholar 

  • Tseng CH, Tambe MJ, Lim SK, Smith MJ, Gradeǎak S (2010) Position controlled nanowire growth through Au nanoparticles synthesized by galvanic reaction. Nanotechnology 21:165605

    Article  Google Scholar 

  • Wang ZL (2009) ZnO nanowire and nanobelt platform for nanotechnology. Mater Sci Eng R 64:33–71

    Article  Google Scholar 

  • Wang XD, Summers CJ, Wang ZL (2004) Large-scale hexagonal-patterned growth of aligned ZnO nanorods for nano-optoelectronics and nanosensor arrays. Nano Lett 4:423–426

    Article  CAS  Google Scholar 

  • Wang Y, Deng JJ, Di JW, Tu YF (2009a) Electrodeposition of large size gold nanoparticles on indium tin oxide glass and application as refractive index sensor. Electrochem Commun 11:1034–1037

    Article  CAS  Google Scholar 

  • Wang ZJ, Qu SC, Zeng XB, Liu JP, Zhang CS, Tan FR, Jin L, Wang ZG (2009b) The application of SnS nanoparticles to bulk heterojunction solar sells. J Alloys Compd 482:203–207

    Article  CAS  Google Scholar 

  • Yun SH, Yoo SI, Jung JC, Zin WC, Sohn BH (2006) Highly ordered arrays of nanoparticles in large areas from diblock copolymer micelles in hexagonal self-assembly. Chem Mater 18:5646–5648

    Article  CAS  Google Scholar 

  • Zhou Z, Deng Y (2009) Kinetics study of ZnO nanorod growth in solution. J Phys Chem C 113(46):19853

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors gratefully acknowledge the China Scholarship Council (CSC) for the fellowship to support Xihong Zu as a visiting student at Georgia Institute of Technology. Thanks to Xiaobo Hu for assisting with the air plasma method, and thanks to Dr. Zhengzhi Zhou and Dr. Ying Wang for general help.

Author information

Authors and Affiliations

  1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou, 510640, Guangdong, People’s Republic of China

    Xihong Zu & Weiping Tu

  2. School of Chemical and Biomolecular Engineering, Georgia Institute of Technology, Atlanta, GA, 30332-0620, USA

    Xihong Zu & Yulin Deng

Authors
  1. Xihong Zu
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Weiping Tu
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yulin Deng
    View author publications

    You can also search for this author in PubMed Google Scholar

Corresponding author

Correspondence to Yulin Deng.

Rights and permissions

Reprints and permissions

About this article

Cite this article

Zu, X., Tu, W. & Deng, Y. General approach for fabricating nanoparticle arrays via patterned block copolymer nanoreactors. J Nanopart Res 13, 1–13 (2011). https://doi.org/10.1007/s11051-010-0059-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • Issue Date:

  • DOI: https://doi.org/10.1007/s11051-010-0059-3

Keywords

Search

Navigation