Improving field emission properties of vertically aligned carbon nanotube arrays through a structure modification

  • Arun Thapa
  • Katherine L. Jungjohann
  • Xuewen Wang
  • Wenzhi LiEmail author
Electronic materials


Vertically aligned carbon nanotube (VACNT) emitters were synthesized directly on stainless steel substrate using DC plasma-enhanced chemical vapor deposition. Remarkable field emission (FE) properties, such as low turn-on electric field (ETO = 1.40 V/μm) and low threshold electric field (ETH = 2.31 V/μm), were observed from VACNT arrays with long length and moderate density. The FE performance was significantly enhanced by a uniquely bundled structure of VACNTs formed through a simple water treatment process. The FE properties of VACNTs were further improved by coating the exterior of CNTs with a uniform layer of crystalline SnO2 nanoparticles; the ETO and ETH were reduced to 1.18 and 2.01 V/μm, respectively. The enhancement of FE properties by SnO2 coating can be attributed to the morphological change of VACNTs caused by the solution phase coating process. The coated samples also exhibited an improved FE stability which is attributed to the enhancement of the mechanical strength and chemical stability of the VACNTs after the SnO2 coating. The VACNT emitters with characteristic features such as a conductive substrate, low contact resistance between the VACNTs and the substrate, uniform coating, and bundled morphology can be ideal candidates for FE devices.



This work is supported by the National Science Foundation under grant DMR-1506640. This work was performed, in part, at the Center for Integrated Nanotechnologies, an Office of Science User Facility operated for the US Department of Energy (DOE) Office of Science. Sandia National Laboratories is a multi-mission laboratory managed and operated by National Technology and Engineering Solutions of Sandia, LLC., a wholly owned subsidiary of Honeywell International, Inc., for the US DOE’s National Nuclear Security Administration under contract DE-NA-0003525. This paper describes objective technical results and analysis. Any subjective views or opinions that might be expressed in the paper do not necessarily represent the views of the US Department of Energy or the US Government. The authors would also like to acknowledge the support from Advanced Materials Engineering Research Institutes (AMERI) at Florida International University.

Compliance with ethical standards

Conflict of interest

The authors declare that they have no conflict of interest.


  1. 1.
    Qian D, Wagner GJ, Liu WK, Yu MF, Ruoff RS (2002) Mechanics of carbon nanotubes. Appl Mech Rev 55(6):495–533CrossRefGoogle Scholar
  2. 2.
    Hone J, Llaguno MC, Biercuk MJ, Johnson AT, Batlogg B, Benes Z et al (2002) Thermal properties of carbon nanotubes and nanotube-based materials. Appl Phys A Mater Sci Process 74(3):339–343CrossRefGoogle Scholar
  3. 3.
    Bockrath M, Cobden DH, McEuen PL, Chopra NG, Zettl A, Thess A et al (1997) Single-electron transport in ropes of carbon nanotubes. Science 275(5308):1922–1925CrossRefGoogle Scholar
  4. 4.
    Poudel YR, Li W (2018) Synthesis, properties, and applications of carbon nanotubes filled with foreign materials: a review. Mater Today Phys 7:7–34CrossRefGoogle Scholar
  5. 5.
    Choi WB, Chung DS, Kang JH, Kim HY, Jin YW, Han IT et al (1999) Fully sealed, high-brightness carbon-nanotube field-emission display. Appl Phys Lett 75(20):3129–3131CrossRefGoogle Scholar
  6. 6.
    Baughman RH, Zakhidov AA, De Heer WA (2002) Carbon nanotubes—the route toward applications. Science 297(5582):787–792CrossRefGoogle Scholar
  7. 7.
    Yue GZ, Qiu Q, Gao B, Cheng Y, Zhang J, Shimoda H et al (2002) Generation of continuous and pulsed diagnostic imaging x-ray radiation using a carbon-nanotube-based field-emission cathode. Appl Phys Lett 81(2):355–357CrossRefGoogle Scholar
  8. 8.
    Milne WI, Teo KBK, Minoux E, Groening O, Gangloff L, Hudanski L et al (2006) Aligned carbon nanotubes/fibers for applications in vacuum microwave amplifiers. J Vacuum Sci Technol B Microelectron Nanometer Struct 24(1):345–348CrossRefGoogle Scholar
  9. 9.
    Li J, Papadopoulos C, Xu J (1999) Growing Y-junction carbon nanotubes. Nature 402:253–254CrossRefGoogle Scholar
  10. 10.
    Morassutto M, Tiggelaar RM, Smithers M, Gardeniers JG (2016) Vertically aligned carbon nanotube field emitter arrays with Ohmic base contact to silicon by Fe-catalyzed chemical vapor deposition. Mater Today Commun 7:89–100CrossRefGoogle Scholar
  11. 11.
    Talapatra S, Kar S, Pal SK, Vajtai R, Ci L, Victor P et al (2006) Direct growth of aligned carbon nanotubes on bulk metals. Nat Nanotechnol 1(2):112–116CrossRefGoogle Scholar
  12. 12.
    Neupane S, Yang Y, Li W, Gao Y (2014) Synthesis and enhanced electron field emission of vertically aligned carbon nanotubes grown on stainless steel substrate. J Nanosci Lett 4:14–20Google Scholar
  13. 13.
    Bonard JM, Weiss N, Kind H, Stöckli T, Forró L, Kern K, Chatelain A (2001) Tuning the field emission properties of patterned carbon nanotube films. Adv Mater 13(3):184–188CrossRefGoogle Scholar
  14. 14.
    Kim D, Lim SH, Guilley AJ, Cojocaru CS, Bourée JE, Vila L et al (2008) Growth of vertically aligned arrays of carbon nanotubes for high field emission. Thin Solid Films 516(5):706–709CrossRefGoogle Scholar
  15. 15.
    Hazra KS, Rai P, Mohapatra DR, Kulshrestha N, Bajpai R, Roy S et al (2009) Dramatic enhancement of the emission current density from carbon nanotube based nanosize tips with extremely low onset fields. ACS Nano 3(9):2617–2622CrossRefGoogle Scholar
  16. 16.
    Gupta BK, Kedawat G, Gangwar AK, Nagpal K, Kashyap PK, Srivastava S et al (2018) High-performance field emission device utilizing vertically aligned carbon nanotubes-based pillar architectures. AIP Adv 8(1):015117CrossRefGoogle Scholar
  17. 17.
    Wang K-Y, Liao C-Y, Cheng H-C (2016) Field-emission characteristics of the densified carbon nanotube pillars array. ECS J Solid State Sci Technol 5(9):M99–M103CrossRefGoogle Scholar
  18. 18.
    Li Z, Yang X, He F, Bai B, Zhou H, Li C et al (2015) High current field emission from individual non-linear resistor ballasted carbon nanotube cluster array. Carbon 89:1–7CrossRefGoogle Scholar
  19. 19.
    Li X, Niu J, Zhang J, Li H, Liu Z (2003) Labeling the defects of single-walled carbon nanotubes using titanium dioxide nanoparticles. J Phys Chem B 107:2453–2458CrossRefGoogle Scholar
  20. 20.
    Green JM, Dong L, Gutu T, Jiao J, Conley JF, Ono Y (2006) ZnO-nanoparticle-coated carbon nanotubes demonstrating enhanced electron field-emission properties. J Appl Phys 99(9):1–4CrossRefGoogle Scholar
  21. 21.
    Chen C-A, Lee K-Y, Chen Y-M, Chi J-G, Lin S-S, Huang Y-S (2010) Field emission properties of RuO2 thin film coated on carbon nanotubes. Vacuum 84(12):1427–1429CrossRefGoogle Scholar
  22. 22.
    Chakrabarti S, Pan L, Tanaka H, Hokushin S, Nakayama Y (2007) Stable field emission property of patterned MgO coated carbon nanotube arrays. Jpn J Appl Phys 46(7R):4364–4369CrossRefGoogle Scholar
  23. 23.
    Sreekanth M, Ghosh S, Barman SR, Sadhukhan P, Srivastava P (2018) Field emission properties of indium-decorated vertically aligned carbon nanotubes: an interplay between type of hybridization, density of states and metal thickness. Appl Phys A 124(8):528–536CrossRefGoogle Scholar
  24. 24.
    Sridhar S, Tiwary C, Vinod S, Taha-Tijerina JJ, Sridhar S, Kalaga K et al (2014) Field emission with ultralow turn on voltage from metal decorated carbon nanotubes. ACS Nano 8(8):7763–7770CrossRefGoogle Scholar
  25. 25.
    Suriani A, Dalila A, Mohamed A, Mamat M, Malek M, Soga T et al (2016) Fabrication of vertically aligned carbon nanotubes–zinc oxide nanocomposites and their field electron emission enhancement. Mater Des 90:185–195CrossRefGoogle Scholar
  26. 26.
    Thapa A, Neupane S, Guo R, Jungjohann KL, Pete D, Li W (2018) Direct growth of vertically aligned carbon nanotubes on stainless steel by plasma enhanced chemical vapor deposition. Diam Relat Mater 90:144–153CrossRefGoogle Scholar
  27. 27.
    Han W-Q, Zettl A (2003) Coating single-walled carbon nanotubes with tin oxide. Nano Lett 3(5):681–683CrossRefGoogle Scholar
  28. 28.
    Masarapu C, Wei B (2007) Direct growth of aligned multiwalled carbon nanotubes on treated stainless steel substrates 23(17):9046–9049Google Scholar
  29. 29.
    Bower C, Zhou O, Zhu W, Werder DJ, Jin S (2000) Nucleation and growth of carbon nanotubes by microwave plasma chemical vapor deposition. Appl Phys Lett 77(17):2767–2769CrossRefGoogle Scholar
  30. 30.
    Chhowalla M, Teo KBK, Ducati C, Rupesinghe NL, Amaratunga GAJ, Ferrari AC et al (2001) Growth process conditions of vertically aligned carbon nanotubes using plasma enhanced chemical vapor deposition. J Appl Phys 90(10):5308–5317CrossRefGoogle Scholar
  31. 31.
    Abadi PPSS, Maschmann MR, Hodson SL, Fisher TS, Baur JW, Graham S et al (2017) Mechanical behavior of carbon nanotube forests grown with plasma enhanced chemical vapor deposition: pristine and conformally coated. J Eng Mater Technol 139(3):034502CrossRefGoogle Scholar
  32. 32.
    Arjmand M, Chizari K, Krause B, Pötschke P, Sundararaj U (2016) Effect of synthesis catalyst on structure of nitrogen-doped carbon nanotubes and electrical conductivity and electromagnetic interference shielding of their polymeric nanocomposites. Carbon 98:358–372CrossRefGoogle Scholar
  33. 33.
    Jang JW, Lee CE, Lyu SC, Lee TJ, Lee CJ (2004) Structural study of nitrogen-doping effects in bamboo-shaped multiwalled carbon nanotubes. Appl Phys Lett 84(15):2877–2879CrossRefGoogle Scholar
  34. 34.
    Lau KK, Bico J, Teo KB, Chhowalla M, Amaratunga GA, Milne WI et al (2003) Superhydrophobic carbon nanotube forests. Nano Lett 3(12):1701–1705CrossRefGoogle Scholar
  35. 35.
    Mashayekhi A, Hosseini SM, Amiri MH, Namdar N, Sanaee Z (2016) Plasma-assisted nitrogen doping of VACNTs for efficiently enhancing the supercapacitor performance. J Nanopart Res 18(6):154–168CrossRefGoogle Scholar
  36. 36.
    Pandey A, Prasad A, Moscatello J, Ulmen B, Yap YK (2010) Enhanced field emission stability and density produced by conical bundles of catalyst-free carbon nanotubes. Carbon 48(1):287–292CrossRefGoogle Scholar
  37. 37.
    Zhang K, Li T, Ling L, Lu H, Tang L, Li C et al (2017) Facile synthesis of high density carbon nanotube array by a deposition-growth-densification process. Carbon 114:435–440CrossRefGoogle Scholar
  38. 38.
    Rudloff-Grund J, Brenker F, Marquardt K, Kaminsky F, Schreiber A (2016) STEM EDX nitrogen mapping of nanoinclusions in milky diamonds from Juina, Brazil, using a windowless silicon drift detector system. Anal Chem 88(11):5804–5808CrossRefGoogle Scholar
  39. 39.
    Barros E, Souza Filho A, Lemos V, Mendes Filho J, Fagan SB, Herbst M et al (2005) Charge transfer effects in acid treated single-wall carbon nanotubes. Carbon 43(12):2495–2500CrossRefGoogle Scholar
  40. 40.
    Wang Z, Chen G, Xia D (2008) Coating of multi-walled carbon nanotube with SnO2 films of controlled thickness and its application for Li-ion battery. J Power Sources 184(2):432–436CrossRefGoogle Scholar
  41. 41.
    Fan W, Gao L, Sun J (2006) Tin oxide nanoparticle-functionalized multi-walled carbon nanotubes by the vapor phase method. J Am Ceram Soc 89(8):2671–2673CrossRefGoogle Scholar
  42. 42.
    Jonge N, Allioux M, Doytcheva M, Kaiser M, Teo KBK, Lacerda RG et al (2004) Characterization of the field emission properties of individual thin carbon nanotubes. Appl Phys Lett 85(9):1607–1609CrossRefGoogle Scholar
  43. 43.
    Doytcheva M, Kaiser M, Verheijen MA, Reyes-Reyes M, Terrones M, de Jonge N (2004) Electron emission from individual nitrogen-doped multi-walled carbon nanotubes. Chem Phys Lett 396(1–3):126–130CrossRefGoogle Scholar
  44. 44.
    Brodie I, Spindt C (1992) Vacuum microelectronics. In: Hawkes PW (ed) Advances in electronics and electron physics. Elsevier, Amsterdam, pp 1–106Google Scholar
  45. 45.
    Gao R, Pan Z, Wang ZL (2001) Work function at the tips of multiwalled carbon nanotubes. Appl Phys Lett 78(12):1757–1759CrossRefGoogle Scholar
  46. 46.
    Kurilich MR, Thapa A, Moilanen A, Miller JL, Li W, Neupane S (2019) Comparative study of electron field emission from randomly-oriented and vertically-aligned carbon nanotubes synthesized on stainless steel substrates. J Vacuum Sci Technol B Nanotechnol Microelectron Mater Process Meas Phenom 37(4):041202Google Scholar
  47. 47.
    Pandey A, Prasad A, Moscatello JP, Yap YK (2010) Stable electron field emission from PMMA− CNT matrices. ACS Nano 4(11):6760–6766CrossRefGoogle Scholar
  48. 48.
    Chhowalla M, Ducati C, Rupesinghe NL, Teo KBK, Amaratunga GAJ (2001) Field emission from short and stubby vertically aligned carbon nanotubes. Appl Phys Lett 79(13):2079–2081CrossRefGoogle Scholar
  49. 49.
    Patra R, Ghosh S, Sharma H, Vankar VD (2013) High stability field emission from zinc oxide coated multiwalled carbon nanotube film. Adv Mater Lett 4(11):849–855Google Scholar
  50. 50.
    Xu J, Xu P, Ou-Yang W, Chen X, Guo P, Li J et al (2015) Outstanding field emission properties of wet-processed titanium dioxide coated carbon nanotube based field emission devices. Appl Phys Lett 106(7):073501CrossRefGoogle Scholar
  51. 51.
    Crespi VH, Chopra NG, Cohen ML, Zettl A, Louie SG (1996) Anisotropic electron-beam damage and the collapse of carbon nanotubes. Phys Rev B 54(8):5927–5931CrossRefGoogle Scholar
  52. 52.
    Zhang K, Stocks GM, Zhong J (2007) Melting and premelting of carbon nanotubes. Nanotechnology 18(28):285703CrossRefGoogle Scholar
  53. 53.
    Doytcheva M, Kaiser M, Jonge N (2006) In situ transmission electron microscopy investigation of the structural changes in carbon nanotubes during electron emission at high currents. Nanotechnology 17(13):3226–3233CrossRefGoogle Scholar
  54. 54.
    Bocharov G, Eletskii A (2013) Theory of carbon nanotube (CNT)-based electron field emitters. Nanomaterials 3(3):393–442CrossRefGoogle Scholar
  55. 55.
    Chen G, Neupane S, Li W, Chen L, Zhang J (2013) An increase in the field emission from vertically aligned multiwalled carbon nanotubes caused by NH3 plasma treatment. Carbon 52:468–475CrossRefGoogle Scholar

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© Springer Science+Business Media, LLC, part of Springer Nature 2019

Authors and Affiliations

  1. 1.Department of PhysicsFlorida International UniversityMiamiUSA
  2. 2.Center for Integrated NanotechnologiesSandia National LaboratoriesAlbuquerqueUSA

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