Synthesis of well-aligned thin multiwalled carbon nanotubes on the silicon substrate and their field emission properties
Synthesis of well-aligned thin multiwalled carbon nanotubes on the silicon substrate and their field emission properties
Carbon letters. 2011. Dec, 12(4): 218-222
Copyright ©2011, Korean Carbon Society
This is an Open Access article distributed under the terms of the Creative Commons Attribution Non-Commercial License ( which permits unrestricted non-commercial use, distribution, and reproduction in any medium, provided the original work is properly cited.
  • Received : September 20, 2011
  • Accepted : November 26, 2011
  • Published : December 30, 2011
Export by style
Cited by
About the Authors
Huajun, Yuan
Dong Hoon, Shin
Bawl, Kim
Cheol Jin, Lee

Well-aligned multi-walled carbon nanotubes (MWCNTs) were successfully synthesized by catalytic chemical vapor deposition using a hydrogen sulfide (H 2 S) additive onto Al/Fe thin film deposited on Si wafers. Transmission electron microscopy images indicated that the as-grown carbon products were thin MWCNTs with small outer diameters of less than 10 nm. H 2 S plays a key role in synthesizing thin MWCNTs with a large inside hollow core. The well-aligned thin MWCNTs showed a low turn-on voltage of about 1.1 V/μm at a current density of 0.1 μA/cm 2 and a high emission current of about 1.0 mA/cm 2 at a bias field of 2.3 V/μm. We suggest a possible growth mechanism for the well-aligned thin MWCNTs with a large inside hollow core.
1. Introduction
Since the discovery of multi-walled carbon nanotubes (MWCNTs) [1] , CNTs have been synthesized with various methods such as arc discharge [2 , 3] , laser vaporization [4] , and chemical vapor deposition (CVD) [5 - 17] . Among various synthesis methods, the CVD technique has an advantage because it can control the diameter, the length, and the structure of CNTs through various process parameters. It is well known that aligned CNTs are important for a number of applications, such as field emission display and sensors. Aligned CNTs were grown on iron oxide particles embedded in mesoporous silica at 600℃ [5] . Subsequently, aligned CNTs were grown by plasma CVD [11 - 14] or thermal CVD [ 6 - 9 , 15 - 19] . Most of the synthesized MWCNTs had thick diameters of 30 to 50 nm.
Recently, the addition of sulfur was found to be effective in promoting the growth and yield of single-walled carbon nanotubes (SWCNTs) and double-walled carbon nanotubes(DWCNTs) [20 - 23] . More recently, vertically aligned SWCNT film was grown by thermal CVD using ethanol decomposition over a mono-dispersed Co-Mo catalyst on quartz substrates [24 , 25] , and water-stimulated enhanced catalytic activity resulted in massive growth of superdense and vertically aligned SWCNT forests with heights up to 2.5 mm [26] . However, there were no reports on the synthesis of well-aligned thin MWCNTs on the substrate. We consider that thin MWCNTs can promise good field emission properties similar to SWCNTs but indicate better emission stability compared with SWCNTs.
In this paper, we report that well-aligned MWCNTs with a thin diameter of about 10 nm were successfully synthesized by catalytic CVD (CCVD) onto Al/Fe thin films on Si wafers. We investigated that an addition of hydrogen sulfide (H 2 S) was found to be effective in increasing the growth rate of CNTs and inducing the vertical direction of CNT growth. Interestingly, the well-aligned thin MWCNTs indicated very a large inside hollow core compared with previous MWCNTs. The well-aligned thin MWCNTs showed good field emission properties and strong emission stability. We also suggest a possible growth mechanism for thin MWCNTs with a large inside hollow core.
Lager Image
Scanning electron microscopy (SEM) images of carbon nanotubes (CNTs) grown at different hydrogen sulfide (H2S) flow rates: (a) 15, (b) 30, (c) 50, (d) 80 sccm and the high magnified SEM images of CNTs grown at a H2S flow rate of 80 sccm (e,f ).
2. Experimental
Well-aligned MWCNTs were successfully synthesized by CCVD on silicon substrate. The MWCNT growth was carried out on a quartz tube furnace with 20 mm diameter and 300 mm heating zone. Initially, Al (10 nm) and then Fe (1 nm) thin films were deposited onto the n-type Si (100) substrates using thermal evaporation. Pure Ar (99.9%), H 2 (99.9%), C 2 H 2 (99.99%), and H 2 S (1%, diluted by Ar) were used in this experiment. The substrates were placed in the center of the heating zone and the furnace was heated to a temperature of 800 o C under 1000 sccm Ar and 50 sccm H 2 at one atmosphere. The CNTs were synthesized at 800℃ with C 2 H 2 (30 sccm) and diluted H 2 S (0~80 sccm) flow under Ar/H 2 (1000/50 sccm) flow for 20 min. Scanning electron microscopy (SEM, S-4700, Hitachi, Japan), high-resolution transmission electron microscopy (HRTEM, H-9000, Hitachi, Ja-pan), and micro-Raman spectroscopy were used to characterize the CNTs. For Raman measurement, the 514.5 nm line of an Ar + laser was used as the excitation source. The emission current was monitored with a Keithley 6517A electrometer and recorded at 1.0 s intervals by applying a sweep step of 20 V.
3. Results and Discussion
Figs.1 a-d show the SEM images of the morphologies of as-grown CNTs on the Fe/Al thin film deposited on Si substrates according to diluted H 2 S flow rate. By supplying less than 15 sccm of diluted H 2 S to the reactor, the CNTs are laid down on the substrate as shown in Fig.1 a. However, the synthesized CNTs are well aligned on the substrate when over 30 sccm of the diluted H 2 S is introduced to the reactor. From SEM observation, after 20 min of reaction time, the lengths of carbon nanotubes
Lager Image
Transmission electron microscopy (TEM) image of as-grownthin multi-walled carbon nanotubes (MWCNTs) grown at a hydrogensulfide flow rate of 80 sccm (a,b) and high-resolution TEM images of thinMWCNTs with large inside hollow with five graphene layers (c) and threegraphene layers (d).
at 30, 50, and 80 sccm H 2 S flow rate are 45, 27, and 17 μm, respectively, as shown in Figs.1 b-d. Under a higher H 2 S flow rate of over 100 sccm, there was no appearance of carbon products on the substrate. Figs.1 e and f show the high-magnified SEM images of the well-aligned multiwalled CNTs, which indicate curly shaped high-purity CNTs. They show a uniform diameter of about 10 nm over the carbon filaments.
Figs. 2 a and b show the TEM images of the as-grown well-aligned MWCNTs after dispersion on a Cu grid. The synthesized carbon products reveal thin MWCNTs with diameters less than 10 nm. From HRTEM observation, besides thin MWCNTs with five grapheme layers ( Fig.2 c), we can see triple-walled CNTs ( Fig.2 d) with a very large inside hollow core. It is interesting to find thin MWCNTs with such a large inside hollow core from this work. We consider that this result may be related to the introduction of an H 2 S additive. Here, we used Al/Fe thin film deposited on Si wafers as a catalyst for CNT growth. When the substrate is heated to 800℃ in a CVD furnace, the Al layer melts and forms small droplets, which absorb the residual oxygen inside the furnace and oxidize quickly to form thermally stable Al 2 O 3 clusters. The formed Al 2 O 3 clusters provide the support for the formation of Fe nanoparticles, which catalyze the growth of the thin MWCNTs.
Sulfur has been found to play a key role in producing carbon filaments by the floating catalyst method and in enhancing the productivity of carbon fibers [27 , 28] . Low coverage of sulfur in the metal surface layers may favor carbon-carbon bond rupture and precipitation of the carbon filament [28] . Our experiments showed that optimal amounts of H 2 S additive are necessary to increase the growth rate of MWCNTs and to produce the well-aligned CNTs. In our experiments, the roles of H 2 S additive may be expressed by the following reactions:
Lager Image
Lager Image
Lager Image
In this reaction, we consider that the growth rate of CNTs largely increase because H 2 S can effectively remove amorphous carbon coating from catalysts (reaction 1). On the other hand, H 2 S additives can partly empoison the catalysts (reaction 2) and change catalyst surface morphology, which can reduce the number of catalytically active sites and would limit the growth direction of the carbon nanotubes. Therefore, well-aligned CNTs are easily synthesized when optimal amounts of H 2 S additive are used. However, H 2 S also might damage CNTs (reaction 3). To synthesize high quality aligned CNTs, the H 2 S partial pressure and the deposition time must be controlled. In general, sulfur can accelerate agglomeration of catalyst particles on the sub-strate, resulting in large sized catalyst particles. We believe that the thin MWCNTs with a large inside hollow core appear in this method. To understand details of the mechanism, further study is necessary. We believe that these thin MWCNT arrays with large inside hollow cores will be more promising in the hydrogen-storage application [29] or element filling application [30] .
Fig. 3 shows a typical Raman spectrum of the as-grown aligned CNTs excited by a 514.5 nm laser. The G-band and the D-band that indicate the tangential stretching mode are located at 1578 and 1335.2 cm -1 , respectively. Radial breathing modes (RBM) are also identified at the low frequency of the Raman spectrum. Four main RBM peaks (239.3, 253.3, 258.5, and 265.5 cm -1 ) identify that the produced carbon products contain a few SWCNTs or DWCNTs besides thin MWCNTs. We could find a few SWCNTs or DWCNTs from HRTEM observation besides thin MWCNTs sometimes.
Lager Image
A typical Raman spectrum of the as-grown well-aligned carbonnanotubes (CNTs). The inset indicates radial breathing modes showingthat the produced carbon materials contain a few single-walled CNTs ordouble-walled CNTs besides thin multi-walled CNTs.
Lager Image
Field emission properties of the well-aligned thin multi-walledcarbon nanotubes.
Fig. 4 shows the field emission properties for as-grown well-aligned thin MWCNTs as shown in Fig.1 d. Before the emission current measurement, we conducted electrical annealing to obtain stable field emission properties. After the electrical annealing process at the current density of about~1 mA/cm 2 for 1 h, we confirmed that the emission current was more stabilized. Fig.4 a illustrates the emission current density and corresponding Fowler-Nordheim (FN) plot. From Fig.4 a, the turn-on electric field (corresponding to the current density of 0.1 μA/cm 2 ) is about 1.1 V/μm and the emission current density is about 2.0 mA/cm 2 at an applied field of 2.7 V/μm, which indicates good field emission performance. We consider that the thin MWCNT array is useful to a field emitter in a flat panel display. The FN plot usually presented in the literature is also shown in the inset of Fig.4 a. The field enhancement factorβ can be calculated from the slope of the FN plot if the work function of the emitter is known. From the inset of Fig. 4 a, the calculated β values at higher and lower electric field regions are about 10 786 and 4217, respectively. Fig.4 b shows emission current stability from the as-grown MWCNT arrays during a long lifetime measurement. MWCNTs reveal stable emission current density over 20 h even though a little fluctuation of emission current appears due to the morphology of CNT tips. The thin MWCNTs promise good emission properties similar to SWCNTs while they indicate much better emission stability compared with SWCNTs.
4. Conclusions
In summary, we successfully synthesized well-aligned thin MWCNTs using a CCVD method with H 2 S additives. The as-grown carbon products indicated thin MWCNTs with diameters less than 10 nm, and they showed 5-7 graphene layers and a large inside hollow core compared with previous MWCNTs. The produced carbon products sometimes contain triple-walled CNTs and tetra-walled CNTs besides thin MWCNTs. The H 2 S additives increased the growth rate of MWCNTs and induced the vertical growth direction of MWCNTs. Moreover, H 2 S played a key role to form thin MWCNTs with a large inside hollow core. The turn-on voltage for the thin MWCNTs arrays was found to be about 1.1 V/μm at current density of 0.1 μA/cm 2 , and the emission current density arrays reached 2.0 mA/cm 2 at a bias field of 2.7 V/μm.
This work was supported by Center for Nanotubes and Nanostructured Composites at Sungkyunkwan Universi-ty (SKKU), by a grant (04K1501-03111) from ‘Center for Nanostructured Materials Technology’ under ‘21st Century Frontier R&D Programs’ of the Ministry of Science and Technology, Korea, and by a grant (R499-Th-ECO-NTRA) from US Air Force Office of Scientific Research.
Iijima S (1991) Helical microtubules of graphitic carbon Nature 354 56 -    DOI : 10.1038/354056a0
Bethune DS , Kiang CH , De Vries MS , Gorman G , Savoy R , Vazquez J , Beyers R (1993) Cobalt-catalysed growth of carbon nanotubes with single-atomic-layer walls Nature 363 605 -    DOI : 10.1038/363605a0
Journet C , Maser WK , Bernier P , Loiseau A , Lamy de la Chapelle M , Lefrant S , Deniard P , Lee R , Fischer JE (1997) Large-scale productionof single-walled carbon nanotubes by the electric-arc technique Nature 388 756 -    DOI : 10.1038/41972
Thess A , Lee R , Nikolaev P , Dai H , Petit P , Robert J , Xu C , Lee YH , Kim SG , Rinzler AG , Colbert DT , Scuseria GE , Tomanek D , Fischer JE , Smalley RE (1996) Crystalline ropes of metallic carbonnanotubes. Science 273 483 -    DOI : 10.1126/science.273.5274.483
Li WZ , Xie SS , Qian LX , Chang BH , Zou BS , Zhou WY , Zhao RA , Wang G (1996) Large-scale synthesis of aligned carbon nano-tubes Science 274 1701 -    DOI : 10.1126/science.274.5293.1701
Fan S , Chapline MG , Franklin NR , Tombler TW , Cassell AM , Dai H (1999) Self-oriented regular arrays of carbon nanotubes and theirfield emission properties Science 283 512 -    DOI : 10.1126/science.283.5401.512
Lee CJ , Kim DW , Lee TJ , Choi YC , Park YS , Lee YH , Choi WB , Lee NS , Park GS , Kim JM (1999) Synthesis of aligned carbon nanotubesusing thermal chemical vapor deposition Chem Phys Lett 312 461 -    DOI : 10.1016/S0009-2614(99)01074-X
Lee CJ , Park J (2001) Growth model for bamboolike structured carbonnanotubes synthesized using thermal chemical vapor deposition J Phys Chem B 105 2365 -    DOI : 10.1021/jp0032762
Rohmund F , Falk LKL , Campbell EEB (2000) A simple method for theproduction of large arrays of aligned carbon nanotubes Chem Phys Lett 328 369 -    DOI : 10.1016/S0009-2614(00)00996-9
Lee CJ , Lyu SC , Kim HW , Park CY , Yang CW (2002) Large-scale produc-tion of aligned carbon nanotubes by the vapor phase growth meth-od Chem Phys Lett 359 109 -    DOI : 10.1016/s0009-2614(02)00648-6
Ren ZF , Huang ZP (1998) Synthesis of large arrays of well-aligned car-bon nanotubes on glass Science 282 1105 -    DOI : 10.1126/science.282.5391.1105
Merkulov VI , Guillorn MA , Lowndes DH , Simpson ML , Voelkl E (2001) Shaping carbon nanostructures by controlling the synthe-sis process. Appl Phys Lett 79 1178 -    DOI : 10.1063/1.1395517
Merkulov VI , Melechko AV , Guillorn MA , Lowndes DH , Simp-son ML (2001) Alignment mechanism of carbon nanofibers produced by plasma-enhanced chemical-vapor deposition Appl Phys Lett 79 2970 -    DOI : 10.1063/1.1415411
Koehne J , Chen H , Li J , Cassell AM , Ye Q , Ng HT , Han J , Meyyappan M (2003) Ultrasensitive label-free DNA analysis using anelectronic chip based on carbon nanotube nanoelectrode arrays. Nanotechnology 14 1239 -    DOI : 10.1088/0957-4484/14/12/001
Mayne M , Grobert N , Terrones M , Kamalakaran R , Ruhle M , Kroto HW , Walton DRM (2001) Pyrolytic production of aligned carbonnanotubes from homogeneously dispersed benzene-based aerosols. Chem Phys Lett 338 101 -    DOI : 10.1016/s0009-2614(01)00278-0
Lee CJ , Son KH , Park J , Yoo JE , Huh Y , Lee JY (2001) Low temperature growth of vertically aligned carbon nanotubes by thermal chemicalvapor deposition. Chem Phys Lett 338 113 -    DOI : 10.1016/s0009-2614(00)01378-6
Lee CJ , Park J , Kang SY , Lee JH (2000) Growth and field electron emis-sionof vertically aligned multiwalled carbon nanotubes. ChemPhys Lett 326 175 -    DOI : 10.1016/S0009-2614(00)00751-X
Liu BC , Lee TJ , Lee SH , Park CY , Lee CJ (2003) Large-scale synthesis of high-purity well-aligned carbon nanotubes using pyrolysis of iron(II) phthalocyanine and acetylene Chem Phys Lett 377 55 -    DOI : 10.1016/s0009-2614(03)01092-3
Lee YT , Park J , Choi YS , Ryu H , Lee HJ (2002) Temperature-depen-dent growth of vertically aligned carbon nanotubes in the range 800-1100oC. J Phys Chem B 106 7614 -    DOI : 10.1021/jp020488l
Ci L , Rao Z , Zhou Z , Tang D , Yan X , Liang Y , Liu D , Yuan H , Zhou W , Wang G , Liu W , Xie S (2002) Double wall carbon nanotubes promoted by sulfur in a floating iron catalyst CVD system Chem Phys Lett 359 63 -    DOI : 10.1016/s0009-2614(02)00600-0
Song L , Ci L , Lv L , Zhou Z , Yan X , Liu D , Yuan H , Gao Y , Wang J , Liu L , Zhao X , Zhang Z , Dou X , Zhou W , Wang G , Wang C , Xie S Direct synthesis of a macroscale single-walled carbon nanotube non-woven material Adv Mater 16 1529 -    DOI : 10.1002/adma.200306393
Saito Y , Nakahira T , Uemura S (2003) Growth conditions of double-walled carbon nanotubes in arc discharge J Phys Chem B 107 931 -    DOI : 10.1021/jp021367o
Ago H , Komatsu T , Ohshima S , Kuriki Y , Yumura M (2000) Dispersion of metal nanoparticles for aligned carbon nanotube arrays. Appl PhysLett 77 79 -    DOI : 10.1063/1.126883
Murakami Y , Chiashi S , Miyauchi Y , Hu M , Ogura M , Okubo T , Maruyama S (2004) Growth of vertically aligned single-walled carbon nanotube films on quartz substrates and their optical anisotropy. Chem Phys Lett 385 298 -    DOI : 10.1016/j.cplett.2003.12.095
Maruyama S , Einarsson E , Murakami Y , Edamura T (2005) Growth process of vertically aligned single-walled carbon nanotubes. Chem Phys Lett 403 320 -    DOI : 10.1016/j.cplett.2005.01.031
Hata K , Futaba DN , Mizuno K , Namai T , Yumura M , Iijima S (2004) Water-assisted highly efficient synthesis of impurity-free single-walled carbon nanotubes. Science 306 1362 -    DOI : 10.1126/science.1104962
Tibbetts GG , Bernardo CA , Gorkiewicz DW , Alig RL (1994) Role of sul-fur in the production of carbon fibers in the vapor phase Carbon 32 569 -    DOI : 10.1016/0008-6223(94)90074-4
Kim MS , Rodriguez NM , Baker RTK (1993) The interplay between sul-fur adsorption and carbon deposition on cobalt catalysts J Catal 143 449 -    DOI : 10.1006/jcat.1993.1289
Dillon AC , Jones KM , Bekkedahl TA , Kiang CH , Bethune DS , He-ben MJ (1997) Storage of hydrogen in single-walled carbon nanotubes Nature 386 377 -    DOI : 10.1038/386377a0
Meyer RR , Sloan J , Dunin-Borkowsk RE , Kirkland AI , Novotny MC , Bailey SR , Hutchison JL , Green MLH (2000) Discrete atom imaging of one-dimensional crystals formed within single-walled carbon nanotubes. Science 289 1324 -    DOI : 10.1126/science.289.5483.1324