Surface brightens up Si quantum dots: direct bandgap-like size-tunable emission

Kateřina Dohnalová; Alexander N Poddubny; Alexei A Prokofiev; Wieteke DAM de Boer; Chinnaswamy P Umesh; Jos MJ Paulusse; Han Zuilhof; Tom Gregorkiewicz

doi:10.1038/lsa.2013.3

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Surface brightens up Si quantum dots: direct bandgap-like size-tunable emission

Original Articles

- Surface brightens up Si quantum dots: direct bandgap-like size-tunable emission
- Light: Science & Applications Vol. 2, Issue 1-2, (2013)
- Affiliations：
  
  1.Van der Waals-Zeeman Institute, University of Amsterdam, NL-1098 XH Amsterdam, The Netherlands
  2.Laboratory of Organic Chemistry, Wageningen University, 6703 HB Wageningen, The Netherlands
  3.Department of Chemical and Materials Engineering, King Abdulaziz University, Jeddah, Saudi Arabia
  4.Ioffe Physical-Technical Institute RAS, 26 Polytechnicheskaya, 194021 Saint-Petersburg, Russia
  5.Current address: MIRA Institute, Department of Biomedical Chemistry, University of Twente, Building Zuidhorst Enschede, The Netherlands
- Author bio：
  
  Dr K Dohnalová, Van der Waals-Zeeman Institute, University of Amsterdam, Science Park 904, NL-1098 XH Amsterdam, The Netherlands E-mail: k.dohnalova@uva.nl
- Funds：
- DOI：10.1038/lsa.2013.3
  CLC：
- Published：2013-06，
  
  Published Online：04 January 2013，
  
  Received：05 July 2012，
  
  Revised：11 September 2012，
  
  Accepted：25 September 2012
- Accepted：
Scan QR Code
Dohnalová, K. et al. Surface brightens up Si quantum dots: direct bandgap-like size-tunable emission. Light: Science & Applications, 2, e47 (2013).
DOI：

Dohnalová, K. et al. Surface brightens up Si quantum dots: direct bandgap-like size-tunable emission. Light: Science & Applications, 2, e47 (2013). DOI： 10.1038/lsa.2013.3.

摘要

Abstract

Colloidal semiconductor quantum dots (QDs) constitute a perfect material for ink-jet printable large area displays

photovoltaics

light-emitting diode

bio-imaging luminescent markers and many other applications. For this purpose

efficient light emission/absorption and spectral tunability are necessary conditions. These are currently fulfilled by the direct bandgap materials. Si-QDs could offer the solution to major hurdles posed by these materials

namely

toxicity (e.g.

Cd-

Pb- or As-based QDs)

scarcity (e.g.

QD with In

Te) and/or instability. Here we show that by combining quantum confinement with dedicated surface engineering

the biggest drawback of Si—the indirect bandgap nature—can be overcome

and a 'direct bandgap' variety of Si-QDs is created. We demonstrate this transformation on chemically synthesized Si-QDs using state-of-the-art optical spectroscopy and theoretical modelling. The carbon surface termination gives rise to drastic modification in electron and hole wavefunctions and radiative transitions between the lowest excited states of electron and hole attain 'direct bandgap-like' (phonon-less) character. This results in efficient fast emission

tunable within the visible spectral range by QD size. These findings are fully justified within a tight-binding theoretical model. When the C surface termination is replaced by oxygen

the emission is converted into the well-known red luminescence

with microsecond decay and limited spectral tunability. In that way

the 'direct bandgap' Si-QDs convert into the 'traditional' indirect bandgap form

thoroughly investigated in the past.

关键词

Keywords

direct bandgapoptical spectroscopyoptoelectronicsorganic cappingsilicon quantum dotstight binding model

references

Delley B, Steigmeier EF. Quantum confinement in Si nanocrystals.Phys Rev B1993;47: 1397..

Hybertsen MS. Absorption and emission of light in nanoscale silicon structures.Phys Rev Lett1994;72: 1514–1517..

Belyakov VA, Burdov VA, Lockwood R, Meldrum A. Silicon nanocrystals: fundamental theory and implications for stimulated emission.Adv Opt Technol2008; 279502.

Kovalev D, Heckler H, Polisski G, Koch F. Optical properties of Si nanocrystals.Phys Status Solidi B1999;215: 871–932..

Wolkin MV, Jorne J, Fauchet PM, Allan G, Delerue C. Electronic states and luminescence in porous silicon quantum dots: the role of oxygen.Phys Rev Lett1999;82: 197–200..

Goller B, Polisski S, Wiggers H, Kovalev D. Freestanding spherical silicon nanocrystals: a model system for studying confined excitons.Appl Phys Lett2010;97: 041110..

Dohnalová K, Kůsová K, Pelant I. Time-resolved photoluminescence study on initial phase oxidation of small silicon nanocrystals.Appl Phys Lett2009;94: 211903..

Veinot JC. Synthesis, surface functionalization, and properties of freestanding silicon nanocrystals.Chem Commun2006;40: 4160..

Zou J, Kauzlarich SM. Functionalization of silicon nanoparticlesviasilanization: alkyl, halide and ester.J Clust Sci2008;19: 341–355..

Ruizendaal L, Pujari SP, Gevaerts V, Paulusse JM, Zuilhof H. Bio- functional silicon nanoparticlesviathiolene click chemistry.Chem Asian J2011;6: 2776–2786..

Hessel CM, Rasch MR, Hueso JL, Goodfellow BW, Akhavan VAet al. Synthesis of ligand stabilized silicon nanocrystals with size-dependent photoluminescence spanning visible to near-infrared wavelengths.Chem Mater2012;24: 393–401..

Rosso-Vasic M, Spruijt E, van Lagen B, de Cola L, Zuilhof H. Alkyl-functionalized oxide-free silicon nanoparticles: synthesis and optical properties.Small2008;4: 1835–1841..

English DS, Pell LE, Yu Z, Barbara PF, Korgel BA. Size tunable visible luminescence from individual organic monolayer stabilized silicon nanocrystal quantum dots.Nano Lett2002;2: 681–685..

Wilcoxon JP, Samara GA, Provencio PN. Optical and electronic properties of Si nanoclusters synthesized in inverse micelles.Phys Rev B1999;60: 2704–2714..

Zou J, Baldwin RK, Pettigrew KA, Kauzlarich SM. Solution synthesis of ultrastable luminescent siloxane-coated silicon nanoparticles.Nano Lett2004;4: 1181–1186..

Warner JH, Hoshino A, Yamamoto K, Tilley RD. Water-soluble photoluminescent silicon quantum dots.Angew Chem Int Ed2005;44: 4550–4554..

Kurumoto N, Yamada T, Uchino T. Enhanced blue photoluminescence from SiCl4-treated nanometer-sized silica particles.J Non-Cryst Sol2007;353: 684–686..

Erratum for publication [12], published in Small. 2009;5: n/a.

Reboredo FA, Galli G. Theory of alkyl-terminated silicon quantum dots.J Phys Chem B2005;109: 1072–1078..

Kůsová K, Cibulka O, Dohnalová K, Pelant I, Valenta Jet al. Brightly luminescent organically capped silicon nanocrystals fabricated at room temperature and atmospheric pressure.ACS Nano2010;4: 4495–4504..

Yang CS, Bley RA, Kauzlarich SM, Lee HW, Delgado GR. Synthesis of alkyl-terminated silicon nanoclusters by a solution route.J Am Chem Soc1999;121: 5191–5195..

Dohnalová K, Fučíková A, Umesh CP, Humpolíčková J, Paulusse JMet al. Microscopic origin of the fast blue-green luminescence of chemically synthesized non-oxidized silicon quantum dots.Small2012;8: 3185–3191..

Takeoka S, Fujii M, Hayashi S. Size-dependent photoluminescence from surface-oxidized Si nanocrystals in a weak confinement regime.Phys Rev B2000;62: 16820–16825..

Godefroo S, Hayne M, Jivanescu M, Stesmans A, Zacharias Met al. Classification and control of the origin of photoluminescence from Si nanocrystals.Nat Nanotechnol2008;3: 174..

Heitmann J, Müller F, Zacharias M, Gösele U. Silicon nanocrystals: size matters.Adv Mater2005;17: 795..

de Boer WD, Timmerman D, Dohnalova K, Yassievich IN, Zhang Het al. Red spectral shift and enhanced quantum efficiency in phonon-free photoluminescence from silicon nanocrystals.Nat Nanotechnol2010;5: 878–884..

Timmerman D, Valenta J, Dohnalová K, de Boer WD, Gregorkiewicz T. Step-like enhancement of luminescence quantum yield of silicon nanocrystals.Nat Nanotechnol2011;6: 710–713..

Mangolini L, Jurbergs D, Rogojina E, Kortshagen U. Plasma synthesis and liquid-phase surface passivation of brightly luminescent Si nanocrystals.J Lumin2006;121: 327–334..

Delerue C, Lannoo M.Nanostructures: theory and modelling. Berlin: Springer-Verlag, 2004.

Wilcoxon JP, Samara GA. Tailorable, visible light emission from silicon nanocrystals.Appl Phys Lett1999;74: 3164–3166..

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