Improved field emission stability from single-walled carbon nanotubes chemically attached to silicon
© Shearer et al.; licensee Springer. 2012
Received: 18 May 2012
Accepted: 16 July 2012
Published: 1 August 2012
Here, we demonstrate the simple fabrication of a single-walled carbon nanotube (SWCNT) field emission electrode which shows excellent field emission characteristics and remarkable field emission stability without requiring posttreatment. Chemically functionalized SWCNTs were chemically attached to a silicon substrate. The chemical attachment led to vertical alignment of SWCNTs on the surface. Field emission sweeps and Fowler-Nordheim plots showed that the Si-SWCNT electrodes field emit with a low turn-on electric field of 1.5 V μm−1 and high electric field enhancement factor of 3,965. The Si-SWCNT electrodes were shown to maintain a current density of >740 μA cm−2 for 15 h with negligible change in applied voltage. The results indicate that adhesion strength between the SWCNTs and substrate is a much greater factor in field emission stability than previously reported.
KeywordsSingle-walled carbon nanotubes Chemical attachment Field emission Field emission stability Nanoelectronics
Carbon nanotubes (CNTs) have a high aspect ratio and high electrical conductivity which make them prime candidates for field emission electrodes [1, 2]. The practical application of a CNT-based field emission device requires both a low turn-on electric field (Eto) and a stable output current . Single-walled carbon nanotubes (SWCNTs) are accepted to have excellent field emission properties including a low turn-on field and high electric field enhancement factor (β) since their small diameter provides the highest aspect ratio compared with multi-walled carbon nanotubes (MWCNTs) [4–6]. Conversely, field emission from SWCNTs is usually regarded to be fragile because the single-shelled SWCNTs are less resilient to emission degradation mechanisms such as ion bombardment and Joule heating. Recently, much work has focused upon improving the field emission properties of MWCNTs due to their inherent emission stability [7, 8]. Posttreatments to SWCNT films, such as plasma exposure, have been shown to significantly increase emission stability but at the cost of increasing Eto. Improving the emission stability from SWCNT electrodes without adversely affecting Eto and β is an ultimate goal in the field .
We have recently reported field emission from SWCNTs chemically attached to silicon and showed that these devices could withstand field emission current densities up to 500 μA cm−2 and were relatively stable, with the voltage required to maintain a current density of 95 μA cm−2 only increasing by 15% after 15 h and by 36% after 65 h . More recently, we investigated field emission properties and stability from functionalized single-, double-, and multi-walled CNTs chemically attached to silicon where we found that the degree of functionalization played a major role in emission stability .
Recent experiments on Si-SWCNT electrodes have shown that a 2-h attachment time yields superior photovoltaic and electrochemical devices [12–14]. The field emission stability of 2-h Si-SWCNT electrodes has not been previously investigated. In this letter, we improve significantly upon previous Si-SWCNT electrodes and demonstrate that the chemical attachment of SWCNTs to a silicon substrate is a simple route toward the fabrication of a SWCNT electrode with stable emission while maintaining excellent values for Eto and β.
Si-SWCNT electrodes were fabricated following the chemical attachment of functionalized SWCNTs as described in detail elsewhere . Briefly, n-type highly antimony-doped Si wafers were cut to 0.25 cm2 and cleaned ultrasonically in acetone for 2 min. The Si wafers were then hydroxylated by stepwise immersion in 1:1:5 NH4OH:H2O2:H2O followed by HCl:H2O2:H2O for 20 min at 80°C. The wafers were then incubated for 2 h in a solution of dimethyl sulfoxide containing 0.2 mg mL−1 carboxylic acid-functionalized SWCNTs and dicyclohexylcarbodiimide . The Si-SWCNT wafers were then washed ultrasonically for 2 min and dried in a stream of nitrogen. Field emission measurements were collected using a parallel plate setup with Si-SWCNT electrodes as the cathode and a stainless steel disk as the anode separated by 1.82 mm as determined by a micrometer screw . All measurements were taken using a LabVIEW-controlled Keithley source measure unit (Keithley Instruments Inc., Cleveland, OH, USA). The base pressure of the field emission testing system was <1 × 10−8 Torr.
Results and discussion
The low Eto and high value for β demonstrate that the Si-SWCNT electrode is an elite field emission device [3, 6, 11, 21, 22]. The measured values are perhaps surprising given the short length and wide bundle diameter of the SWCNTs as determined by AFM. We hypothesize that by using a solution containing SWCNTs with a variety of lengths, we have produced a surface whereby the electrical field screening between SWNTs is minimal, leading to the excellent field emission characteristics observed . Indeed, this hypothesis is supported by Chhowalla et al. who showed that short and stubby CNTs outperformed taller and thinner CNTs . They argued that electrical field screening between adjacent CNTs was reduced when the CNT forest did not have a uniform height and the CNTs had a greater spacing.
For t < 0.5 h, the field emission is relatively unstable with both V and J fluctuating as a function of time, which is consistent with previous observations  and is most probably related to field-induced desorption of adsorbates, causing fluctuations in both the work function and β [26–28].
For 0.5 < t < 2.5 h, V is essentially constant while J increases to 770 μA cm−2 at t = 2.5 h. This observation is consistent with a decrease in sample resistance due to the removal of amorphous carbon or non-emitting SWCNTs, resulting in improved field emission .
For 2.5 < t < 15, J remains constant while V increases slowly from 5,500 V to approximately 5,700 V at t = 15 h, which is consistent with slow degradation of the field emission properties of the SWCNT film most likely due to ion bombardment and Joule heating processes [27–30].
A total voltage change of 1.8% over 15 h for an applied current of approximately 750 μA cm−2 is very low for a SWCNT field-emitting electrode. The only SWCNT electrode in the literature with greater stability was a screen-printed SWCNT electrode that was treated with an Xe/Ne plasma to improve stability to the point where a current density of 100 μA cm−2 was maintained for >50 h with minimal degradation . However, the plasma treatment increased the Eto of the electrode from 2.9 V μm−1 to 4.3 V μm−1, effectively negating the advantages of using SWCNTs. Moreover, the output current density described here is over seven times greater with negligible field emission degradation observed.
The highly stable electron field emission at a relatively high J that is observed for the Si-SWCNT electrodes reported in this letter is attributed to a number of factors. First, the strong chemical attachment between the SWCNTs and the substrate will reduce the occurrence of field-induced CNT desorption, resulting in a more consistent field emission. Second, the bundling of the SWCNTs on the surface may also assist with the observed low degradation, with the outermost SWCNTs protecting the inner SWCNTs from ion bombardment. Third, as we have previously shown, the high crystallinity of these SWCNTs improves emission stability . Finally, we propose that variation in the length of the emitting structures results in low electric field screening of the surface and a concomitant large population of emitting SWCNTs, leading to a high field emission current density .
In summary, a field-emitting electrode consisting of SWCNTs chemically attached to a silicon substrate has been produced. The Si-SWCNT electrode was shown to field emit with an Eto of 1.5 V μm−1 and β of 3,965. The emission was shown to be remarkably stable with a current of approximately 750 μA cm−2 maintained for 15 h with a net voltage increase of only 1.8%. The chemical attachment of SWCNTs to Si is a simple, upscalable approach to produce SWCNT field emission electron sources with excellent characteristics and stability without the need for posttreatment.
This work was funded by Flinders University, Westfälische Wilhelms-Universität Münster, University of Newcastle and the Australian Research Council.
1Institut für Physikalische Chemie, Westfälische Wilhelms-Universität Münster, Münster 48149, Germany. 2Flinders Centre for Nanoscale Science and Technology, School of Chemical and Physical Sciences, Flinders University, Bedford Park, Adelaide 5042, Australia. 3Centre for Organic Electronics, School of Physics, University of Newcastle, Callaghan, Newcastle 2308, Australia.
- Wei BQ, Vajtai R, Ajayan PM: Reliability and current carrying capacity of carbon nanotubes. Appl Phys Lett 2001, 79: 1172. 10.1063/1.1396632View Article
- Bonard JM, Kind H, Stokli T, Nilsson L-O: Field emission from carbon nanotubes: the first five years. Solid State Electron 2001, 45: 893–914. 10.1016/S0038-1101(00)00213-6View Article
- de Jonge N, Bonard J-M: Carbon nanotube electron sources and applications. Philos Trans R Soc London, Ser A 2004, 362: 2239–2266. 10.1098/rsta.2004.1438View Article
- Bonard JM, Salvetat J-P, Stokli T, De Heer WA: Field emission from single-walled carbon nanotube films. Appl Phys Lett 1998, 73: 918. 10.1063/1.122037View Article
- Bonard JM, Croci M, Klinke C, Kurt R, Noury O, Weiss N: Carbon nanotube films as electron field emitters. Carbon 2002, 40: 1715–1728. 10.1016/S0008-6223(02)00011-8View Article
- Milne WI, Teo KBK, Amaratunga GAJ, Legagneux P, Gangloff L, Schnell JP, Semet V, Thien Binh V, Groening O: Carbon nanotubes as field emission sources. J Mater Chem 2004, 14: 933–943. 10.1039/b314155cView Article
- Hazra KS, Gigras T, Misra DS: Tailoring the electrostatic screening effect during field emission from hollow multiwalled carbon nanotube pillars. Appl Phys Lett 2011, 98: 123116. 10.1063/1.3565243View Article
- Li C, Zhang Y, Mann M, Hasko D, Lei W, Wang BP, Chu DP, Pribat D, Amaratunga GAJ, Milne WI: High emission current density, vertically aligned carbon nanotube mesh, field emitter array. Appl Phys Lett 2010, 97: 3.
- Kim WS, Lee J, Jeong TW, Heo JN, Kong BY, Jin YW, Kimb JM: Improved emission stability of single-walled carbon nanotube field emitters by plasma treatment. Appl Phys Lett 2005, 87: 163112. 10.1063/1.2099538View Article
- Shearer CJ, Shapter JG, Quinton JS, Dastoor PC, Thomsen L, O'Donnell KM: Highly resilient field emission from aligned single-walled carbon nanotube arrays chemically attached to n-type silicon. J Mater Chem 2008, 18: 5753–5760. 10.1039/b811546jView Article
- Shearer CJ, Fahy A, Barr MG, Moore KE, Dastoor PC, Shapter JG: Field emission from single-, double-, and multi-walled carbon nanotubes chemically attached to silicon. J Appl Phys 2012, 111: 044326–044328. 10.1063/1.3687363View Article
- Bissett MA, Shapter JG: Photocurrent response from vertically aligned single-walled carbon nanotube arrays. J Phys Chem C 2010, 114: 6778–6783. 10.1021/jp1003193View Article
- Flavel BS, Yu J, Shapter JG, Quinton JS: Patterned attachment of carbon nanotubes to silane modified silicon. Carbon 2007, 45: 2551–2558. 10.1016/j.carbon.2007.08.026View Article
- Flavel BS, Yu J, Shapter JG, Quinton JS: Electrochemical characterisation of patterned carbon nanotube electrodes on silane modified silicon. Electrochim Acta 2008, 53: 5653–5659. 10.1016/j.electacta.2008.03.022View Article
- Yu J, Shapter JG, Quinton JS, Johnston MR, Beattie DA: Direct attachment of well-aligned single-walled carbon nanotube architectures to silicon (100) surfaces: a simple approach for device assembly. Phys Chem Chem Phys 2007, 9: 510–520.View Article
- Liu Z, Shen Z, Zhu T, Hou S, Ying L: Organizing single-walled carbon nanotubes on gold using a wet chemical self-assembling technique. Langmuir 2000, 16: 3569–3573. 10.1021/la9914110View Article
- Yu J, Mathew S, Flavel BS, Johnston MR, Shapter JG: Ruthenium porphyrin functionalized single-walled carbon nanotube arrays-a step toward light harvesting antenna and multibit information storage. J Am Chem Soc 2008, 130: 8788–8796. 10.1021/ja801142kView Article
- Constantopoulos KT, Shearer CJ, Ellis AV, Voelcker NH, Shapter JG: Carbon nanotubes anchored to silicon for device fabrication. Adv Mater 2010, 22: 557–571. 10.1002/adma.200900945View Article
- Jonge N, Allioux M, Doytdcheva M, Kaiser M, Teo KBK, Lacerda RG, Milne WI: Characterization of the field emission properties of individual thin carbon nanotubes. Appl Phys Lett 2004, 85: 1607. 10.1063/1.1786634View Article
- Liu P, Sun Q, Zhu F, Liu K, Jiang K, Liu L, Li Q, Fan S: Measuring the work function of carbon nanotubes with thermionic method. Nano Lett 2008, 8: 647–651. 10.1021/nl0730817View Article
- Fang X, Bando Y, Gautam UK, Ye C, Golberg D: Inorganic semiconductor nanostructures and their field-emission applications. J Mater Chem 2008, 18: 509–522. 10.1039/b712874fView Article
- Fang Y, Wong KM, Lei Y: Synthesis and field emission properties of different ZnO nanostructure arrays. Nanoscale Res Lett 2012, 7: 197. 10.1186/1556-276X-7-197View Article
- Nilsson L, Groening O, Emmenegger C, Kuettel O, Schaller E, Schlapbach L, Kind H, Bonard JM, Kern K: Scanning field emission from patterned carbon nanotube films. Appl Phys Lett 2000, 76: 2071–2073. 10.1063/1.126258View Article
- Chhowalla M, Ducati N, Rupesinghe NL, Teo KBK, Aramatunga GAJ: Field emission from short and stubby vertically aligned carbon nanotubes. Appl Phys Lett 2001, 79: 2079–2081. 10.1063/1.1406557View Article
- Li C, Zhang Y, Mann M, Hiralal P, Unalan HE, Lei W, Wang BP, Chu DP, Pribat D, Amaratunga GAJ, Milne WI: Stable, self-ballasting field emission from zinc oxide nanowires grown on an array of vertically aligned carbon nanofibers. Appl Phys Lett 2010, 96: 3.
- Fahy A, Donnell KMO, Barr M, Zhou XJ, Allison W, Dastoor PC: Development of an improved field ionization detector incorporating a secondary electron stage. Meas Sci Technol 2011, 22: 115902. 10.1088/0957-0233/22/11/115902View Article
- O'Donnell KM, Fahy A, Barr M, Allison W, Dastoor PC: Field ionization detection of helium using a planar array of carbon nanotubes. Physical Review B 2012, 85: 113404.View Article
- Bormashov VS, Baturin AS, Nikolskiy KN, Tchesov RG, Sheshin EP: The current stability of field emission cathodes of carbon nanotubes under ion bombardment. Surf Interface Anal 2007, 39: 155–158. 10.1002/sia.2480View Article
- Purcell ST, Vincent P, Journet C, Binh VT: Hot nanotubes: stable heating of individual multiwall carbon nanotubes to 2000 K induced by the field-emission current. Phys Rev Lett 2002, 88: 105502.View Article
- Vincent P, Purcell ST, Journet C, Binh VT: Modelization of resistive heating of carbon nanotubes during field emission. Physical Review B 2002, 66: 075406.View Article
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