Abstract
Silicon nanoparticles are an emerging and promising material in many fields including electronics, catalysis, and biomaterial engineering. Synthesis in the gas phase via aerosol routes allows tuning and engineering material features such as primary particle size distribution, agglomerate size distribution, crystallite size, and morphology. Proper control of these features as well as post-synthesis processing such as surface oxidation is very relevant for making the nanoparticles chemically stable. Therefore, a kinetic expression for determining the extent of oxidation in silicon nanoparticles is necessary. Significant work has been devoted to understanding the kinetics of monocrystalline silicon, and generally accepted models such as the one by Deal and Grove provide a very accurate description of bulk silicon oxidation. However, these models are not as accurate for the first hundreds of angstroms of the oxidation. While this might be acceptable for bulk wafers, it has critical results for silicon nanoparticles with diameters around such range. Furthermore, many applications involve silicon nanoparticle aggregates with a shape far away from perfect spheres. For this reason, in this work, we propose an expression for the parabolic oxidation kinetics of polycrystalline silicon nanoparticle aggregates at 1000 °C with surface area in the range of 3 to 19 m2/g. and crystallite sizes from 50 to 70 nm. The activation energy of the process is also reported to be linked to the crystallite size.
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References
Sofield CJ, Stoneham AM (1995) Oxidation of silicon - the VLSI gate dielectric. Semicond Sci Technol 10(3):215–244. https://doi.org/10.1088/0268-1242/10/3/001
Deal BE, Grove AS (1965) General relationship for the thermal oxidation of silicon. J Appl Phys 36(12):3770–3778. https://doi.org/10.1063/1.1713945
Doremus RH (1984) Oxidation of silicon: strain and linear kinetics. Thin Solid Films 122(3):191–196
Pieraggi B (1987) Calculations of parabolic reaction-rate constants. Oxid Met 27(3–4):177–185. https://doi.org/10.1007/bf00667057
Irene E (1978) Silicon oxidation studies: some aspects of the initial oxidation regime. J Electrochem Soc 125(10):1708–1714
Marcus RB, Sheng TT (1982) The oxidation of shaped silicon surfaces. J Electrochem Soc 129(6):1278–1282. https://doi.org/10.1149/1.2124118
Marcus R, Sheng T, Lin P (1982) Polysilicon/SiO2 interface microtexture and dielectric breakdown. J Electrochem Soc 129(6):1282–1289
Jimin W, Yu L, Ruiwei L (2003) An improved silicon-oxidation-kinetics and accurate analytic model of oxidation. Solid State Electron 47(10):1699–1705
Fargeix A, Ghibaudo G, Kamarinos G (1983) A revised analysis of dry oxidation of silicon. J Appl Phys 54(5):2878–2880. https://doi.org/10.1063/1.332286
EerNisse EP (1979) Stress in thermal SiO2 during growth. Appl Phys Lett 35(1):8–10. https://doi.org/10.1063/1.90905
EerNisse EP (1977) Viscous flow of thermal SiO2. Appl Phys Lett 30(6):290–293. https://doi.org/10.1063/1.89372
Fargeix A, Ghibaudo G (1983) Dry oxidation of silicon: a new model of growth including relaxation of stress by viscous flow. J Appl Phys 54(12):7153–7158. https://doi.org/10.1063/1.331986
Irene EA (1983) Silicon oxidation studies: a revised model for thermal oxidation. J Appl Phys 54(9):5416–5420. https://doi.org/10.1063/1.332722
Kim BH, Pamungkas M, Park M, Kim G, Lee KR, Chung YC (2011) Stress evolution during the oxidation of silicon nanowires in the sub-10 nm diameter regime. Appl Phys Lett 99(14). https://doi.org/10.1063/1.3643038
Yang DQ, Gillet JN, Meunier M, Sacher E (2005) Room temperature oxidation kinetics of Si nanoparticles in air, determined by x-ray photoelectron spectroscopy. J Appl Phys 97(2). https://doi.org/10.1063/1.1835566
Agnello S, Di Francesca D, Alessi A, Iovino G, Cannas M, Girard S, Boukenter A, Ouerdane Y (2013) Interstitial O2 distribution in amorphous SiO2 nanoparticles determined by Raman and photoluminescence spectroscopy. J Appl Phys 114(10):104305. https://doi.org/10.1063/1.4820940
Li S, Silvers SJ, El-Shall MS (1997) Surface oxidation and luminescence properties of Weblike agglomeration of silicon Nanocrystals produced by a laser vaporization− controlled condensation technique. J Phys Chem B 101(10):1794–1802
Ostraat ML, Brongersma M, Atwater HA, Flagan RC (2005) Nanoengineered silicon/silicon dioxide nanoparticle heterostructures. Solid State Sci 7(7):882–890. https://doi.org/10.1016/j.solidstatesubstances.2005.01.019
Mangolini L (2013) Synthesis, properties, and applications of silicon nanocrystals. J Vac Sci Technol B 31(2). https://doi.org/10.1116/1.4794789
Yoo B, Ma K, Zhang L, Burns A, Sequeira S, Mellinghoff I, Brennan C, Wiesner U, Bradbury MS (2015) Ultrasmall dual-modality silica nanoparticle drug conjugates: design, synthesis, and characterization. Biorg med Chem 23(22):7119–7130. https://doi.org/10.1016/j.bmc.2015.09.050
Pereira RN, Rowe DJ, Anthony RJ, Kortshagen U (2011) Oxidation of freestanding silicon nanocrystals probed with electron spin resonance of interfacial dangling bonds. PhRvB 83(15):9. https://doi.org/10.1103/PhysRevB.83.155327
Diebolder P, Vazquez-Pufleau M, Bandara N, Mpoy C, Raliya R, Thimsen E, Biswas P, Rogers BE (2018) Aerosol-synthesized siliceous nanoparticles: impact of morphology and functionalization on biodistribution. Int J Nanomedicine 13:7375
Wiggers H, Starke R, Roth P (2001) Silicon particle formation by pyrolysis of silane in a hot wall gasphase reactor. Chem Eng Technol 24(3):261–264
Vazquez-Pufleau M, Yamane M (2019) Relative kinetics of nucleation and condensation of silane pyrolysis in a helium atmosphere provide mechanistic insight in the initial stages of particle formation and growth. Chem Eng Sci:115230
Vazquez-Pufleau M (2019) The effect of nanoparticle morphology in the filtration efficiency and saturation of a silicon beads fluidized bed. AIChE J
Vazquez-Pufleau M, Wang Y, Biswas P, Thimsen E (2020) Measurement of sub-2 nm stable clusters during silane pyrolysis in a furnace aerosol reactor, just accepted. J Chem Phys
Vazquez-Pufleau M, Chadha TS, Yablonsky G, Biswas P (2017) Carbon elimination from silicon kerf: Thermogravimetric analysis and mechanistic considerations. Sci Rep 7:40535. https://doi.org/10.1038/srep40535http://www.nature.com/articles/srep40535#supplementary-information
Vazquez-Pufleau M, Chadha TS, Yablonsky G, Erk HF, Biswas P (2015) Elimination of carbon contamination from silicon kerf using a furnace aerosol reactor methodology. Ind Eng Chem Res 54(22):5914–5920
Liao Y-C, Nienow AM, Roberts JT (2006) Surface chemistry of aerosolized nanoparticles: thermal oxidation of silicon. J Phys Chem B 110(12):6190–6197
Das D, Farjas J, Roura P, Viera G, Bertran E (2001) Enhancement of oxidation rate of a-Si nanoparticles during dehydrogenation. Appl Phys Lett 79(22):3705–3707. https://doi.org/10.1063/1.1420533
Yang DQ, Meunier M, Sacher E (2006) Room temperature air oxidation of nanostructured Si thin films with varying porosities as studied by x-ray photoelectron spectroscopy. J Appl Phys 99(8). https://doi.org/10.1063/1.2193168
Winters BJ, Holm J, Roberts JT (2011) Thermal processing and native oxidation of silicon nanoparticles. J Nanopart Res 13(10):5473–5484
Okada R, Iijima S (1991) Oxidation property of silicon small particles. Appl Phys Lett 58(15):1662–1663
Holm J, Roberts JT (2009) Sintering, coalescence, and compositional changes of hydrogen-terminated silicon nanoparticles as a function of temperature. J Phys Chem C 113(36):15955–15963
Yu DK, Zhang RQ, Lee ST (2002) Structural properties of hydrogenated silicon nanocrystals and nanoclusters. J Appl Phys 92(12):7453–7458. https://doi.org/10.1063/1.1513878
Holm J, Roberts JT (2007) Thermal oxidation of 6 nm aerosolized silicon nanoparticles: size and surface chemistry changes. Langmuir 23(22):11217–11224. https://doi.org/10.1021/la7010869
Lu ZH, Sacher E, Yelon A (1988) Kinetics of the room-temperature air oxidation of hydrogenated amorphous-silicon and crystalline silicon. Philos Mag B-Phys Condens Matter Stat Mech Elec Optical Magn Prop 58(4):385–388. https://doi.org/10.1080/13642818808218381
Fritzsche H (1984) Chapter 9 electronic properties of surfaces in a-Si: H. in: Jacques IP (ed) semiconductors and semimetals, vol volume 21, part C. Elsevier, pp 309-345. Doi:https://doi.org/10.1016/S0080-8784(08)63073-2
Mills RL, Dhandapani B, He J (2003) Highly stable amorphous silicon hydride. Sol Energy Mater Sol Cells 80(1):1–20. https://doi.org/10.1016/S0927-0248(03)00107-7
Vazquez-Pufleau M (2016) Applications of aerosol Technologies in the Silicon Industry. Washington University in St. Louis, Saint Louis MO
Nichols G, Byard S, Bloxham MJ, Botterill J, Dawson NJ, Dennis A, Diart V, North NC, Sherwood JD (2002) A review of the terms agglomerate and aggregate with a recommendation for nomenclature used in powder and particle characterization. J Pharm Sci 91(10):2103–2109
Walter D (2013) Primary particles–agglomerates–aggregates. Nanomaterials:9–24
Rodelsperger K, Podhorsky S, Bruckel B, Dahmann D, Hartfiel G-D, Woitowitz H-J (2003) Charakterisierung von Aerosolen ultrafeiner Teilchen fur den Arbeitsschutz (characterization of ultrafine particle aerosols for occupational safety, final report of project F1804) (German). ARBEITSMEDIZIN SOZIALMEDIZIN UMWELTMEDIZIN 38(3):174–174
Ding Y, Riediker M (2015) A system to assess the stability of airborne nanoparticle agglomerates under aerodynamic shear. J Aerosol Sci 88:98–108
Pap AE, Kordas K, George TF, Leppavuori S (2004) Thermal oxidation of porous silicon: study on reaction kinetics. J Phys Chem B 108(34):12744–12747. https://doi.org/10.1021/jp049323y
Bohling C, Sigmund W (2016) Self-limitation of native oxides explained. Silicon 8(3):339–343. https://doi.org/10.1007/s12633-015-9366-8
Vyazovkin S, Burnham AK, Criado JM, Perez-Maqueda LA, Popescu C, Sbirrazzuoli N (2011) ICTAC kinetics committee recommendations for performing kinetic computations on thermal analysis data. Thermochim Acta 520(1–2):1–19. https://doi.org/10.1016/j.tca.2011.03.034
Filipovic L (2012) Topography simulation of novel processing techniques. Thesis, Technische Universität Wien, Vienna, Austria
Vyazovkin S (2016) A time to search: finding the meaning of variable activation energy. PCCP 18(28):18643–18656
Licciardello A, Puglisi O, Pignataro S (1986) Effect of organic contaminants on the oxidation-kinetics of silicon at room-temperature. Appl Phys Lett 48(1):41–43. https://doi.org/10.1063/1.96755
Acknowledgements
We would like to thank Prof. Pratim Biswas for useful discussions that helped in the materialization of this work, also Prof. Sofia Hayes for interesting discussions leading to the NMR measurements that were carried out by Jinlei Cui, to Prof. James Ballard for revising and proofreading this manuscript. This work was partially supported by the National Science Foundation, the Solar Energy Research Institute for India and the United States (SERIIUS), funded jointly by the U.S. Department of Energy (Office of Science, Office of Basic Energy Sciences, and Energy Efficiency and Renewable Energy, Solar Energy Technology Program, under Subcontract DE-AC36-08GO28308 to the National Renewable Energy Laboratory, Golden, Colorado) and the Government of India, through the Department of Science and Technology under Subcontract IUSSTF/JCERDC-SERIIUS/2012. Also thanks to the Secretaria de Educacion Publica of Mexico for their support. The Nano Research Facility (NRF) at Washington University in St. Louis, a member of the National Nanotechnology Infrastructure Network (NNIN) was used for SEM and TEM.
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Vazquez-Pufleau, M. A Simple Model for the High Temperature Oxidation Kinetics of Silicon Nanoparticle Aggregates. Silicon 13, 189–200 (2021). https://doi.org/10.1007/s12633-020-00415-3
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DOI: https://doi.org/10.1007/s12633-020-00415-3