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Nano Research 2016, 9(2): 517-529 https://doi.org/10.1007/s12274-015-0933-5
Research Article | Issue | Published: 10 December 2015

Increased chemical reactivity of single-walled carbon nanotubes on oxide substrates: In situ imaging and effect of electron and laser irradiations

Show Author's Information Hasan-al Mehedi1,  Johann Ravaux2,  Khadija Yazda1,  Thierry Michel1,  Saïd Tahir1,  Michaël Odorico2,  Renaud Podor2,  Vincent Jourdain1( )
Laboratoire Charles Coulomb (L2C)UMR 5221 CNRS-Université de Montpellier34095Montpellier, France
Institut de Chimie Séparative de MarcouleUMR 5257 CEA-CNRS-UM2-ENSCM Site de MarcouleBat 426BP 1717130207Bagnols sur Cèze cedex, France
Keywords:
single-walled carbon nanotubes, environmental scanning electron microscopy, oxidative etching, substrate-trapped charges, electron and laser irradiations
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Mehedi H-a, Ravaux J, Yazda K, et al. Increased chemical reactivity of single-walled carbon nanotubes on oxide substrates: In situ imaging and effect of electron and laser irradiations. Nano Research, 2016, 9(2): 517-529. https://doi.org/10.1007/s12274-015-0933-5
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Abstract Full text Electronic supplementary material About this article

We studied the oxygen etching of individual single-walled carbon nanotubes on silicon oxide substrates using atomic force microscopy and high-temperature environmental scanning electron microscopy. Our in situ observations show that carbon nanotubes are not progressively etched from their ends, as frequently assumed, but disappear segment by segment. Atomic force microscopy, before and after oxidation, reveals that the oxidation of carbon nanotubes on substrates proceeds through a local cutting that is followed by a rapid etching of the disconnected nanotube segment. Unexpectedly, semiconducting nanotubes appear more reactive under these conditions than metallic ones. We also show that exposure to electron and laser beams locally increases the chemical reactivity of carbon nanotubes on such substrates. These results are rationalized by considering the effect of substrate-trapped charges on the nanotube density of states close to the Fermi level, which is impacted by the substrate type and the exposure to electron and laser beams.


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About this article

Increased chemical reactivity of single-walled carbon nanotubes on oxide substrates: In situ imaging and effect of electron and laser irradiations

Show Author's information Hasan-al Mehedi1, Johann Ravaux2, Khadija Yazda1, Thierry Michel1, Saïd Tahir1, Michaël Odorico2, Renaud Podor2, Vincent Jourdain1( )
Laboratoire Charles Coulomb (L2C)UMR 5221 CNRS-Université de Montpellier34095Montpellier, France
Institut de Chimie Séparative de MarcouleUMR 5257 CEA-CNRS-UM2-ENSCM Site de MarcouleBat 426BP 1717130207Bagnols sur Cèze cedex, France

Abstract

We studied the oxygen etching of individual single-walled carbon nanotubes on silicon oxide substrates using atomic force microscopy and high-temperature environmental scanning electron microscopy. Our in situ observations show that carbon nanotubes are not progressively etched from their ends, as frequently assumed, but disappear segment by segment. Atomic force microscopy, before and after oxidation, reveals that the oxidation of carbon nanotubes on substrates proceeds through a local cutting that is followed by a rapid etching of the disconnected nanotube segment. Unexpectedly, semiconducting nanotubes appear more reactive under these conditions than metallic ones. We also show that exposure to electron and laser beams locally increases the chemical reactivity of carbon nanotubes on such substrates. These results are rationalized by considering the effect of substrate-trapped charges on the nanotube density of states close to the Fermi level, which is impacted by the substrate type and the exposure to electron and laser beams.

Keywords: single-walled carbon nanotubes, environmental scanning electron microscopy, oxidative etching, substrate-trapped charges, electron and laser irradiations

References(58)

1

Dean, K. A.; Chalamala, B. R. The environmental stability of field emission from single-walled carbon nanotubes. Appl. Phys. Lett. 1999, 75, 3017-3019.
DOI Google Scholar
2

Bonard, J. -M.; Maier, F.; Stöckli, T.; Châtelain, A.; de Heer, W. A.; Salvetat, J. -P.; Forró, L. Field emission properties of multiwalled carbon nanotubes. Ultramicroscopy 1998, 73, 7-15.
DOI Google Scholar
3

Futaba, D. N.; Hata, K.; Yamada, T.; Mizuno, K.; Yumura, M.; Iijima, S. Kinetics of water-assisted single-walled carbon nanotube synthesis revealed by a time-evolution analysis. Phys. Rev. Lett. 2005, 95, 056104.
DOI Google Scholar
4

Nasibulin, A. G.; Brown, D. P.; Queipo, P.; Gonzalez, D.; Jiang, H.; Kauppinen, E. I. An essential role of CO2 and H2O during single-walled CNT synthesis from carbon monoxide. Chem. Phys. Lett. 2006, 417, 179-184.
DOI Google Scholar
5

Yu, B.; Liu, C.; Hou, P. X.; Tian, Y.; Li, S. S.; Liu, B. L.; Li, F.; Kauppinen, E. I.; Cheng, H. M. Bulk synthesis of large diameter semiconducting single-walled carbon nanotubes by oxygen-assisted floating catalyst chemical vapor deposition. J. Am. Chem. Soc. 2011, 133, 5232-5235.
DOI Google Scholar
6

Dillon, A. C.; Gennett, T.; Jones, K. M.; Alleman, J. L.; Parilla, P. A.; Heben, M. J. A simple and complete purification of single-walled carbon nanotube materials. Adv. Mater. 1999, 11, 1354-1358.
DOI
7

Wiltshire, J. G.; Khlobystov, A. N.; Li, L. J.; Lyapin, S. G.; Briggs, G. A. D.; Nicholas, R. J. Comparative studies on acid and thermal based selective purification of HiPCO produced single-walled carbon nanotubes. Chem. Phys. Lett. 2004, 386, 239-243.
DOI Google Scholar
8

Zhang, G. Y.; Mann, D.; Zhang, L.; Javey, A.; Li, Y. M.; Yenilmez, E.; Wang, Q.; McVittie, J. P.; Nishi, Y.; Gibbons, J. et al. Ultra-high-yield growth of vertical single-walled carbon nanotubes: Hidden roles of hydrogen and oxygen. Proc. Natl. Acad. Sci. USA 2005, 102, 16141-16145.
DOI Google Scholar
9

Xu, Y. Q.; Peng, H. Q.; Hauge, R. H.; Smalley, R. E. Controlled multistep purification of single-walled carbon nanotubes. Nano Lett. 2005, 5, 163-168.
DOI Google Scholar
10

Chen, Z. Y.; Ziegler, K. J.; Shaver, J.; Hauge, R. H.; Smalley, R. E. Cutting of single-walled carbon nanotubes by ozonolysis. J. Phys. Chem. B 2006, 110, 11624-11627.
DOI Google Scholar
11

Yu, B.; Hou, P. X.; Li, F.; Liu, B. L.; Liu, C.; Cheng, H. M. Selective removal of metallic single-walled carbon nanotubes by combined in situ and post-synthesis oxidation. Carbon 2010, 48, 2941-2947.
DOI Google Scholar
12

Chiang, I. W.; Brinson, B. E.; Huang, A. Y.; Willis, P. A.; Bronikowski, M. J.; Margrave, J. L.; Smalley, R. E.; Hauge, R. H. Purification and characterization of single-wall carbon nanotubes (SWNTs) obtained from the gas-phase decomposition of CO (HiPco process). J. Phys. Chem. B 2001, 105, 8297-8301
DOI Google Scholar
13

Ajayan, P. M.; Ebbesen, T. W.; Ichihashi, T.; Iijima, S.; Tanigaki, K.; Hiura, H. Opening carbon nanotubes with oxygen and implications for filling. Nature 1993, 362, 522-525.
DOI Google Scholar
14

Tsang, S. C.; Harris, P. J. F.; Green, M. L. H. Thinning and opening of carbon nanotubes by oxidation using carbon dioxide. Nature 1993, 362, 520-522.
DOI Google Scholar
15

Dresselhaus, M. S.; Dresselhaus, G.; Eklund, P. C. Chapter 1-Historical introduction. In Science of Fullerenes and Carbon Nanotubes; Academic Press: San Diego, 1996; pp 1-14.
DOI Google Scholar
16

Saito, R.; Dresselhaus, G.; Dresselhaus, M. S. Physical Properties of Carbon Nanotubes; Imperial College Press: London, 1998; Vol. 3.
DOI
17

Cao, Q.; Rogers, J. A. Ultrathin films of single-walled carbon nanotubes for electronics and sensors: A review of fundamental and applied aspects. Adv. Mater. 2009, 21, 29-53.
DOI Google Scholar
18

Gabor, N. M.; Zhong, Z. H.; Bosnick, K.; Park, J.; McEuen, P. L. Extremely efficient multiple electron-hole pair generation in carbon nanotube photodiodes. Science 2009, 325, 1367-1371.
DOI Google Scholar
19

Allen, B. L.; Kichambare, P. D.; Star, A. Carbon nanotube field-effect-transistor-based biosensors. Adv. Mater. 2007, 19, 1439-1451.
DOI Google Scholar
20

Burghard, M.; Klauk, H.; Kern, K. Carbon-based field-effect transistors for nanoelectronics. Adv. Mater. 2009, 21, 2586-2600.
DOI Google Scholar
21

Lolli, G.; Zhang, L.; Balzano, L.; Sakulchaicharoen, N.; Tan, Y. Q.; Resasco, D. E. Tailoring (n, m) structure of single-walled carbon nanotubes by modifying reaction conditions and the nature of the support of CoMo catalysts. J. Phys. Chem. B 2006, 110, 2108-2115.
DOI Google Scholar
22

Li, X. L.; Tu, X. M.; Zaric, S.; Welsher, K.; Seo, W. S.; Zhao, W.; Dai, H. J. Selective synthesis combined with chemical separation of single-walled carbon nanotubes for chirality selection. J. Am. Chem. Soc. 2007, 129, 15770-15771.
DOI Google Scholar
23

Miyata, Y.; Kawai, T.; Miyamoto, Y.; Yanagi, K.; Maniwa, Y.; Kataura, H. Chirality-dependent combustion of single-walled carbon nanotubes. J. Phys. Chem. C 2007, 111, 9671-9677.
DOI Google Scholar
24

Borowiak-Palen, E.; Pichler, T.; Liu, X.; Knupfer, M.; Graff, A.; Jost, O.; Pompe, W.; Kalenczuk, R. J.; Fink, J. Reduced diameter distribution of single-wall carbon nanotubes by selective oxidation. Chem. Phys. Lett. 2002, 363, 567-572.
DOI Google Scholar
25

Nagasawa, S.; Yudasaka, M.; Hirahara, K.; Ichihashi, T.; Iijima, S. Effect of oxidation on single-wall carbon nanotubes. Chem. Phys. Lett. 2000, 328, 374-380.
DOI Google Scholar
26

Zhou, W. W.; Zhan, S. T.; Ding, L.; Liu, J. General rules for selective growth of enriched semiconducting single walled carbon nanotubes with water vapor as in situ etchant. J. Am. Chem. Soc. 2012, 134, 14019-14026.
DOI Google Scholar
27

Zhang, G. Y.; Qi, P. F.; Wang, X. R.; Lu, Y. R.; Li, X. L.; Tu, R.; Bangsaruntip, S.; Mann, D.; Zhang, L.; Dai, H. J. Selective etching of metallic carbon nanotubes by gas-phase reaction. Science 2006, 314, 974-977.
DOI Google Scholar
28

Yang, C. M.; An, K. H.; Park, J. S.; Park, K. A.; Lim, S. C.; Cho, S. H.; Lee, Y. S.; Park, W.; Park, C. Y.; Lee, Y. H. Preferential etching of metallic single-walled carbon nanotubes with small diameter by fluorine gas. Phys. Rev. B 2006, 73, 075419.
DOI Google Scholar
29

Zhang, H. L.; Liu, Y. Q.; Cao, L. C.; Wei, D. C.; Wang, Y.; Kajiura, H.; Li, Y. M.; Noda, K.; Luo, G. F.; Wang, L. et al. A facile, low-cost, and scalable method of selective etching of semiconducting single-walled carbon nanotubes by a gas reaction. Adv. Mater. 2009, 21, 813-816.
DOI Google Scholar
30

Miyata, Y.; Maniwa, Y.; Kataura, H. Selective oxidation of semiconducting single-wall carbon nanotubes by hydrogen peroxide. J. Phys. Chem. B 2006, 110, 25-29.
DOI Google Scholar
31

Hodge, S. A.; Bayazit, M. K.; Coleman, K. S.; Shaffer, M. S. P. Unweaving the rainbow: A review of the relationship between single-walled carbon nanotube molecular structures and their chemical reactivity. Chem. Soc. Rev. 2012, 41, 4409-4429.
DOI Google Scholar
32

Kawai, T.; Miyamoto, Y. Chirality-dependent C-C bond breaking of carbon nanotubes by cyclo-addition of oxygen molecule. Chem. Phys. Lett. 2008, 453, 256-261.
DOI Google Scholar
33

Moon, C. Y.; Kim, Y. S.; Lee, E. C.; Jin, Y. G.; Chang, K. J. Mechanism for oxidative etching in carbon nanotubes. Phys. Rev. B 2002, 65, 155401.
DOI Google Scholar
34

An, K. H.; Park, J. S.; Yang, C.; Jeong, S. Y.; Lim, S. C.; Kang, C.; Son, J.; Jeong, M. S.; Lee, Y. H. A diameter-selective attack of metallic carbon nanotubes by nitronium ions. J. Am. Chem. Soc. 2005, 127, 5196-5203.
DOI Google Scholar
35

Ye, J. T.; Tang, Z. K. Raman spectra and thermal stability analysis of 0.4 nm freestanding single-walled carbon nanotubes. Phys. Rev. B 2005, 72, 045414.
DOI Google Scholar
36

Kroes, J. M. H.; Pietrucci, F.; Curioni, A.; Jaafar, R.; Gröning, O.; Andreoni, W. Atomic oxygen chemisorption on carbon nanotubes revisited with theory and experiment. J. Phys. Chem. C 2013, 117, 1948-1954.
DOI Google Scholar
37

Doyle, C. D.; Rocha, J. D. R.; Weisman, R. B.; Tour, J. M. Structure-dependent reactivity of semiconducting single-walled carbon nanotubes with benzenediazonium salts. J. Am. Chem. Soc. 2008, 130, 6795-6800.
DOI Google Scholar
38

Yamamoto, M.; Einstein, T. L.; Fuhrer, M. S.; Cullen, W. G. Charge inhomogeneity determines oxidative reactivity of graphene on substrates. ACS Nano 2012, 6, 8335-8341.
DOI Google Scholar
39

Zhou, W. W.; Rutherglen, C.; Burke, P. J. Wafer scale synthesis of dense aligned arrays of single-walled carbon nanotubes. Nano Res. 2008, 1, 158-165.
DOI Google Scholar
40

Zhang, L. J.; Gao, F. L.; Huang, S. M. The imaging mechanism of single-walled carbon nanotubes on Si/SiO2 wafer in scanning electron microscopy. J. Micros. 2011, 241, 188-194.
DOI Google Scholar
41

Li, J.; He, Y. J.; Han, Y. M.; Liu, K.; Wang, J. P.; Li, Q. Q.; Fan, S. S.; Jiang, K. L. Direct identification of metallic and semiconducting single-walled carbon nanotubes in scanning electron microscopy. Nano Lett. 2012, 12, 4095-4101.
DOI Google Scholar
42

Javey, A.; Guo, J.; Paulsson, M.; Wang, Q.; Mann, D.; Lundstrom, M.; Dai, H. J. High-field quasiballistic transport in short carbon nanotubes. Phys. Rev. Lett. 2004, 92, 106804.
DOI Google Scholar
43

Javey, A.; Guo, J.; Farmer, D. B.; Wang, Q.; Yenilmez, E.; Gordon, R. G.; Lundstrom, M.; Dai, H. J. Self-aligned ballistic molecular transistors and electrically parallel nanotube arrays. Nano Lett. 2004, 4, 1319-1322.
DOI Google Scholar
44

Chu, X.; Schmidt, L. D. Reactions of NO, O2, H2O, and CO2 with the basal plane of graphite. Surf. Sci. 1992, 268, 325-332.
DOI Google Scholar
45

Smith, B. W.; Luzzi, D. E. Electron irradiation effects in single wall carbon nanotubes. J. Appl. Phys. 2001, 90, 3509-3515.
DOI Google Scholar
46

Warner, J. H.; Schäffel, S.; Zhong, G. F.; Rümmeli, M. H.; Büchner, B.; Robertson, J.; Briggs, G. A. D. Investigating the diameter-dependent stability of single-walled carbon nanotubes. ACS Nano 2009, 3, 1557-1563.
DOI Google Scholar
47

Rau, E. I.; Fakhfakh, S.; Andrianov, M. V.; Evstafeva, E. N.; Jbara, O.; Rondot, S.; Mouze, D. Second crossover energy of insulating materials using stationary electron beam under normal incidence. Nucl. Instrum. Methods Phys. Res., Sect. B 2008, 266, 719-729.
DOI Google Scholar
48

Joo, J.; Chow, B. Y.; Jacobson, J. M. Patterning on insulating substrates by critical energy electron beam lithography. Nano Lett. 2006, 6, 2021-2015.
DOI Google Scholar
49

Liu, L.; Ryu, S.; Tomasik, M. R.; Stolyarova, E.; Jung, N.; Hybertsen, M. S.; Steigerwald, M. L.; Brus, L. E.; Flynn, G. W. Graphene oxidation: Thickness-dependent etching and strong chemical doping. Nano Lett. 2008, 8, 1965-1970.
DOI Google Scholar
50

Martin, J.; Akerman, N.; Ulbricht, G.; Lohmann, T.; Smet, J. H.; von Klitzing, K.; Yacoby, A. Observation of electron-hole puddles in graphene using a scanning single-electron transistor. Nat. Phys. 2008, 4, 144-148.
DOI Google Scholar
51

Zhang, Y. B.; Brar, V. W.; Girit, C.; Zettl, A.; Crommie, M. F. Origin of spatial charge inhomogeneity in graphene. Nat. Phys. 2009, 5, 722-726.
DOI Google Scholar
52

Deal, B. E. Standardized terminology for oxide charges associated with thermally oxidized silicon. J. Electrochem. Soc. 1980, 127, 979-981.
DOI Google Scholar
53

Mack, S.; Wolf, A.; Brosinsky, C.; Schmeisser, S.; Kimmerle, A.; Saint-Cast, P.; Hofmann, M.; Biro, D. Silicon surface passivation by thin thermal oxide/PECVD layer stack systems. IEEE J. Photovolt. 2011, 1, 135-145.
DOI Google Scholar
54

Biercuk, M. J.; Ilani, S.; Marcus, C. M.; McEuen, P. L. Electrical transport in single-wall carbon nanotubes. In Carbon Nanotubes, Topics in Applied Physics; Jorio, A.; Dresselhaus, G.; Dresselhaus, M. S., Eds.; Springer-Verlag: Berlin Heidelberg, 2008; pp 455-493.
DOI
55

Kim, Y. D.; Bae, M. -H.; Seo, J. -T.; Kim, Y. S.; Kim, H.; Lee, J. H.; Ahn, J. R.; Lee, S. W.; Chun, S. -H.; Park, Y. D. Focused-laser-enabled p-n junctions in graphene field-effect transistors. ACS Nano 2013, 7, 5850-5857.
DOI Google Scholar
56

Harutyunyan, A. R.; Chen, G. G.; Paronyan, T. M.; Pigos, E. M.; Kuznetsov, O. A.; Hewaparakrama, K.; Kim, S. M.; Zakharov, D.; Stach, E. A.; Sumanasekera, G. U. Preferential growth of single-walled carbon nanotubes with metallic conductivity. Science 2009, 326, 116-120.
DOI Google Scholar
57

Schneider, G. F.; Calado, V. E.; Zandbergen, H.; Vandersypen, L. M. K.; Dekker, C. Wedging transfer of nanostructures. Nano Lett. 2010, 10, 1912-1916.
DOI Google Scholar
58

Podor, R.; Pailhon, D.; Ravaux, J.; Brau, H. -P. Development of an integrated thermocouple for the accurate sample temperature measurement during high temperature environmental scanning electron microscopy (HT-ESEM) experiments. Microsc. Microanal. 2015, 21, 307-312.
DOI Google Scholar
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Publication history
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Acknowledgements

Publication history

Received: 04 September 2015
Revised: 26 October 2015
Accepted: 29 October 2015
Published: 10 December 2015
Issue date: February 2016

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2015

Acknowledgements

Acknowledgements

This work was supported by European Office of Aerospace Research and Development (EOARD) and United States Air Force (USAF) (No. FA8655-12-1-2059).

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