Influence of solvent electron affinity on paramagnetic defects in hybrid Si/SiOx luminescent nanoparticles
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Luminescence of 1-octadecene-coated silicon nanoparticles with 8 nm crystalline core in hexane and CCl4 colloidal solutions and its reversible photobleaching were examined. In agreement with previous reports, anti-correlation of luminescence intensity and the number of paramagnetic defects were found in hexane. Luminescence intensity is decreased by 75% during 30 min of 405 nm laser irradiation while the number of paramagnetic defects is increased by 65%. Paramagnetic defects were supposed to be silicon dangling bonds. In CCl4 colloidal solution, this correlation is lost: photobleaching is similar to hexane colloidal solution, while the number of paramagnetic defects is not changed during irradiation. Electron trapping and subsequent breaking of weak Si-Si bonds are proposed to be the reason of formation of silicon dangling bonds during irradiation. DFT calculation of geometry and g-tensor of Si-vacancy on the boundary of crystalline silicon core and oxide shell was performed. Formation of paramagnetic defects is supposed to be a by-process responsible only for a minor effect on luminescence intensity.
KeywordsLuminescent nanoparticles EPR spectroscopy Defects DFT calculations Silicon
The authors are grateful to Prof. G.V. Fetisov for performing SAXS measurements. The research is carried out using the equipment of the shared research facilities of HPC computing resources at Lomonosov Moscow State University (Sadovnichy et al. 2013). The electron microscopy was performed using the equipment of the Shared Research Center “Structural diagnostics of materials” and partially supported by the Ministry of Science and Higher Education within the State assignment FSRC “Crystallography and Photonics” RAS. O.I.G. and E.D.F. acknowledge (partial) support from M.V. Lomonosov Moscow State University Program of Development.
The research is partially supported by the Russian Foundation for Basic Research (Grant No. 16-29-11741).
Compliance with ethical standards
Conflict of interest
The authors declare that they have no conflict of interest.
- Arrigo A, Mazzaro R, Romano F, Bergamini G, Ceroni P (2016) Photoinduced electron-transfer quenching of luminescent silicon nanocrystals as a way to estimate the position of the conduction and valence bands by Marcus theory. Chem Mater 28:6664–6671. https://doi.org/10.1021/acs.chemmater.6b02880 CrossRefGoogle Scholar
- Bagratashvili VN, Dorofeev SG, Ischenko AA, Kononov NN, Panchenko VY, Rybaltovskii AO, Sviridov AP, Senkov SN, Tsypina SI, Yusupov VI, Yuvchenko SA, Zimnyakov DA (2013) Effects of laser-induced quenching and restoration of photoluminescence in hybrid Si/SiO x nanoparticles. Laser Phys Lett 10:095901. https://doi.org/10.1088/1612-2011/10/9/095901 CrossRefGoogle Scholar
- Chumakova NA, Vorobiev AK (2012) Simulation of rigid-limit and slow-motion EPR spectra for extraction of quantitative dynamic and orientational information. In: Kokorin AI (ed) Nitroxides - theory, experiment and applications [Internet]. InTech, Rijeka, pp 57–112. https://doi.org/10.5772/74052 Google Scholar
- Dietmueller R, Stegner AR, Lechner R, Niesar S, Pereira RN, Brandt MS, Ebbers A, Trocha M, Wiggers H, Stutzmann M (2009) Light-induced charge transfer in hybrid composites of organic semiconductors and silicon nanocrystals. Appl Phys Lett 94:113301. https://doi.org/10.1063/1.3086299 CrossRefGoogle Scholar
- Goñi AR, Muniz LR, Reparaz JS, Alonso MI, Garriga M, Lopeandia AF, Rodríguez-Viejo J, Arbiol J, Rurali R (2014) Using high pressure to unravel the mechanism of visible emission in amorphous Si/SiOx nanoparticles. Phys Rev B 89:045428. https://doi.org/10.1103/PhysRevB.89.045428 CrossRefGoogle Scholar
- Hannah DC, Yang J, Podsiadlo P, Chan MKY, Demortière A, Gosztola DJ, Prakapenka VB, Schatz GC, Kortshagen U, Schaller RD (2012) On the origin of photoluminescence in silicon nanocrystals: pressure-dependent structural and optical studies. Nano Lett 12:4200–4205. https://doi.org/10.1021/nl301787g CrossRefGoogle Scholar
- Hessel CM, Reid D, Panthani MG, Rasch MR, Goodfellow BW, Wei J, Fujii H, Akhavan V, Korgel BA (2012) Synthesis of ligand-stabilized silicon nanocrystals with size-dependent photoluminescence spanning visible to near-infrared wavelengths. Chem Mater 24:393–401. https://doi.org/10.1021/cm2032866 CrossRefGoogle Scholar
- Kumar V (ed) (2007) Nanosilicon. Elsevier Ltd, AmsterdamGoogle Scholar
- Ondič L, Kůsová K, Ziegler M, Fekete L, Gärtnerová V, Cháb V, Holý V, Cibulka O, Herynková K, Gallart M, Gilliot P, Hönerlage B, Pelant I (2014) A complex study of the fast blue luminescence of oxidized silicon nanocrystals: the role of the core. Nanoscale 6:3837–3845. https://doi.org/10.1039/c3nr06454a CrossRefGoogle Scholar
- Pacchioni G, Skuja L, Griscom DL (eds) (2000) Defects in SiO2 and related dielectrics : science and technology. NATO science series. Springer Science+Business Media, DordrechtGoogle Scholar
- Rybaltovskii AO, Zavorotnyi YS, Ishchenko AA, Parshutkin AE, Radtsig VA, Sviridov AP, Feklichev ED, Bagratashvili VN (2018) Effect of Electron-acceptor compounds on the laser burning of photoluminescence of hybrid Si/SiOx silicon nanoparticles. Nanotechnologies Russ 13:141–151. https://doi.org/10.1134/S199507801802009X CrossRefGoogle Scholar
- Rybaltovskiy AO, Ischenko AA, Zavorotny YS, Garshev AV, Dorofeev SG, Kononov NN, Minaev NV, Minaeva SA, Sviridov AP, Timashev PS, Khodos II, Yusupov VI, Lazov MA, Panchenko VY, Bagratashvili VN (2015) Synthesis of photoluminescent Si/SiO x core/shell nanoparticles by thermal disproportionation of SiO: structural and spectral characterization. J Mater Sci 50:2247–2256. https://doi.org/10.1007/s10853-014-8787-x CrossRefGoogle Scholar
- Sadovnichy V, Tikhonravov A, Voevodin V, Opanasenko V (2013) “Lomonosov”: supercomputing at Moscow State University. In: Vetter JS (ed) Contemporary high performance computing: from Petascale toward Exascale. CRC Press, Boca Raton, pp 283–307Google Scholar
- Watkins GD (1986) The lattice vacancy in silicon. In: Pantelides ST (ed) Deep centers in semiconductors. Gordon and Breach, New York, p 147Google Scholar