One-step growth of vertical graphene sheets on carbon nanotubes and their field emission properties

Jianlong Liu, Baoqing Zeng, Xiangru Wang, Wenzhong Wang, and Honglong Shi Citation: Appl. Phys. Lett. 103, 053105 (2013); doi: 10.1063/1.4816751 View online: http://dx.doi.org/10.1063/1.4816751 View Table of Contents: http://apl.aip.org/resource/1/APPLAB/v103/i5 Published by the AIP Publishing LLC.

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APPLIED PHYSICS LETTERS 103, 053105 (2013)

One-step growth of vertical graphene sheets on carbon nanotubes and their field emission properties
1 National Key Laboratory of Science and Technology on Vacuum Electronics, School of Physical Electronics, University of Electronic Science and Technology of China, Chengdu 610054, China 2 Department of Electronic Engineering, Zhongshan Institute, University of Electronic Science and Technology of China, Zhongshan 528402, China 3 School of Science, Minzu University of China, Beijing 100081, China

Jianlong Liu (),1 Baoqing Zeng (),1,2,a) Xiangru Wang (),1 Wenzhong Wang (),3 and Honglong Shi ()3

(Received 11 March 2013; accepted 10 July 2013; published online 29 July 2013) Graphene-carbon nanotube hybrid is prepared by an in situ growth of vertical graphene sheets on carbon nanotubes (CNTs), using one-step plasma-enhanced chemical vapor deposition, without catalyst. TEM analysis indicates that the growth of graphene is in accordance with the defects of carbon nanotubes introduced by high-energy ion bombardment in microwave plasma and expands by epitaxial growth. The results suggest that the method is ideal for preparing uniform graphenecarbon nanotube hybrid and demonstrate a categorical explanation for the growth mechanism of graphene-CNTs hybrid. Because of its uniform networks and multistage structure, the grapheneC 2013 AIP Publishing LLC. CNTs hybrid exhibits good eld emission properties. V [http://dx.doi.org/10.1063/1.4816751] Graphene has gained signicant research interest because of its unique physical properties originating from its two-dimensional (2D) structure. Furthermore, it is considered as a potential candidate for applications in energy storage and electrical devices owing to its high surface area and excellent conductivity.1,2 Despite these exceptional properties, the planar structure of graphene sheets (GSs) has the inherent limitation of agglomeration because of van der Waals forces, which tends to drastically decrease the surface area. However, comparing with graphene, carbon nanotubes (CNTs) have lower surface area. Nevertheless, the uniform one-dimensional (1D) structure of CNTs can hinder agglomeration better than GS. In order to combine the merits of the 2D GS and 1D CNTs, many attempts have been made to fabricate GSCNTs hybrid, with an aim to preserve the high surface area of GS using 1D CNTs as a matrix.3,4 However, these GSCNTs hybrids are conventionally prepared by mixing CNTs and GS, which hardly results in GS uniformly separated by CNTs. In reality, GSCNTs hybrid prepared by simple mixing CNTs and GS cannot be considered as an effective approach to overcome agglomeration. Therefore, it is of critical need to develop new synthesis methodologies that will enable the uniform growth of individual GS on CNTs network. So far, several synthesis methods, including mechanical exfoliation,5 chemical exfoliation6,7 and chemical vapor deposition (CVD),8 have been proposed for the preparation of GS. It has been realized that the GS synthesized by mechanical or chemical exfoliation has a planar structure, and depends on the structure of original graphite. Other method, such as thermal CVD, results in the growth of GS by planar catalyst at high temperature. Consequently, the structures of GS obtained by the methods mentioned above are limited on
a)

Author to whom correspondence should be addressed. Electronic mail: bqzeng@uestc.edu.cn. Tel.: 86-28-83200158. Fax: 86-28-83203371

in-plane shape, which is difcult to be designed for eld emission research. On the other hand, plasma-enhanced chemical vapor deposition (PECVD) is an intensively used technique for the growth of carbon nanotubes,9,10 GS, and related carbon naonostructure with good conductivity because of their high temperature growth condition. The catalytic PECVD provides possibility for the well controlled growth of CNTs or carbon nanobers (CNFs). However, carbon nanostructures synthesized via PECVD technique suffer from limitations, such as plasma etching, which results in defects and bamboo structures. Notably, free-standing GS can also be synthesized by PECVD on various substrates without catalyst.1114 Recently, reports indicated that GS can be made from unzipping the carbon nanotube15 or etching the top side walls of CNTs imbedded in polymer by argon plasma.16 Because this strategy relies on the conversion of GS from CNTs, the structure of GS depends on the structure of original CNTs. Moreover, because CNTs and GS share the same structure and growth conditions, it is reasonable to assume that it is possible to synthesize GSCNTs compatible structure17 by using PECVD. Intriguingly, another interesting report indicated that the shorten cut single-wall carbon nanotube (SWCNT) can act as a template for elongation growth when catalyst was introduced. The cloned SWCNT grew from short segment with well dened diameter and chirality.18,19 This indicates the probable growth of GS on the defects of CNTs. Herein, we have made an innovative approach to synthesize GSCNTs hybrid by an in situ growth of GS on the defects of CNTs, without using catalyst during the PECVD. The resulting GSCNTs hybrid is composed of GS grown on uniform CNTs network, exhibiting high conductivity and multistage structure without agglomeration. Experiment was carried out with 5000 W2.45 GHz microwave plasma-enhanced chemical vapor deposition (MPECVD) system. Prior to the growth, 20 nm nickel layer
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was deposited on silicon substrates by sputtering as catalyst for growing the CNTs. First, hydrogen was used as protection gas and 500 W microwave power was applied to heat the substrate to 950  C. Then mixture gas composed of 200 sccm hydrogen and 100 sccm methane was induced to the reactor and kept the pressures at 1000 Pa. After that, the microwave power was switched at different condition and kept for 20 min as growth time. Substrates were put on a platform at the center of reaction cavity, where the electric eld was largest. In contrast with the sample put away from plasma,20 our samples were put in the center of plasma. To enhance the bombardment and make the defect, they were placed on the top of copper pillar. The plasma area was on the top of the pillar and made the violent bombardment on the sample. Scanning electron microscopy (SEM) was employed to examine the CNTs and the GS-CNTs hybrid. SEM images in Figs. 1(a) and 1(b) show the CNTs grown with 1000 W for 20 min. Because of the violent bombardment, the structure of CNTs is disordered and has a lot of defects. Comparing with the conventional method, our higher growth temperature makes the diameter of CNTs bigger. To introduce more defects on the CNTs, microwave power was increased to 1200 W for 20 min. Fig. 1(c) shows the CNTs/CNFs structure after growth. The methane decomposes faster with higher power plasma, which raises the growth speed and enlarges the diameter of CNTs/CNFs. The crimple of the CNTs/CNFs is due to the high bombardment and fast growing. Further increasing the microwave power to 1500 W, the grown structure is shown in Figs. 2(a) and 2(b). The structure of CNTs/CNFs does not obviously change, but the GS is partly covering on the surface of CNTs. It must be violent plasma that makes the bombardment and results the defects. When the defect appears on the CNTs/CNFs, the intensive electric eld and continuous carbonic feedstock makes the GS grown in situ on the defects. It can be seen from Fig. 2(b)

FIG. 2. SEM images of GS-CNTs hybrid grown with different microwave power. (a), (b) 1500 W and (c), (d) 2000 W.

FIG. 1. SEM images of CNTs grown with different microwave power. (a), (b) 1000 W and (c), (d) 1200 W.

that the GS is rst grown on the corner of the crimple according to the defects, where the defects and amorphous carbon would more easily be removed by the plasma etching. While in other place, the CNTs had a little or no defect, and it is difcult to be destroyed by plasma etching in this level. Noteworthy, we did not nd the change of the coverage rate when the growth time is increased. To make a full coverage of GS on CNTs, the microwave power was increased to 2000 W. SEM images in Figs. 2(c) and 2(d) show the GS-CNTs hybrid has uniform networks and is fully covered by vertical GS. Comparing with the lower growth microwave power, the higher one has higher local electric eld intensity to make more defects during the growth. This high local electric eld intensity also makes the GS grown in situ on the defects of CNTs to form a uniform GS-CNTs hybrid. Since increasing the growth time could not change the GS coverage rate, we suggest the defects were not formed by bombarding the surface of CNTs after growing, but the intensive bombardment and etching made the CNTs grown with a lot of defects. The GS was rst grown on the defect and then made the epitaxial growth. This GS-CNTs hybrid was put in ethanol and ultrasonicated for 1 h, and then deposited on the substrate for transmission electron microscopy (TEM) measurement. TEM image in Fig. 3(a) shows the structure of CNTs/CNFs that has ordered walls of multiwalled CNTs (MWCNTs) with lots of defects. Fig. 3(b) shows the higher magnication image of section A and defects could be found on the wall of MWCNTs. These defects appear on the walls during the growth of CNTs because of the bombardment of local plasma. With high local electric eld and continuous carbonic feedstock, multilayered graphene sheets (MLGs) were grown in situ on the defects. Another high resolution TEM image from section B also shows, in Fig. 3(c), that bilayer graphene was rst grown on the defect from a double wall of CNTs. And then the bilayer graphene made epitaxial growth to turn 3 layer graphene (LG). This 3 LG kept growing and nally turn to 4 LG with a little disorder on the conjunction

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FIG. 3. TEM images of exfoliated GS. (a) Low magnication of CNTs/ CNFs with a lot of defects. (b) High magnication image of section A in (a), the MLG grown on the defect of MWCNTs. (c) High magnication image of section B in (a), the bilayer GS grows from defect turns to 3 layer GS and nally turns to 4 layer GS by epitaxial growth. (d) The epitaxial grown GS, from 11 layers to 14 layers.

during the growth, as shown in Fig. 4(b). The high-energy ion bombardment acts throughout the growth and makes the CNTs grown with a lot of defects, as shown in Fig. 4(c). With the high temperature and plentiful carbonic groups, the GS grow in situ on the defect of CNTs as a start. Without the catalyst on the defects, the graphene does not grow according to the structure of CNTs as before.18 Orientation of original graphene may depend on the local electric eld.13,14,21 When original graphene was formed on the defects, it not only makes epitaxial growth to increase the layers but also transversely stretches and expands, as shown in Fig. 4(d). After expanding, the thickness of GS is about several nanometers while the transversal size of GS has more than two orders of magnitude with several hundred nanometers, as shown in Fig. 2(d). So that the GS mainly makes the transversal expansion rather than thickness increase, and makes the full coverage on CNTs without agglomeration. Field emission is electron tunneling escape from the Fermi level when an external electric eld is applied. When specic structure of emitter is subjected to electric eld, the local electric eld would be enhanced by the geometry of the emitter and its surface morphology. Previous reports indicate that the enhancement factor would be dramatically increased by multistage geometry.2225 Due to the in situ growth at high temperature, this GS-CNTs hybrid would also have

because of the bombardment from local plasma. This point of view can also be proved in Fig. 3(d) that the GS had 11 LG during the growth, while the epitaxy made the GS turn to 14 LG at the end with a little disorder on the conjunction. Mechanism of growing this GS-CNTs hybrid is illustrated by the scheme in Fig. 4. Fig. 4(a) shows the structure of MWCNTs, which is composed of multilayer GS. When the substrate with catalyst was placed on the center of plasma, the CNTs grow with the help of catalyst. The plasma consists of high-energy ion and keeps bombarding the CNTs

FIG. 4. Schematic of GS-CNTs hybrid. (a) Model of MWCNTs consist of MLG. (b) CNTs are bombarded by high power ion from plasma during the growing duration. (c) The bombardment results in the defects on the CNTs. (d) Graphene grows in situ on the defects of CNTs and makes epitaxial growth to turn MLG.

FIG. 5. Field emission tests of GS and CNTs. (a) Emission current density of GS-CNTs hybrid and CNTs (b) corresponding F-N plot.

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PECVD without catalyst. With multistage structure and intrinsic low contact resistance in nature, this hybrid structure has good eld emission properties. This work was partially supported by NSFC (Grant Nos. 60071043 and 11074312), the Doctor Station Foundation of the Ministry of Education of China (Grant No. 200806140007), National Key Laboratory of Science and Technology on Vacuum Electronics, and the Fundamental Research Funds for the Central Universities.
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FIG. 6. Field emission stability tests of GS-CNTs hybrid.

good conductivity. With the good conductivity and multistage enhancement, this GS structure may have a good eld emission property. Field emission measurement was carried out with parallel electrodes in a high vacuum chamber. The diameter of anode was 2 mm. Distance between anode and cathode remained 400 lm. The vacuum was kept at about 6.0 107 Torr. Experimental results show that the eld emission properties of GS-CNTs hybrid are signicantly improved, as shown in Fig. 5(a). Field emission test indicates that the turn-on eld of CNTs grown with the same method is about 2.1 V/lm, and threshold-eld at 1 mA/cm2 was 3.2 V/lm. While for the GS-CNTs hybrid, the turn-on eld is 0.6 V/lm and the threshold-eld is 1.6 V/lm. This improvement is attributed in great deal to GS, which was grown in situ on the CNTs and results in multistage geometry enhancement. Corresponding FowlerNordheim (FN) plots are shown in Fig. 5(b). By assuming the work function of GS to be 5 eV, the enhancement factor for CNTs is calculated at 3670. The eld enhancement factor of GS-CNTs hybrid is 7710. Field emission stability test of GS-CNTs hybrid is also shown in Fig. 6. The eld emission is stable with only 8% decline after 10 h continuous emission. This may be due to the more emission sites for GS-CNTs hybrid, which act as emitters and share the emission current to make the emission stable. In summary, we demonstrate a GS-CNTs hybrid grown by high power microwave PECVD. The GS is grown in situ on the elaborately induced defects of CNTs by high energy ion bombardment of plasma. High resolution TEM indicates that the GS is grown according to the defect as a start and then makes epitaxial growth without catalyst. The GS mainly makes the transversal expand and uniformly covers on CNTs without agglomeration. This kind of evidence may also hint the mechanism of various graphene structure grown by

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