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Generation of an ordered layer of silver nanoparticles in mesostructured dielectric films

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Abstract

Mesostructured organic–inorganic silica films containing AgNO3 are used as template to form ordered and dense layers of silver nanoparticles embedded in a dielectric matrix. The hybrid silica films are mesostructured by a triblock copolymer polyethylene oxide-polypropylene oxide-polyethylene oxide ((PEO)106(PPO)70(PEO)106, F127) and contain the silver precursor (AgNO3) which is dissolved directly in the silica sol prior to deposition. The films are reacted with a sodium borohydride solution (NaBH4), which leads to the formation of a plane ordered network of silver oblate nanoparticles with a narrow size distribution located just below the film surface, and observed by Transmission Electron Microscopy (TEM). The minor and major axis lengths are equal to 5.3 ± 0.5 and 7.2 ± 0.6 nm, respectively. The characterization of the mesostructured film before and after the reductive treatment evidences that silver particles grow in place of copolymer micelles in the upper layer of the mesostructured thin film. Rutherford Backscattering Spectrometry (RBS) measurements support the hypothesis that silver ions initially dispersed in the film volume migrate toward the film surface to form the monolayer of silver nanoparticles, organized and stabilized by the copolymer micelles in the film. IR and ellipsometric measurements are used to characterize the changes in the hybrid copolymer-silica matrix.

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References

  • Adhyapak PV, Karandikar P, Vijayamohanan K, Athawale AA, Chandwadkar AJ (2004) Synthesis of silver nanowires inside mesoporous MCM-41 host. Mater Lett 58(3–4):1168–1171

    Article  CAS  Google Scholar 

  • Besson S, Gacoin T, Ricolleau C, Jacquiod C, Boilot JP (2002) 3D quantum dot lattice inside mesoporous silica films. Nano Lett 2(4):409–414

    Article  CAS  ADS  Google Scholar 

  • Besson S, Gacoin T, Ricolleau C, Boilot JP (2003a) Silver nanoparticle growth in 3D-hexagonal mesoporous silica films. Chem Commun 9(3):360–361

    Article  Google Scholar 

  • Besson S, Ricolleau C, Gacoin T, Jacquiod C, Boilot JP (2003b) Highly ordered orthorhombic mesoporous silica films. Microporous Mesoporous Mater 60(1–3):43–49

    Article  CAS  Google Scholar 

  • Bi H, Cai W, Kan C, Zhang L, Martin D, Träger F (2002a) Optical study of redox process of Ag nanoparticles at high temperature. J Appl Phys 92(12):7491–7497

    Article  CAS  ADS  Google Scholar 

  • Bi H, Cai W, Shi H, Liu X (2002b) Optical absorption of Ag oligomers dispersed within pores of mesoporous silica. Chem Phys Lett 357(3–4):249–254

    Article  CAS  ADS  Google Scholar 

  • Boal AK, Ilhan F, DeRouchey JE, Thurn-Albrecht T, Russell TP, Rotello VM (2000) Self-assembly of nanoparticles into structured spherical and network aggregates. Nature 404:746–748

    Article  CAS  PubMed  ADS  Google Scholar 

  • Bois L, Bessueille F, Chassagneux F, Battie Y, Destouches N, Hubert C, Boukenter A, Parola S (2008) Silver nanoparticles growth in a mesoporous silica film templated with the F127 triblock copolymer. Colloids Surf A 325(1–2):86–92

    Article  CAS  Google Scholar 

  • Bois L, Chassagneux F, Parola S, Bessueille F, Battie Y, Destouches N, Boukenter A, Moncoffre N, Toulhoat N (2009) Growth of ordered silver nanoparticles in silica film mesostructured with a triblock copolymer PEO-PPO-PEO. J Solid State Chem 182:1700–1707

    Article  CAS  ADS  Google Scholar 

  • Boissiere C, Grosso D, Lepoutre SQ, Nicole L, Brunet Bruneau A, Sanchez C (2005) Porosity and mechanical properties of mesoporous thin films assessed by environmental ellipsometric porosimetry. Langmuir 21(26):12362–12371

    Article  CAS  PubMed  Google Scholar 

  • Bönnemann H, Richards RM (2001) Nanoscopic metal particles—synthetic methods and potential applications. Eur J Inorg Chem 10:2455–2480

    Article  Google Scholar 

  • Cai W, Zhang L (1997) Synthesis and structural and optical properties of mesoporous silica containing silver nanoparticles. J Phys Condens Matter 9(34):7257–7267

    Article  Google Scholar 

  • Cai W, Hofmeister H, Rainer T, Chen W (2001) Optical properties of Ag and Au nanoparticles dispersed within the pores of monolithic mesoporous silica. J Nanopart Res 3(5–6):443–453

    CAS  Google Scholar 

  • Chen Z, Gao Q, Wu C, Ruan M, Shi J (2004) Preparation and properties of an ordered, uniform 0.9 nm Ag array assembled in a nanoporous VSB-1 by a simple soft chemical method. Chem Commun 17:1998–1999

    Article  Google Scholar 

  • Daniel MC, Astruc D (2004) Gold nanoparticles: assembly, supramolecular chemistry, quantum-size-related properties, and applications toward biology, catalysis, and nanotechnology. Chem Rev 104(1):293–346

    Article  CAS  PubMed  Google Scholar 

  • Dourdain S,. Bardeau J F, Colas M, Smarsly B, Mehdi A, Ocko B M, Gibaud A (2005) Determination by x-ray reflectivity and small angle x-ray scattering of the porous properties of mesoporous silica thin films. Appl Phys Lett 86(11):113108 1–3

    Google Scholar 

  • Eustis S, Krylova G, Smirnova N, Eremenko A, Tabor C, Huang W, El-Sayed MA (2006) Using silica films and powders modified with benzophenone to photoreduce silver nanoparticles. J Photochem Photobiol A 181:385–393

    Article  CAS  Google Scholar 

  • Fendler JH (2001) Chemical self-assembly for electronic applications. Chem Mater 13(10):3196–3210

    Article  CAS  Google Scholar 

  • Freeman RG, Grabar KC, Allison KJ, Bright RM, Davis JA, Guthrie AP, Hommer MB, Jackson MA, Smith PC, Walter DG, Natan MJ (1995) Self-assembled metal colloid monolayers: an approach to SERS substrates. Science 267(5204):1629–1632

    Article  CAS  PubMed  ADS  Google Scholar 

  • Gacoin T, Besson S, Boilot JP (2006) Organized mesoporous silica films as templates for the elaboration of organized nanoparticle networks. J Phys Condens Matter 18:S85–S95

    Article  CAS  ADS  Google Scholar 

  • Ghosh SK, Pal T (2007) Interparticle coupling effect on the surface plasmon resonance of gold nanoparticles: from theory to applications. Chem Rev 107(11):4797–4862

    Article  CAS  PubMed  Google Scholar 

  • Hamon RF, Khan AS, Chow A (1982) The cation-chelation mechanism of metal-ion sorption by polyurethanes. Talanta 29(4):313–326

    Article  CAS  PubMed  Google Scholar 

  • Hornebecq V, Antonietti M, Cardinal T, Treguer-Delapierre M (2003) Stable silver nanoparticles immobilized in mesoporous silica. Chem Mater 15(10):1993–1999

    Article  CAS  Google Scholar 

  • Koretsky GM, Knickelbein MB (1997) The reactions of silver clusters with ethylene and ethylene oxide: Infrared and photoionization studies of Ag n (C2H4) m , Ag n (C2H4O) m and their deuterated analogs. J Chem Phys 107(24):10555–10566

    Article  CAS  ADS  Google Scholar 

  • Li J, Kamata K, Iyoda T (2008) Tailored Ag nanoparticle array fabricated by block copolymer photolithography. Thin Solid Films 516(9):2577–2581

    Article  CAS  ADS  Google Scholar 

  • Liu J, Alvarez J, Kaifer AE (2000) Metal nanoparticles with a knack for molecular recognition. Adv Mater 12(18):1381–1383

    Article  CAS  Google Scholar 

  • Luo C, Zhang Y, Zeng X, Zeng Y, Wang Y (2005) The role of poly(ethylene glycol) in the formation of silver nanoparticles. J Colloid Interface Sci 288(2):444–448

    Article  CAS  PubMed  Google Scholar 

  • Mayer M (1997) SIMNRATM User’s guide, Technical report IPP 9/113. Max Planck Institut für Plasmaphysik Garching. Available via DIALOG. http://www.rzg.mpg.de/~mam/

  • Mirkin CA, Letsinger RL, Mucic RC, Storhoff JJ (1996) A DNA-based method for rationally assembling nanoparticles into macroscopic materials. Nature 382(6592):607–609

    Article  CAS  PubMed  ADS  Google Scholar 

  • Murray CB, Kagan CR, Bawendi MG (2000) Synthesis and characterization of monodisperse nanocrystals and close-packed nanocrystal assemblies. Annu Rev Mat Sci 30:545–610

    Article  CAS  ADS  Google Scholar 

  • Naik SP, Yamakita S, Ogura M, Okubo T (2004) Studies on mesoporous silica fillms synthesized using F127, a triblock co-polymer. Microporous Mesoporous Mat 75(1–2):51–59

    Article  CAS  Google Scholar 

  • Pan AL, Zheng HG, Yang ZP, Liu FX, Zhu Y, Su X, Ding ZJ, Qian YT (2003) Optical absorption properties of Ag/SiO2 composite films induced by gamma irradiation. J Phys Condens Matter 15:9–16

    Article  CAS  ADS  Google Scholar 

  • Park JH, Park JK, Shin HY (2007) The preparation of Ag/mesoporous silica by direct silver reduction and Ag/functionalized mesoporous silica by in situ formation of adsorbed silver. Mater Lett 61(1):156–159

    Article  CAS  Google Scholar 

  • Renard C, Ricolleau C, Fort E, Besson S, Gacoin T, Boilot JP (2002) Coupled technique to produce two-dimensional superlattices of nanoparticles. Appl Phys Lett 80(2):300–302

    Article  CAS  ADS  Google Scholar 

  • Shenhar R, Norsten TB, Rotello VM (2005) Polymer-mediated nanoparticle assembly: structural control and applications. Adv Mater 17(6):657–669

    Article  CAS  Google Scholar 

  • Shipway N, Katz E, Willner I (2000) Nanoparticle arrays on surfaces for electronic, optical, and sensor applications. ChemPhysChem 1(1):18–52

    Article  CAS  Google Scholar 

  • Soler-Illia GJAA, Crepaldi EL, Grosso D, Durand D, Sanchez C (2002a) Structural control in self-standing mesostructured silica oriented membranes and xerogels. Chem Commun 20:2298–2299

    Article  Google Scholar 

  • Soler-Illia GJAA, Sanchez C, Lebeau B, Patarin J (2002b) Chemical strategies to design textured materials: from microporous and mesoporous oxides to nanonetworks and hierarchical structures. Chem Rev 102(11):4093–4138

    Article  PubMed  Google Scholar 

  • Stewart G, Millar C, Laybourn P, Wilkinson C, DelaRue R (1977) Planar optical waveguides formed by silver-ion migration in glass. IEEE J Quantum Elect 13(4):192–200

    Article  ADS  Google Scholar 

  • Sun J, Ma D, Zhang H, Liu X, Han X, Bao X, Weinberg G, Pfänder N, Su D (2006) Toward monodispersed silver nanoparticles with unusual thermal stability. J Am Chem Soc 128(49):15756–15764

    Article  CAS  PubMed  Google Scholar 

  • Taleb A, Russier V, Courty A, Pileni MP (1999) Collective optical properties of silver nanoparticles organized in two-dimensional superlattices. Phys Rev B 59(20):13350–13358

    Article  CAS  ADS  Google Scholar 

  • Van Hyning DL, Klemperer WG, Zukoski CF (2001) Silver nanoparticle formation: predictions and verification of the aggregative growth model. Langmuir 17(11):3128–3135

    Article  Google Scholar 

  • Wang LZ, Shi JL, Zhang WH, Ruan ML, Yu J, Yan DS (1999) Self-organization of ordered silver nanocrystal arrays on cubic mesoporous silica surfaces. Chem Mater 11(11):3015–3017

    Article  CAS  Google Scholar 

  • Wu QZ, Yin Q, Liao JF, Deng JH, Li YG (2005) Fully accessible Ag nanoparticles within three-dimensionally ordered macroporous SiO2. Chin J Chem 23(6):689–692

    Article  CAS  Google Scholar 

  • Yanagida S, Takahashi K, Okahara M (1977) Metal-ion complexation of noncyclic poly(oxyethylene) derivatives. I. Solvent extraction of alkali and alkaline earth metal thiocyanates and iodides. Bull Chem Soc Jpn 50(6):1386–1390

    Article  CAS  Google Scholar 

  • Zhao D, Yang P, Melosh N, Feng J, Chmelka BF, Stucky GD (1998) Continuous mesoporous silica films with highly ordered large pore structures. Adv Mater 10(16):1380–1385

    Article  CAS  Google Scholar 

Download references

Acknowledgments

The authors thank Annie Rivoire from Centre Technologique des Microstructures, Université Claude Bernard—Lyon I for the cutting of the sample cross-sections. They also thank Francis Vocanson (Laboratoire Hubert Curien, Saint-Etienne) for his assistance in the treatment of IR measurements. The authors gratefully acknowledge the Région Rhône Alpes for the financial support of Y. B.. This work is carried out in the framework of the POMESCO project supported by the Agence Nationale de la Recherche.

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Authors and Affiliations

  1. Université de Lyon, 42023, Saint-Etienne, France

    Yann Battie, Nathalie Destouches, Youcef Ouerdane & Aziz Boukenter

  2. CNRS, UMR 5516, Laboratoire Hubert Curien, 18 rue Pr. Lauras, 42000, Saint-Etienne, France

    Yann Battie, Nathalie Destouches, Youcef Ouerdane & Aziz Boukenter

  3. Université de Saint-Etienne, Jean-Monnet, 42000, Saint-Etienne, France

    Yann Battie, Nathalie Destouches, Youcef Ouerdane & Aziz Boukenter

  4. Université De Lyon, Laboratoire Multimatériaux et Interfaces UMR 5615 CNRS Université Claude Bernard Lyon 1, 43 bd 11 novembre 1918, 69622, Villeurbanne, France

    Laurence Bois, Fernand Chassagneux & Stéphane Parola

  5. Université Lyon, IPNL, Université de Lyon 1, CNRS/IN2P3, 4 rue E. Fermi, 69622, Villeurbanne cedex, France

    Nathalie Moncoffre & Nelly Toulhoat

  6. CEA/DEN, Centre de Saclay, 91191, Gif sur Yvette cedex, France

    Nelly Toulhoat

  7. Université de Lyon, Laboratoire DIOM EA 3526, Université Jean Monnet, Saint-Etienne, France

    Damien Jamon

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  1. Yann Battie
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  2. Nathalie Destouches
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  9. Stéphane Parola
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Correspondence to Nathalie Destouches.

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Battie, Y., Destouches, N., Bois, L. et al. Generation of an ordered layer of silver nanoparticles in mesostructured dielectric films. J Nanopart Res 12, 1073–1082 (2010). https://doi.org/10.1007/s11051-009-9794-8

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  • DOI: https://doi.org/10.1007/s11051-009-9794-8

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