Synthesis of low-oxide blue luminescent alkyl-functionalized silicon nanoparticles with no nitrogen containing surfactant

  • Jason A. Thomas
  • Shane P. Ashby
  • Frederik Huld
  • Timothy J. Pennycook
  • Yimin Chao
Research Paper


Of ever growing interest in the fields of physical chemistry and materials science, silicon nanoparticles show a great deal of potential. Methods for their synthesis are, however, often hazardous, expensive or otherwise impractical. In the literature, there is a safe, fast and cheap inverse micelle-based method for the production of alkyl-functionalized blue luminescent silicon nanoparticles, which nonetheless found limitations, due to undesirable Si-alkoxy and remaining Si–H functionalization. In the following work, these problems are addressed, whereby an optimisation of the reaction mechanism encourages more desirable capping, and the introduction of alcohol is replaced by the use of anhydrous copper (II) chloride. The resulting particles, when compared with their predecessors through a myriad of spectroscopic techniques, are shown to have greatly reduced levels of ‘undesirable’ capping, with a much lower surface oxide level; whilst also maintaining long-term air stability, strong photoluminescence and high yields.


Silicon Nanoparticles Oxidation STEM XPS Inverse micelle 



SPA is grateful to an industry CASE studentship sponsored by EPSRC and European Thermodynamics Ltd. X-ray photoelectron spectra were obtained at the National EPSRC XPS User’s Service (NEXUS) at Newcastle University, an EPSRC Mid-Range Facility. Aberration-corrected STEM measurements were performed at the EPSRC UK National Facility for Aberration-Corrected STEM managed by the SuperSTEM consortium.

Conflict of interest

The authors declare that they have no conflict of interest.


  1. Ahire JH, Wang Q, Coxon PR, Malhotra G, Brydson R, Chen R, Chao Y (2012) Highly luminescent and nontoxic amine-capped nanoparticles from porous silicon: synthesis and their use in biomedical imaging. ACS Appl Mater Interfaces 4:3285–3292CrossRefGoogle Scholar
  2. Ahire JH, Chambrier I, Mueller A, Bao Y, Chao Y (2013) Synthesis of d-mannose capped silicon nanoparticles and their interactions with MCF-7 human breast cancerous cells. ACS Appl Mater Interfaces 5:7384–7391CrossRefGoogle Scholar
  3. Alivisatos AP (1996) Perspectives on the physical chemistry of semiconductor nanocrystals. J Phys Chem 100:13226–13239CrossRefGoogle Scholar
  4. Ashby S, Thomas J, Coxon P, Bilton M, Brydson R, Pennycook T, Chao Y (2013) The effect of alkyl chain length on the level of capping of silicon nanoparticles produced by a one-pot synthesis route based on the chemical reduction of micelle. J Nanopart Res 15:1425CrossRefGoogle Scholar
  5. Brus L (1991) Semiconductors—squeezing light from silicon. Nature 353:301–302CrossRefGoogle Scholar
  6. Canham LT (1990) Silicon quantum wire array fabrication by electrochemical and chemical dissolution of wafers. Appl Phys Lett 57:1046–1048CrossRefGoogle Scholar
  7. Chao Y, Wang Q, Pietzsch A, Hennies F, Ni H (2011) Soft X-ray induced oxidation on acrylic acid grafted luminescent silicon quantum dots in ultrahigh vacuum. Phys Status Solidi A 208:2424–2429CrossRefGoogle Scholar
  8. Coxon PR, Wang Q, Chao Y (2011) An abrupt switch between the two photoluminescence bands within alkylated silicon nanocrystals. J Phys D Appl Phys 44:495301CrossRefGoogle Scholar
  9. Dasog M, Yang Z, Regli S, Atkins TM, Faramus A, Singh MP, Muthuswamy E, Kauzlarich SM, Tilley RD, Veinot JGC (2013) Chemical insight into the origin of red and blue photoluminescence arising from freestanding silicon nanocrystals. ACS Nano 7:2676–2685CrossRefGoogle Scholar
  10. Erogbogbo F, Yong K-T, Roy I, Xu G, Prasad PN, Swihart MT (2008) Biocompatible luminescent silicon quantum dots for imaging of cancer cells. ACS Nano 2:873–878CrossRefGoogle Scholar
  11. Fendler JH, Meldrum FC (1995) The colloid chemical approach to nanostructured materials. Adv Mater 7:607–632CrossRefGoogle Scholar
  12. Fuzell J, Thibert A, Atkins TM, Dasog M, Busby E, Veinot JGC, Kauzlarich SM, Larsen DS (2013) Red states versus blue states in colloidal silicon nanocrystals: exciton sequestration into low-density traps. J Phys Chem Lett 4:3806–3812CrossRefGoogle Scholar
  13. Hagfeldt A, Graetzel M (1995) Light-induced redox reactions in nanocrystalline systems. Chem Rev 95:49–68CrossRefGoogle Scholar
  14. Henglein A (1989) Small-particle research: physicochemical properties of extremely small colloidal metal and semiconductor particles. Chem Rev 89:1861–1873CrossRefGoogle Scholar
  15. Kang Z, Liu Y, Lee ST (2010) Small-sized silicon nanoparticles: new nanolights and nanocatalysts. Nanoscale 3:777–791CrossRefGoogle Scholar
  16. Kovalev D, Diener J, Heckler H, Polisski G, Kunzner N, Koch F (2000) Optical absorption cross sections of si nanocrystals. Phys Rev B 61:4485–4487CrossRefGoogle Scholar
  17. Littau KA, Szajowski PJ, Muller AJ, Kortan AR, Brus LE (1993) A luminescent silicon nanocrystal colloid via a high-temperature aerosol reaction. J Phys Chem 97:1224–1230CrossRefGoogle Scholar
  18. Mayne AH, Bayliss SC, Barr P, Tobin M, Buckberry LD (2000) Biologically interfaced porous silicon devices. Phys Status Solidi A Appl Res 182:505–513CrossRefGoogle Scholar
  19. M’Gaieth R, Maaref H, Mihalcescu I, Vial JC (1999) Porous silicon: photoluminescence decay in the nanosecond range. Microelectron J 30:695–698CrossRefGoogle Scholar
  20. Priolo F, Gregorkiewicz T, Galli M, Krauss TF (2014) Silicon nanostructures for photonics and photovoltaics. Nat Nanotechnol 9:19–32CrossRefGoogle Scholar
  21. Uchida N, Tada T, Ohishi Y, Miyazaki Y, Kurosaki K, Yamanaka S (2013) Heavily doped silicon and nickel silicide nanocrystal composite films with enhanced thermoelectric efficiency. J Appl Phys 114:134311CrossRefGoogle Scholar
  22. Veinot JG (2006) Synthesis, surface functionalization, and properties of freestanding silicon nanocrystals. Chem Commun 40:4160–4168CrossRefGoogle Scholar
  23. Wang J, Sun S, Peng F, Cao L, Sun L (2011) Efficient one-pot synthesis of highly photoluminescent alkyl-functionalised silicon nanocrystals. Chem Commun 47:4941–4943CrossRefGoogle Scholar
  24. Wang Q, Bao Y, Ahire J, Chao Y (2013) Co-encapsulation of biodegradable nanoparticles with silicon quantum dots and quercetin for monitored delivery. Adv Health Mater 2:459–465CrossRefGoogle Scholar
  25. Warner JH, Hoshino A, Yamamoto K, Tilley RD (2005) Water-soluble photoluminescent silicon quantum dots. Angew Chem Int Ed 44:4550–4554CrossRefGoogle Scholar
  26. Wilcoxon JP, Samara GA, Provencio PN (1999) Optical and electronic properties of Si nanoclusters synthesized in inverse micelles. Phys Rev B 60:2704–2714CrossRefGoogle Scholar
  27. Wilson WL, Szajowski PF, Brus LE (1993) Quantum confinement in size-selected, surface-oxidized silicon nanocrystals. Science 262:1242–1244CrossRefGoogle Scholar
  28. Woggon U, Gaponenko S, Langbein W, Uhrig A, Klingshirn C (1993) Homogeneous linewidth of confined electron-hole-pair states in II–VI-quantum dots. Phys Rev B 47:3684–3689CrossRefGoogle Scholar
  29. Wolkin MV, Jorne J, Fauchet PM, Allan G, Delerue C (1999) Electronic states and luminescence in porous silicon quantum dots: the role of oxygen. Phys Rev Lett 82:197–200CrossRefGoogle Scholar
  30. Xiong HM, Wang ZD, Xia YY (2006) Polymerization initiated by inherent free radicals on nanoparticle surfaces: a simple method of obtaining ultrastable (ZnO) polymer core-shell nanoparticles with strong blue fluorescence. Adv Mater 18:748–751CrossRefGoogle Scholar

Copyright information

© Springer Science+Business Media Dordrecht 2015

Authors and Affiliations

  • Jason A. Thomas
    • 1
  • Shane P. Ashby
    • 1
  • Frederik Huld
    • 1
  • Timothy J. Pennycook
    • 2
    • 3
  • Yimin Chao
    • 1
  1. 1.School of ChemistryUniversity of East AngliaNorwichUK
  2. 2.SuperSTEM Laboratory, STFC Daresbury CampusWarringtonUK
  3. 3.Department of MaterialsUniversity of OxfordOxfordUK

Personalised recommendations