Preparation of Luminescent Silicon Nanoparticles: A Novel Sonochemical Approach N. Arul Dhas, C. Paul Raj, and A. Gedanken* Department of Chemistry, Bar-Ilan University, Ramat-Gan 52900, Israel Received June 5, 1998 Revised Manuscript Received August 4, 1998 Currently porous silicon has been attracted a great deal of attention because of its novel optoelectronic properties due to visible light emission. 1 The electronic properties of bulk silicon cannot explain the above phenomenon, as silicon has the indirect band gap of 1.1 eV. In early investigations, the predominant view was that the surface structure, especially surface defects, controlled the luminescence properties. 2 However, re- cent work on quantum dot particles has suggested that the visible luminescence of porous silicon results from the quantum confinement of electron-hole pairs and controls the band gap widening into the visible range. 3 Therefore, the processing of silicon nanoparticles (q- particles) has generated extensive speculation over the possibilities of new applications for silicon. In this paper we describe a novel sonochemical procedure for generat- ing porous silicon nanoparticles in high yields that exhibit luminescence, attributed to quantum confine- ment effects. In the literature, relatively little headway has been made in the solution synthesis of porous silicon nano- particles, primarily due to the difficulty involved in devising a synthetic strategy compatible with the solu- tion chemistry of silicon. Such a strategy would be advantageous because it would provide a better means of controlling surface passivation of the clusters. To date, three basic methods have been used to produce silicon nanoclusters. The most successful method is the gas-phase decomposition of organic compounds of sili- con. 4 This produces silicon nanoparticles with a rela- tively small size distribution, but does not lend itself to the easy manipulation of the surface of the particles nor to their large-scale manufacture. A second method, 5 investigated by several groups, is the electrochemical etching of silicon wafers in various solvents to produce colloidal suspensions of silicon nanoparticles. The solu- tion route 6 developed to date to synthesize these nano- particles employs reacting Zintl compound KSi with SiCl 4 to produce crystalline silicon nanoparticles (yield of ∼8%). Heath 7 has prepared nanosized silicon pow- ders through the reduction of SiCl 4 and RSiCl 3 by sodium metal in a nonpolar organic solvent at a high temperature (385 °C) and high pressures (>1000 atm). The reduction takes place for 3-7 days under an argon atmosphere in a high-pressure bomb. The chemical effects of ultrasound (sonochemistry) arise from acoustic cavitation, that is, the formation, growth, and implosive collapse of bubbles in liquid. 8 The implosive collapse of the bubble generates localized hot spots through adiabatic compression or shock wave formation within the gas phase of the collapsing bubble. The conditions formed in these hot spots have been experimentally determined, with transient tempera- tures of ∼5000 K, pressures of 1800 atm, and cooling rates in excess of 10 10 K/s. Since sonochemical hot spots have a high-pressure component, one might be able to produce, on a microscopic scale, the same macroscopic conditions of high-temperature-pressure “bomb” reac- tions or explosive shock-wave synthesis of solids. In light of these methodological perspectives, many researchers have been interested in using sonochemical methods to prepare unusual materials that cannot be obtained by conventional techniques. 9 Herein, we re- port a sonochemical procedure for the preparation of technologically important luminescent silicon nanopar- ticles. 10 The sonochemical reduction of Si 4+ f Si 0 is most conveniently carried out by using an alkali metal and a dry alkane solvent whose vapor pressure is low at the sonication temperature. The choice of the solvent and the reactant seems to be a particularly important factor. The preparation is based on ultrasound-induced reduction of tetraethyl orthosilicate (TEOS) by colloidal sodium in toluene solvent at -70 °C. The combined cavitational effects and the highly electropositive char- acter of metallic sodium are believed to provide the driving force for the formation of silicon nanoparticles. The primary reaction for the sonochemical generation of silicon particles can be written as: All manipulations for the preparation of silicon nano- particles were carried out in a dry nitrogen glovebox (<10 ppm level of oxygen). Dry toluene was used as the solvent. Sulfur free toluene was refluxed over * Corresponding author. E-mail: gedanken@mail.cc.biu.ac.il. (1) Canham, L. T. Appl. Phys. Lett. 1990, 57, 1046. Brus, L. E. J. Phys. Chem. 1994, 98, 3575. (2) O’Neil, M.; Marohn, J.; McLendon, G. J. Phys. Chem. 1990, 94, 4356. Hasselbarth, A.; Eychmuller, A.; Weller, H. Chem. Phys. Lett. 1993, 203, 271. Takagi, H.; Ogawa, H.; Yamazaki, Y.; Ishizaki, A.; Nakagiri, T.; T. Appl. Phys. Lett. 1990, 56, 2379. (3) Norris, D. J.; Bawendi, M. G. Phys. Rev. 1996, B53, 16338. 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Okitsu, K.; Bandow, H.; Maeda, Y.; Nagata, Y. Chem. Mater. 1996, 8, 315. Grieser, F. Stud. Surf. Sci. Catal. 1997, 103, 57. Gutierrez, M.; Henglein, A.; Dohrmann, J. J. Phys. Chem. 1987, 91, 1, 6687. (10) Arul Dhas, N.; Gedanken, A. Silicon Nanoclusters and a Method For Producing Same. US Patent, P-1340-USP (pending). Si(OC 2 H 5 ) 4 + 4Na (colloid) )))) Si (q-particles) + 4NaOC 2 H 5 (1) 3278 Chem. Mater. 1998, 10, 3278-3281 10.1021/cm980408j CCC: $15.00 © 1998 American Chemical Society Published on Web 09/24/1998