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Nano Research 2020, 13(1): 145-150 https://doi.org/10.1007/s12274-019-2587-1
Research Article | Open Access | Issue | Published: 02 January 2020

Combining scanning tunneling microscope (STM) imaging and local manipulation to probe the high dose oxidation structure of the Si(111)-7×7 surface

Show Author's Information Dogan Kaya1,2,  Richard J. Cobley3( ),  Richard E. Palmer3
Department of Electronics and Automation, Vocational School of Adana, Cukurova University, 01160 Cukurova, Adana, Turkey
Nanoscale Physics Research Laboratory, School of Physics and Astronomy, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
College of Engineering, Swansea University, Bay Campus, Fabian Way, Swansea, SA1 8EN, UK
Keywords:
oxidation, scanning tunneling microscopy (STM), local manipulation, Si(111)
Topics:
OxidationOxide filmsScanning tunneling microscopy
Cite this article:
Kaya D, Cobley RJ, Palmer RE. Combining scanning tunneling microscope (STM) imaging and local manipulation to probe the high dose oxidation structure of the Si(111)-7×7 surface. Nano Research, 2020, 13(1): 145-150. https://doi.org/10.1007/s12274-019-2587-1
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Abstract Full text About this article

Understanding the atomistic formation of oxide layers on semiconductors is important for thin film fabrication, scaling down conventional devices and for the integration of emerging research materials. Here, the initial oxidation of Si(111) is studied using the scanning tunneling microscope. Prior to the complete saturation of the silicon surface with oxygen, we are able to probe the atomic nature of the oxide layer formation. We establish the threshold for local manipulation of inserted oxygen sites to be +3.8 V. Only by combining imaging with local atomic manipulation are we able to determine whether inserted oxygen exists beneath surface-bonded oxygen sites and differentiate between sites that have one and more than one oxygen atom inserted beneath the surface. Prior to the creation of the thin oxide film we observe a flip in the manipulation rates of inserted oxygen sites consistent with more oxygen inserting beneath the silicon surface.


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About this article

Combining scanning tunneling microscope (STM) imaging and local manipulation to probe the high dose oxidation structure of the Si(111)-7×7 surface

Show Author's information Dogan Kaya1,2, Richard J. Cobley3( ), Richard E. Palmer3
Department of Electronics and Automation, Vocational School of Adana, Cukurova University, 01160 Cukurova, Adana, Turkey
Nanoscale Physics Research Laboratory, School of Physics and Astronomy, University of Birmingham, Edgbaston, Birmingham, B15 2TT, UK
College of Engineering, Swansea University, Bay Campus, Fabian Way, Swansea, SA1 8EN, UK

Abstract

Understanding the atomistic formation of oxide layers on semiconductors is important for thin film fabrication, scaling down conventional devices and for the integration of emerging research materials. Here, the initial oxidation of Si(111) is studied using the scanning tunneling microscope. Prior to the complete saturation of the silicon surface with oxygen, we are able to probe the atomic nature of the oxide layer formation. We establish the threshold for local manipulation of inserted oxygen sites to be +3.8 V. Only by combining imaging with local atomic manipulation are we able to determine whether inserted oxygen exists beneath surface-bonded oxygen sites and differentiate between sites that have one and more than one oxygen atom inserted beneath the surface. Prior to the creation of the thin oxide film we observe a flip in the manipulation rates of inserted oxygen sites consistent with more oxygen inserting beneath the silicon surface.

Keywords: oxidation, scanning tunneling microscopy (STM), local manipulation, Si(111)

References(52)

[1]
Tilli, M.; Motooka, T.; Airaksinen, V. M.; Franssila, A.; Paulasto-Kröckel, M.; Lindroos, V. Handbook of Silicon Based MEMS Materials and Technologies, 2nd ed.; Amsterdam: William Andrew, 2015.
[2]
McNerny, D. Q.; Viswanath, B.; Copic, D.; Laye, F. R.; Prohoda, C.; Brieland-Shoultz, A. C.; Polsen, E. S.; Dee, N. T.; Veerasamy, V. S.; Hart, A. J. Direct fabrication of graphene on SiO2 enabled by thin film stress engineering. Sci. Rep. 2014, 4, 5049.
DOI Google Scholar
[3]
Zhu, W. H.; Zheng, G.; Cao, S.; He, H. Thermal conductivity of amorphous SiO2 thin film: A molecular dynamics study. Sci. Rep. 2018, 8, 10537.
DOI Google Scholar
[4]
Wang, Y. M.; Ding, K.; Sun, B. Q.; Lee, S. T.; Jie, J. S. Two-dimensional layered material/silicon heterojunctions for energy and optoelectronic applications. Nano Res. 2016, 9, 72-93.
DOI Google Scholar
[5]
Yu, M.; Xu, W.; Benjalal, Y.; Barattin, R.; Lægsgaard, E.; Stensgaard, I.; Hliwa, M.; Bouju, X.; Gourdon, A.; Joachim, C. et al. STM manipulation of molecular moulds on metal surfaces. Nano Res. 2009, 2, 254-259.
DOI Google Scholar
[6]
Li, Z.; Schouteden, K.; Iancu, V.; Janssens, E.; Lievens, P.; van Haesendonck, C.; Cerdá, J. I. Chemically modified STM tips for atomic-resolution imaging of ultrathin NaCl films. Nano Res. 2015, 8, 2223-2230.
DOI Google Scholar
[7]
Murata, Y.; Cavallucci, T.; Tozzini, V.; Pavliček, N.; Gross, L.; Meyer, G.; Takamura, M.; Hibino, H.; Beltram, F.; Heun, S. Atomic and electronic structure of Si dangling bonds in quasi-free-standing monolayer graphene. Nano Res. 2018, 11, 864-873.
DOI Google Scholar
[8]
Krasnikov, S. A.; Lübben, O.; Murphy, B. E.; Bozhko, S. I.; Chaika, A. N.; Sergeeva, N. N.; Bulfin, B.; Shvets, I. V. Writing with atoms: Oxygen adatoms on the MoO2/Mo(110) surface. Nano Res. 2013, 6, 929-937.
DOI Google Scholar
[9]
MacLeod, J. M.; Lipton-Duffin, J.; Fu, C. Y.; Rosei, F. Inducing nonlocal reactions with a local probe. ACS Nano 2009, 3, 3347-3351.
DOI Google Scholar
[10]
Maeda, K.; Nakamura, Y. Spreading effects in surface reactions induced by tunneling current injection from an STM tip. Surf. Sci. 2003, 528, 110-114.
DOI Google Scholar
[11]
Nakamura, Y.; Mera, Y.; Maeda, K. Nanoscale imaging of electronic surface transport probed by atom movements induced by scanning tunneling microscope current. Phys. Rev. Lett. 2002, 89, 266805.
DOI Google Scholar
[12]
Lu, X. K.; Polanyi, J. C.; Yang, J. A reversible molecular switch based on pattern-change in chlorobenzene and toluene on a Si(111)-(7×7) surface. Nano Lett. 2006, 6, 809-814.
DOI Google Scholar
[13]
Maksymovych, P.; Dougherty, D. B.; Zhu, X. Y.; Yates, J. T., Jr. Nonlocal dissociative chemistry of adsorbed molecules induced by localized electron injection into metal surfaces. Phys. Rev. Lett. 2007, 99, 016101.
DOI Google Scholar
[14]
Persson, B. N. J.; Avouris, P. Local bond breaking via STM-induced excitations: The role of temperature. Surf. Sci. 1997, 390, 45-54.
DOI Google Scholar
[15]
Schull, G.; Berndt, R. Orientationally ordered (7×7) superstructure of C60 on Au(111). Phys. Rev. Lett. 2007, 99, 226105.
DOI Google Scholar
[16]
Sloan, P. A.; Sakulsermsuk, S.; Palmer, R. E. Nonlocal desorption of chlorobenzene molecules from the Si(111)-(7×7) surface by charge injection from the tip of a scanning tunneling microscope: Remote control of atomic manipulation. Phys. Rev. Lett. 2010, 105, 048301.
DOI Google Scholar
[17]
Sakulsermsuk, S.; Sloan, P. A.; Palmer, R. E. A new mechanism of atomic manipulation: Bond-selective molecular dissociation via thermally activated electron attachment. ACS Nano 2010, 4, 7344-7348.
DOI Google Scholar
[18]
Sloan, P. A.; Palmer, R. E. Two-electron dissociation of single molecules by atomic manipulation at room temperature. Nature 2005, 434, 367-371.
DOI Google Scholar
[19]
Stipe, B. C.; Rezaei, M. A.; Ho, W. Site-specific displacement of Si adatoms on Si(111)- (7×7). Phys. Rev. Lett. 1997, 79, 4397-4400.
DOI Google Scholar
[20]
Inami, E.; Hamada, I.; Ueda, K.; Abe, M.; Morita, S.; Sugimoto, Y. Room-temperature-concerted switch made of a binary atom cluster. Nat. Commun. 2015, 6, 6231.
DOI Google Scholar
[21]
Ko, E.; Lee, K. R.; Choi, H. J. Tunneling properties versus electronic structures in Si/SiO2/Si junctions from first principles. Phys. Rev. B 2013, 88, 035318.
Google Scholar
[22]
Medina, H.; Lin, Y. C.; Jin, C. H.; Lu, C. C.; Yeh, C. H.; Huang, K. P.; Suenaga, K.; Robertson, J.; Chiu, P. W. Metal-free growth of nanographene on silicon oxides for transparent conducting applications. Adv. Funct. Mater. 2012, 22, 2123-2128.
Google Scholar
[23]
Tan, H. R.; Babal, P.; Zeman, M.; Smets, A. H. M. Wide bandgap p-type nanocrystalline silicon oxide as window layer for high performance thin-film silicon multi-junction solar cells. Solar Energy Mater. Solar Cells 2015, 132, 597-605.
Google Scholar
[24]
Ishizaka, A.; Iwata, S. Si-SiO2 interface characterization from angular dependence of X-ray photoelectron spectra. Appl. Phys. Lett. 1980, 36, 71-73.
Google Scholar
[25]
Muller, D. A.; Sorsch, T.; Moccio, S.; Baumann, F. H.; Evans-Lutterodt, K.; Timp, G. The electronic structure at the atomic scale of ultrathin gate oxides. Nature 1999, 399, 758-761.
Google Scholar
[26]
Hollinger, G.; Himpsel, F. J. Probing the transition layer at the SiO2-Si interface using core level photoemission. Appl. Phys. Lett. 1984, 44, 93-95.
Google Scholar
[27]
Oh, J. H.; Yeom, H. W.; Hagimoto, Y.; Ono, K.; Oshima, M.; Hirashita, N.; Nywa, M.; Toriumi, A.; Kakizaki, A. Chemical structure of the ultrathin SiO2\Si(100) interface: An angle-resolved Si 2p photoemission study. Phys. Rev. B 2001, 63, 205310.
Google Scholar
[28]
Höfer, U.; Morgen, P.; Wurth, W.; Umbach, E. Initial stages of oxygen adsorption on Si(111). II. The molecular precursor. Phys. Rev. B 1989, 40, 1130-1145.
Google Scholar
[29]
Mayne, A. J.; Rose, F.; Comtet, G.; Hellner, L.; Dujardin, G. Variable temperature STM studies of the adsorption of oxygen on the Si(111)-7×7 surface. Surf. Sci. 2003, 528, 132-137.
Google Scholar
[30]
Martel, R.; Avouris, P.; Lyo, I. W. Molecularly adsorbed oxygen species on Si(111)-(7×7): STM-induced dissociative attachment studies. Science 1996, 272, 385-388.
Google Scholar
[31]
Rusimova, K. R.; Purkiss, R. M.; Howes, R.; Lee, F.; Crampin, S.; Sloan, P. A. Regulating the femtosecond excited-state lifetime of a single molecule. Science 2018, 361, 1012-1016.
Google Scholar
[32]
Rusimova, K. R.; Bannister, N.; Harrison, P.; Lock, D.; Crampin, S.; Palmer, R. E.; Sloan, P. A. Initiating and imaging the coherent surface dynamics of charge carriers in real space. Nat. Commun. 2016, 7, 12839.
Google Scholar
[33]
Rusimova, K. R.; Sloan, P. A. Molecular and atomic manipulation mediated by electronic excitation of the underlying Si(111)-7×7 surface. Nanotechnology 2016, 28, 054002.
Google Scholar
[34]
Lock, D.; Rusimova, K. R.; Pan, T. L.; Palmer, R. E.; Sloan, P. A. Atomically resolved real-space imaging of hot electron dynamics. Nat. Commun. 2015, 6, 8365.
Google Scholar
[35]
Lock, D.; Sakulsermsuk, S.; Palmer, R. E.; Sloan, P. A. Mapping the site-specific potential energy landscape for chemisorbed and physisorbed aromatic molecules on the Si(1 1 1)-7×7 surface by time-lapse STM. J. Phys. Condens. Matter 2015, 27, 054003.
Google Scholar
[36]
Pan, T. L.; Sloan, P. A.; Palmer, R. E. Concerted thermal-plus-electronic nonlocal desorption of chlorobenzene from Si(111)-7×7 in the STM. J. Phys. Chem. Lett. 2014, 5, 3551-3554.
Google Scholar
[37]
Pan, T. L.; Sloan, P. A.; Palmer, R. E. Non-local atomic manipulation on semiconductor surfaces in the STM: The case of chlorobenzene on Si(111)-7×7. Chem. Rec. 2014, 14, 841-847.
Google Scholar
[38]
Sakulsermsuk, S.; Sloan, P. A.; Theis, W.; Palmer, R. E. Calibrating thermal and scanning tunnelling microscope induced desorption and diffusion for the chemisorbed chlorobenzene/Si(111)7×7 system. J. Phys. Condens. Matter 2010, 22, 084002.
Google Scholar
[39]
Sloan, P. A.; Hedouin, M. F. G.; Palmer, R. E.; Persson, M. Mechanisms of molecular manipulation with the scanning tunneling microscope at room temperature: Chlorobenzene/Si(111)-(7×7). Phys. Rev. Lett. 2003, 91, 118301.
Google Scholar
[40]
Lyo, I. W.; Avouris, P. Field-induced nanometer- to atomic-scale manipulation of silicon surfaces with the STM. Science 1991, 253, 173-176.
Google Scholar
[41]
Lee, S. H.; Kang, M. H. Origin of O 1s core-level shifts on oxygen adsorbed Si(111)-(7×7). Phys. Rev. Lett. 2000, 84, 1724-1727.
Google Scholar
[42]
Lee, S. H.; Kang, M. H. Identification of the initial-stage oxidation products on Si(111)-(7×7). Phys. Rev. Lett. 1999, 82, 968-971.
Google Scholar
[43]
Comtet, G.; Hellner, L.; Dujardin, G.; Bobrov, K. Adsorption of O2 on Si(111)-7×7 at 300 and 30 K studied by ion photodesorption and electron photoemission. Phys. Rev. B 2001, 65, 035315.
Google Scholar
[44]
Sakamoto, K.; Doi, S.; Ushimi, Y.; Ohno, K.; Yeom, H. W.; Ohta, T.; Suto, S.; Uchida, W. Adsorption process of metastable molecular oxygen on a Si(111)-7×7 surface. Phys. Rev. B 1999, 60, R8465-R8468.
Google Scholar
[45]
Onoda, J.; Ondráček, M.; Yurtsever, A.; Jelínek, P.; Sugimoto, Y. Initial and secondary oxidation products on the Si(111)-(7 × 7) surface identified by atomic force microscopy and first principles calculations. Appl. Phys. Lett. 2014, 104, 133107.
Google Scholar
[46]
Leibsle, F. M.; Samsavar, A.; Chiang, T. C. Oxidation of Si(111)-(7×7) as studied by scanning tunneling microscopy. Phys. Rev. B 1988, 38, 5780-5783.
Google Scholar
[47]
Tokumoto, H.; Miki, K.; Murakami, H.; Bando, H.; Ono, M.; Kajimura, K. Real-time observation of oxygen and hydrogen adsorption on silicon surfaces by scanning tunneling microscopy. J. Vac. Sci. Technol. A 1990, 8, 255-258.
Google Scholar
[48]
Kaya, D. The effect of electric field on a fullerene molecule on a metal surface by a nano STM tip. Phys. B Condens. Matter 2019, 557, 126-131.
Google Scholar
[49]
Niu, C. Y.; Wang, J. T. Adsorption and dissociation of oxygen molecules on Si(111)-(7×7) surface. J. Chem. Phys. 2013, 139, 194709.
Google Scholar
[50]
Wiggins, B.; Avila-Bront, L. G.; Edel, R.; Sibener, S. J. Temporally and spatially resolved oxidation of Si(111)-(7×7) using kinetic energy controlled supersonic beams in combination with scanning tunneling microscopy. J. Phys. Chem. C 2016, 120, 8191-8197.
Google Scholar
[51]
Hasegawa, T.; Kohno, M.; Hosoki, S. Initial stage of oxygen adsorption onto a Si(111)-7×7 surface studied by scanning tunneling microscopy. Jpn. J. Appl. Phys. 1994, 33, 3702-3705.
Google Scholar
[52]
Caldas, M. J.; Baierle, R. J.; Capaz, R. B.; Artacho, E. Ab initio study of atomic oxygen adsorption on the Si(111)7×7 surface. Phys. B Condens. Matter 2001, 308-310, 329-332.
Google Scholar
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Publication history

Received: 15 August 2019
Revised: 04 November 2019
Accepted: 28 November 2019
Published: 02 January 2020
Issue date: January 2020

Copyright

© The Authors 2019

Acknowledgements

The authors thank the Engineering and Physical Sciences Research Council (UK) for financial support of this research (No. EP/K006061/2). D. K. thanks the Republic of Turkey Ministry of National Education for a PhD scholarship.

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