Synthesis and Characterization of Silicon Carbide (SiC) Microstructures

E. Thymour Legba Electrical and Computer Engineering Department, University of Kentucky, Lexington, KY Enagnon.Legba@uky.edu D. Patrick Hunley Department of Physical Sciences Morehead State University dphunl01@moreheadst.edu Nikki Olida Electrical Engineering Department Pennsylvannia State University npo104@psu.edu Ingrid St. Omer Electrical and Computer Engineering Department, University of Kentucky, Lexington, KY istomer@engr.uky.edu

Abstract
The purpose of this research was to synthesize and physically characterize silicon carbide microtubes. This was done by reacting silicon monoxide (SiO) powder with multi-walled carbon nanotubes (MWCNTs) at high temperature. Several experiments were conducted under vacuum in a high-temperature furnace varying temperature (1300C-1450C), time and reactant material mass. The resulting samples were then physically characterized using X-ray diffraction (XRD) and scanning electron microscopy (SEM). XRD analysis revealed the presence of dominant silicon carbide phases. SEM images revealed a unique morphology in comparison with the starting materials.

hexagonal sequences which repeat every 4 and 6 layers respectively. In general, all noncubic polytypes are collectively known as -SiC. Table 1 also highlights the attractive nature of SiC as a semiconducting material in comparison with silicon for high-temperature, high-power, high-frequency, and harsh-environmental applications. Table 1: Comparison of silicon and silicon carbide properties[1-3]. Youngs Band Thermal Knoop Conductivity Hardness Modulus Gap 2 (eV) (Watts/cm(kg/mm ) (GPa) C) SiC ~3.5 ~2480 ~430 2.9 3.2 Silicon 1.57 1150 129 1.10 187 Growth of SiC nanostructures has been achieved by several research groups. Morisada et. al. developed a process for coating multi-walled carbon nanotubes (MWCNTs) using SiO vapor.[4] The MWCNTs were placed inside of a covered alumina crucible and heated at different temperatures ranging from 1150 to 1550 C. Xray diffraction (XRD) patterns for the coated structures exhibited - and -SiC peaks as a function of temperature. An interesting feature of these results was the decline of the as-received MWCNT peaks, and the increase in SiC phases with increasing temperature. The focus of this work was the reinforcement of a WC-10wt.% Co matrix, and no electrical measurements were conducted. The study published by Sun et. al. reported the creation of SiC nanotubes and nanowires using CNTs as templates[5]. The CNTs were placed downstream of a crucible of SiO powder at various points along the length of the furnace. The range of temperatures at these positions was estimated to be 980 to 850 C using a calibration curve. The resulting structures were characterized using scanning
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1. Introduction
Silicon carbide (SiC) has been the focus of many microstructure research applications. It offers various excellent and useful mechanical, electrical and chemical properties. Its high thermal conductivity, mechanical hardness, resistance and chemical inertness give it the ability to function in high temperature and harsh environment applications. Therefore, it appears as a more attractive material than its traditional counterpart carbon nanotubes (CNT). On the macro scale, silicon carbide exists in several different crystal structures called polytypes. Although each polytype chemically consists of equal amounts of carbon atoms bonded covalently with silicon atoms, each polytype has a distinct set of electrical characteristics, as indicated by the wide ranges listed in Table 1. The most common silicon carbide polytypes presently in use for electronic devices are 3C-SiC, 4H-SiC, and 6H-SiC. These polytypes are identified by the stacking sequence of the siliconcarbon (Si/C) bilayers. The only cubic polytype, referred to as 3C- or -SiC, has 3 Si/C bilayers in its repeating periodic sequence. Both 4H-SiC and 6H-SiC are complex
1-4244-1029-0/07/$25.00 2007 IEEE.

electron microscopy (SEM), high-resolution transmission electron microscopy (HRTEM), electron energy loss spectroscopy (EELS), and elemental mapping. Using the interlayer spacings, the authors claim to have produced a new polytype of multi-walled SiCNT, in addition to -SiC nanowires. Other researchers also reported successful growth of -SiC nanotubes using SiO vapors and methodology comparable to Mo et. al. and Sun et. al.[6-8]

2. Experimental Methods
This work reports the successful fabrication of SiC microstructures based on thermal methods reported in the literature. Silicon carbide was synthesized through a gassolid reaction between MWCNTs and silicon monoxide vapor under vacuum at high temperature (1300C -1450C). Reaction between SiC and MWCNTs occurred according to the following reaction : SiO (gas) +2C (solid) SiC (solid) + CO (gas) Reactants were arranged inside an alumina crucible as shown in Figure 1. SiO powder (Aldrich -325mesh) was placed at the bottom of the alumina crucible, separated from the MWCNTs by a thin sheet of graphite felt (Alpha Aesar 99%). Loose MWCNTs (University of Kentucky Center for Advanced Energy Research) were positioned on the graphite felt. The assembled crucible was then placed in a Barnstead Thermolyne F54548CM high-temperature furnace. Pressure in the furnace was kept to approximately 60 mTorr during the fabrication process. Heating the SiO powder resulted in a vapor phase which diffused through the graphite felt to react with the MWCNTs and form SiC microtubes.

Table 2. Experimental conditions for preliminary work. Total time listed includes soak time and furnace ramp up/down times. Total Weight Temperature Time Time Color 4hrs SiO .852g 1300 C 3hrs 50mins Greenish CNTs .460g 6hrs BluishSiO .470g 1300 C 3hrs 17mins Greenish CNTs .270g 5hrs BrownishSiO .440g 1300 C 3hrs 10mins Blackish CNT .390g 6hrs BrownishSiO .400g 1300 C 5hrs 22mins Blackish CNT .290g 6hrs SiO .405g 1450 C 3hrs 37mins Grayish CNT .351g Grayish 8hrs with SiO .700g 1450 C 5hrs 35mins White CNT .365g 6hrs SiO .730g 1450 C 3hrs 28mins Grayish CNT .400g 8hrs Black, SiO .380g 1450 C 5hrs 34mins Brown, CNT .380g White The measurements were completed using a duration scan of 1.2 s and a small step scan of 0.02 from 10 to 90 2. Bulk silicon carbide materials are usually greenish or grayish in color. The samples prepared at 1300 C looked green but those that were prepared at 1450 C had a grey cast. Of the eight samples, only those samples prepared above 1300C exhibited any SiC phases, and two of the samples prepared at 1450C showed minimal - and significant - SiC phases. Increasing the growth time did not improve the XRD peaks as expected based on the results of others, and further investigation is warranted. The formation of SiC microtubes was found to be strongly dependent upon temperature and time. Higher temperatures and longer growth times generally increased the diameter of the SiC microtubes formed. The amount of SiC microtubes formed was also dependent on the amount of reactants. A typical X-ray spectrum is illustrated in Figure 2. The initial reactants were imaged on an S-3200 SEM to allow comparison with the reaction results. Figure 3 shows the morphology of the MWCNTs before reaction.

Carbon Nanotubes Carbon Felt Alumina Crucible Silicon Monoxide Powder

Figure 1: Schematic diagram of raw materials in alumina crucible. Temperature, time and weight of reactants were varied to find the optimum way of synthesizing SiC. A summary of the process parameters is illustrated in Table 2.

3. Characterization and Results

Physical characterization of the various samples was conducted using XRD (Bruker AXS D8 Discover). First the samples were crushed into powder using an agate mortar and pestle then placed onto a powder mount. The mount was then positioned into the machine for analysis.

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Figure 4. SEM image of SiO powder prior to reaction. Figure 2. XRD results for a sample prepared at 1450 C for a duration of 3 hours at temperature and a higher weight fraction of SiO. The five peak markers on the right highlight the dominant cubic phase.

Figure 5. Silicon carbide microrods after reaction at 1450 C for 3 hrs.

Figure 3. SEM image of MWCNTs prior to reaction. Figure 4 illustrates the morphology of the SiO powder before reaction. Figures 5 and 6 illustrate the resulting asgrown sample structures following reaction at 1450 C for a duration of 3 hours. The larger microstructures in Figure 5 appear to be the result of a comparable reaction between the fibers of the carbon felt and the silicon monoxide vapor. Results depicted in Figure 6, typical of the intended reaction with MWCNTs, appear larger in diameter than the original starting material. These samples were not calcinated in air as described by Keller et. al., thus any unreacted carbon remains.[8 ]

Figure 6. Material morphology present after hightemperature processing. Remnants of unreacted silicon monoxide powder are clearly visible.

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4. Conclusion
SiC microstructures were successfully fabricated in a series of experimental reactions using SiO powder and MWCNTs XRD analysis of the resulting material identified - and SiC phases, although the latter was dominant in all samples. SEM images indicated a corresponding change in the morphology of the samples. Additional research is in process to develop definitive correlations between process parameters and resulting morphology. Rmmeli et. al. have proposed a 5-state transition beginning with a SiC coating on the CNT, to SiC nanorod coated in C, to solid SiC nanorod, to porous SiC nanorod, and finally to hollow SiC nanostructure.[9] Our preliminary results did not agree with this time based model, however we have not yet conducted TEM studies. Further experiments will also explore reducing reactant residues, maximizing the amount of synthesized SiC, and establishing general electrical and mechanical properties of the synthesized SiC.

6. References
[1] M. N. Yoder, Diamond Films and Coatings: development, properties, and applications, R. F. Davis, Ed., Noyes Publications, Park Ridge, NJ, 1993. [2] J. C. Beam, High-Speed Semiconductor Devices, S. M. Sze, Ed., Wiley, New York, 1990. [3] P.G. Neudeck, The VLSI Handbook, The Electrical Engineering Handbook Series, W.-K. Chen, Ed., CRC Press and IEEE Press, Boca Raton, FL, 2000. [4]Y. Morisada and Y. Miayamoto, SiC-coated carbon nanotubes and their application as reinforcements for cemented carbides, Mater. Sci. Eng. A, 381 pp57-61 (2004). [5] X. Sun, C. Li, W. Wong, N. Wong, C. Lee, S. Lee, and B. Teo, Formation of Silicon Carbide Nanotubes and Nanowires via Reaction of Silicon (from Disproportionation of Silicon Monoxide) with Carbon Nanotubes, J. Am.Chem. Soc. 124 pp14464-14471 (2002). [6] Y. H. Mo, M. D. Shajahan, Y. S. Lee, Y. B. Hahn, and K. S. Nahm, Structural transformation of carbon nanotubes to silicon carbide nanorods or microcrystals by the reaction with different silicon sources in rf induced CVD reactor, Synth. Met. 140 pp309-315 (2004). [7] C.C. Tang, S. S. Fan, H. Y. Dang, J. H. Zhao, C. Zhang, P. Li, and Q. Gu, Growth of SiC nanorods prepared by carbon nanotubes-con"ned reaction, J. of Crystal Growth, 210 pp595599 (2000). [8] N. Keller, C. Pham-Huu, G. Ehret, V. Keller, and M. J. Ledoux, Synthesis and characterisation of medium surface area silicon carbide nanotubes, Carbon 41 pp2131-2139 (2003). [9] M. H. Rmmeli, E. Borowiak-Palen, T. Gemming, M. Knupfer, K. Bierdermann, R. J. Kalenczuk, and T. Pichler, On the formation process of silicon carbide nanophases via hydrogenated thermally induced templated synthesis, Appl. Phys. A 80 pp1653-1656 (2005).

5. Acknowledgements
This work was funded in part through the National Science Foundation Research Experiences for Undergraduates Site at the University of Kentucky (grant #0552854). The authors would also like to acknowledge the UK Center for Advanced Energy Research (CAER), Dr. Henry Francis at the Harry D. Rowe X-ray facility, and Larry Rice at the UK Microscopy Center.

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