Epitaxially oriented silicon nanowires (SiNWs) were grown on (111) Si substrates by the vapor–liquid–solid technique in an atmospheric-pressure chemical vapor deposition (APCVD) system using Au as the catalyst and SiCl4 as the source gas. The dependencies of SiNW growth rate on the growth temperature and SiCl4 partial pressure (PSiCl4) were investigated, and the experimental results were compared with calculated supersaturation curves for Si obtained from a gas phase equilibrium model of the SiCl4–H2 system. The SiNW growth rate was found to be weakly dependent on temperature but strongly dependent on the PSiCl4, exhibiting a maximum value qualitatively similar to that predicted from the equilibrium model. The results indicate that SiNW growth from SiCl4 is limited by gas phase chemistry and transport of reactant species to the growth surface under APCVD conditions. The experimental results are discussed within the context of a gas phase mass transport model that takes into account changes in equilibrium partial pressure due to curvature-related Gibbs–Thomson effects.
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R.S. Wagner and W.C. Ellis: Vapor–liquid–solid mechanism of single crystal growth. Appl. Phys. Lett. 4(5), 89 (1964).
R.S. Wagner and C.J. Doherty: Controlled vapor–liquid–solid growth of silicon crystals. J. Electrochem. Soc. 113(12), 1300 (1966).
D.W.F James and C. Lewis: Silicon whisker growth and epitaxy by vapor–liquid–solid mechanism. Br. J. Appl. Phys. 16(8), 1089 (1965).
E.I. Givargizov: Fundamental aspects of VLS growth. J. Cryst. Growth. 31, 20 (1975).
A.P. Goodey, S.M. Eichfeld, K.K. Lew, J.M. Redwing, and T.E. Mallouk: Silicon nanowire photoelectrochemical cells. J. Am. Chem. Soc. 129(41), 12344 (2007).
M.D. Kelzenberg, D.B. Turner-Evans, B.M. Kayes, M.A. Filler, M.C. Putnam, N.S. Lewis, and H.A. Atwater: Photovoltaic measurements in single-nanowire silicon solar cells. Nano Lett. 8(2), 710 (2008).
B.Z. Tian, X.L. Zhang, T.J. Kempa, Y. Fang, N.F. Yu, G.H. Yu, J.L. Huang, and C.M. Lieber: Coaxial silicon nanowires as solar cell and nanoelectronic power sources. Nature 449(7164), 885 (2007).
E.C. Garnett and P.D. Yang: Silicon nanowire radial p-n junction solar cells. J. Am. Chem. Soc. 130(29), 9224 (2008).
J. Goldberger, A.I. Hochbaum, R. Fan, and P.D. Yang: Silicon vertically integrated nanowire field effect transistors. Nano Lett. 6(5), 973 (2006).
A.I. Hochbaum, R. Fan, R.R. He, and P.D. Yang: Controlled growth of silicon nanowire arrays for device integration. Nano Lett. 5(3), 457 (2005).
S. Sharma, T.I. Kamins, and R.S. Williams: Synthesis of thin silicon nanowires using gold-catalyzed chemical vapor deposition. Appl. Phys. A Mater. Sci. Process. 80(6), 1225 (2005).
B.M. Kayes, M.A. Filler, M.C. Putnam, M.D. Kelzenberg, N.S. Lewis, and H.A. Atwater: Growth of vertically aligned Si wire arrays over large areas (>1 cm2) with Au and Cu catalysts. Appl. Phys. Lett. 91(10), 103110 (2007).
C.E. Kendrick, H.P. Yoon, Y.A. Yuwen, G.D. Barber, H.T. Shen, T.E. Mallouk, E.C. Dickey, T.S. Mayer, and J.M. Redwing: Radial junction silicon wire array solar cells fabricated by gold-catalyzed vapor–liquid–solid growth. Appl. Phys. Lett. 97(14), 143108 (2010).
H. Jeong, T.E. Park, H.K. Seong, M. Kim, U. Kim, and H.J. Choi: Growth kinetics of silicon nanowires by platinum assisted vapour–liquid–solid mechanism. Chem. Phys. Lett. 467(4–6), 331 (2009).
J. Weyher: Some notes on growth kinetics and morphology of VLS silicon-crystals grown with platinum and gold as liquid-forming agents. J. Cryst. Growth 43(2), 235 (1978).
A. Mao, H.T. Ng, P. Nguyen, M. McNeil, and M.J. Meyyappan: Silicon nanowire synthesis by a vapor–liquid–solid approach. J. Nanosci. Nanotechnol. 5(5), 831 (2005).
Y.J. Zhang, Q. Zhang, N.L. Wang, Y.J. Yan, H.H. Zhou, and J. Zhu: Synthesis of thin Si whiskers (nanowires) using SiCl4. J. Cryst. Growth 226(2/3), 185 (2001).
V. Schmidt, S. Senz, and U. Gosele: Diameter dependence of the growth velocity of silicon nanowires synthesized via the vapor–liquid–solid mechanism. Phys. Rev. B 75(4), 045335 (2007).
H.C. Theuerer: Epitaxial silicon films by the hydrogen reduction of SiCl4. J. Electrochem. Soc. 108(7), 649 (1961).
J. Bloem, Y.S. Oei, H.H.C Demoor, J.H.L Hanssen, and L.J. Giling: Epitaxial growth of silicon by CVD in a hot-wall furnace. J. Electrochem. Soc. 132(8), 1973 (1985).
L.P. Hunt and E. Sirtl: Thorough thermodynamic evaluation of silicon–hydrogen–chlorine system. J. Electrochem. Soc. 119(12), 1741 (1972).
E. Sirtl, L.P. Hunt, and D.H. Sawyer: High-temperature reactions in silicon–hydrogen–chlorine system. J. Electrochem. Soc. 121(7), 919 (1974).
E.G. Bylander: Kinetics of silicon crystal growth from SiCl4 decomposition. J. Electrochem. Soc. 109(12), 1171 (1962).
J. Bloem, Y.S. Oei, H.H.C Demoor, J.H.L Hanssen, and L.J. Giling: Near equilibrium growth of silicon by CVD I. The Si–Cl–H system. J. Cryst. Growth 65(1–3), 399 (1983).
S.A. Dayeh and S.T. Picraux: Direct observation of nanoscale size effects in Ge semiconductor nanowire growth. Nano Lett. 10(10), 4032 (2010).
L.E. Froberg, W. Seifert, and J. Johansson: Diameter-dependent growth rate of InAs nanowires. Phys. Rev. B 76(15), 4 (2007).
E. De Jong, R.R. LaPierre, and J.Z. Wen: Detailed modeling of the epitaxial growth of GaAs nanowires. Nanotechnology 21(4), 10 (2010).
V.G. Dubrovskii, N.V. Sibirev, G.E. Cirlin, I.P. Soshnikov, W.H. Chen, R. Larde, E. Cadel, P. Pareige, T. Xu, B. Grandidier, J.P. Nys, D. Stievenard, M. Moewe, L.C. Chuang, and C. Chang-Hasnain: Gibbs-Thomson and diffusion-induced contributions to the growth rate of Si, InP, and GaAs nanowires. Phys. Rev. B 79, 205316 (2009).
K.K. Lew and J.M. Redwing: Growth characteristics of silicon nanowires synthesized by vapor–liquid–solid growth in nanoporous alumina templates. J. Cryst. Growth 254(1/2), 14 (2003).
J. Bloem, W.A.P Claassen, and W. Valkenburg: Rate-determining reactions and surface species in CVD silicon 4. The SiCl4–H2–N2 and the SiHCl3–H2–N2 system. J. Cryst. Growth 57(1), 177 (1982).
P. Van der Putte, L.J. Giling, and J. Bloem: Growth and etching of silicon in chemical vapor-deposition systems-influence of thermal-diffusion and temperature-gradient. J. Cryst. Growth 31, 299 (1975).
M. Ohring: The Materials Science of Thin Films, 2nd ed. (Academic Press, San Diego, 2002).
This work was supported by the Department of Energy under contracts DE-FG02-05ER15749 and DE-FG36-08GO18010 and by the National Science Foundation under grant ECS-0609282. The TEM work was performed in the electron microscopy facility of the Materials Characterization Laboratory at Penn State.
This author was an editor of this journal during the review and decision stage. For the JMR policy on review and publication of manuscripts authored by editors, please refer to http://www.mrs.org/jmr-editor-manuscripts/
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Eichfeld, S.M., Shen, H., Eichfeld, C.M. et al. Gas phase equilibrium limitations on the vapor–liquid–solid growth of epitaxial silicon nanowires using SiCl4. Journal of Materials Research 26, 2207–2214 (2011). https://doi.org/10.1557/jmr.2011.144