Facile synthesis 3D flexible core-shell graphene/glass fiber via chemical vapor deposition
© Yang et al.; licensee Springer. 2014
Received: 31 May 2014
Accepted: 20 July 2014
Published: 13 August 2014
Direct deposition of graphene layers on the flexible glass fiber surface to form the three-dimensional (3D) core-shell structures is offered using a two-heating reactor chemical vapor deposition system. The two-heating reactor is utilized to offer sufficient, well-proportioned floating C atoms and provide a facile way for low-temperature deposition. Graphene layers, which are controlled by changing the growth time, can be grown on the surface of wire-type glass fiber with the diameter from 30 nm to 120 um. The core-shell graphene/glass fiber deposition mechanism is proposed, suggesting that the 3D graphene films can be deposited on any proper wire-type substrates. These results open a facile way for direct and high-efficiency deposition of the transfer-free graphene layers on the low-temperature dielectric wire-type substrates.
81.05.U-; 81.07.-b; 81.15.Gh
KeywordsFlexible Graphene core-shell structure Two-heating reactor
Graphene as typical sp2 hybridized carbon has been attracting extensive scientific interest from both experimental and theoretical communities in the recent years. Graphene has been reported by numerous papers on the growth[1–6], properties[7, 8], and applications[9–11]. In most applications, such as supercapacitor, sensor, catalysis, battery, and water treatment applications, a small quantity of graphene is not sufficient; 2D graphene sheets with superior physical and electronic properties must be integrated into large-surface-area macroscopic three-dimensional (3D) carbon nanostructures[13–25]. Different carbon allotropes or complex compound structures, e.g., carbon nanotubes[13, 15], carbon nanofibers, graphene networks[14, 16, 17, 23], and carbon-based hybrid nanostructures[12, 25], have been used to prepare the 3D nanostructured carbon materials. Several fabrication approaches such as chemical or thermal reduction of graphene oxide[17, 18], hydrothermal carbonization, laser-based, and CVD approach have been reported for the preparation of carbonaceous nanostructures. Graphene films or composites (reduced graphene oxide r-GO,) have been traditionally grown by chemical or thermal reduction of graphene oxide exfoliated from low-cost graphite[17, 18]. The resulting r-GO, however, exhibits severely compromised conductivity due to the abundant defects, numerous non-ideal contacts between graphene sheets and functional moieties created during the synthesis procedures. In addition, this method is time-consuming due to the multi-step processes, including the high-temperature reduction process and a transfer process. The performance of graphene-based supercapacitors, sensors, and other devices is seriously limited by such shortcomings. These problems can potentially be overcome by the macroscopic CVD graphene-based foam (GF) structures. Three-dimensional architectures, with the continuous covalently bonded two-dimensional graphene building blocks, greatly reduce or eliminate the internal contact thermal resistance. The porous nature of this new-type 3D graphene material, with a large specific surface area (up to 850 m2 g-1), is also suitable to make functional composites by filling the pores with nanoparticles, polymers, or other functional materials. However, the CVD graphene foam, which is formed on the nickel or copper foam, requires an etching processes to be transferred onto a foreign substrate. The process remains expensive and time-consuming[14, 24, 25]. Herein, we report a simple two-heating reactor CVD method for the direct formation of self-assembled flexible 3D core-shell graphene/glass fiber. This method presents us a promising transfer-free technique for fabrication 3D graphene nanostructures. Our new method involves a single-step, lower-temperature (600°C), yet its properties including the conductivity are comparable to those of CVD graphene foam.
Following growth, the morphology of the sample was characterized with scanning electron microscope (SEM, Zeiss Gemini Ultra-55, Carl Zeiss, Inc., Oberkochen, Germany) and transmission electron microscope (TEM, JEM-2100 F, JEOL Ltd., Akishima-shi, Japan). Raman spectra were obtained with a HORIBA HR800 Raman microscopy system (HORIBA, Kyoto, Japan) (laser wavelength 473 nm and laser spot size about 0.5 mm). The resistance of the sample was measured by depositing the silver electrode on the surface.
Results and discussion
In our experiment, the lower-temperature (600°C) growth is necessary due to the lower melting point of the glass fiber, which can be obtained by the revised CVD system with the two-heating reactor. The mechanism of synthesis of core-shell graphene/glass fiber structures by using such revised CVD system has been discussed here. The higher constant-temperature zone offers enough power for the dissociation of methane with the assist of copper catalyst, and the lower constant-temperature zone makes that the decomposed carbon atoms deposit readily on the substrate. Meanwhile, the distinct form of the temperature variation effectively controls the regions that the evaporated Cu atoms and the decomposed carbon atoms deposit. The gently declined temperature zone can make the evaporated Cu atoms deposit on the region close to the higher constant-temperature zone. Higher-temperature (approximately 1,050°C) zone is required in our experiment. As is well known, thermal dissociation of methane is facile at temperatures above 1,000°C, and it is hard to proceed at the low temperature below 600°Χ, even though Cu catalyst is presented. The copper foil is used here to catalyze the methane thermal dissociation.
In fact, graphene growth on the plant SiO2 substrate are predominantly monolayer, due to the growth process is self-limited. As is well known, SiO2 has higher surface energy than after it is covered by graphene. Namely, the cohesion energy between SiO2 and graphene is higher than that of graphene-to-graphene. Therefore, after being covered by a layer of graphene, the carbon species become hard to nucleate on the graphene-covered area due to the relatively weak cohesion energy, refusing to form the second layer. But, one exception occurs at the defects where the dangling bonds give more opportunities for carbon adsorption to form the multilayer or many-layered graphene. For the glass fiber case, there are many overlaps and defects on the surface. From the EDX spectrum (shown in the inset of Figure 4c), there are also many metal element existed in the SiO2 wires. The metal elements existed in the SiO2 wires are caused by the formation of the glass membranes. All of the overlaps and defects can be used as the catalyst sites to further grow the graphene layers. From Figure 4c, many graphene layers have been covered on the overlaps of the glass fibers, which revealed that carbon species are easily nucleate on such areas.
We also measured the sheet resistance (Rs) of the prepared graphene film obtained at room temperature. The calculated average value of the Rs is approximately 700, 300, and 180 Ω/sq for the plant SiO2, SMF, and glass fiber membrane substrate. The excellent electrical properties further demonstrate that high-quality graphene layers can be prepared using such two-heating reactor CVD system in the relatively low temperature. The lower sheet resistance of the glass fiber membrane samples is caused by the more layers of the graphene films.
We have demonstrated the facile low-temperature growth of 3D graphene/glass fiber wire-type structures using a two-heating reactor. The higher constant-temperature zone offers enough power for the dissociation of methane with the assist of copper catalyst, and the lower constant-temperature zone makes that the decomposed carbon atoms deposit readily on the substrate. Graphene layers can be grown on the different diameter wire-type glass fiber surface to form graphene/glass fiber wire-type structures. The morphology and electrical properties of such structures can be controlled by changing the growth time. These results suggest that the 3D graphene films can be deposited on any proper wire-type substrates.
BM is a professor in the college of Physics and Electronics at Shandong Normal University, China. He is a Ph.D. supervisor. His main research interests include nanomaterials and laser plasma. CY has graduated from SungKyunKwan University (SKKU), Korea. Currently, he works at Shandong Normal University. His research subject is nanomaterials and their applications. YY, CZ, and ZS are currently doing their Ph.D. at Shandong Normal University. Their research subjects are related to 2D nanomaterials such as graphene, Bi2Se3, and MoS2. XL works in Lishan College at Shandong Normal University; her research focus is solar materials. SJ and CC are professors in the College of Physics and Electronics at Shandong Normal University. They are M.S. Supervisor. Their main interests include nanomaterials, mode-locked lasers, and laser plasma.
The authors are grateful for the financial support from the National Natural Science Foundation of China (11474187, 11274204, 61205174, and 61307120), Specialized research Fund for the Doctoral Program of Higher Education of China (20133704120008), Shandong Excellent Young Scientist Research Award Fund (BS2012CL034 and BS2013CL011), and Shandong Province Higher Educational Science and Technology Program (J12LA07).
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