Large-scale Synthesis of β-SiC Nanochains and Their Raman/Photoluminescence Properties
© Meng et al. 2010
Received: 1 July 2010
Accepted: 9 September 2010
Published: 26 September 2010
Although the SiC/SiO2 nanochain heterojunction has been synthesized, the chained homogeneous nanostructure of SiC has not been reported before. Herein, the novel β-SiC nanochains are synthesized assisted by the AAO template. The characterized results demonstrate that the nanostructures are constructed by spheres of 25–30 nm and conjoint wires of 15–20 nm in diameters. Raman and photoluminescence measurements are used to explore the unique optical properties. A speed-alternating vapor–solid (SA-VS) growth mechanism is proposed to interpret the formation of this typical nanochains. The achieved nanochains enrich the species of one-dimensional (1D) nanostructures and may hold great potential applications in nanotechnology.
Controlled, rational, and designed growth of 1D nanostructures, such as nanowire, nanorod, nanotube, and nanobelt have attracted considerable attentions in nanotechnology due to the distinct potential applications in functional electronic, photonic, and mechanical nanodevices [1–4].
1D SiC nanostructures, as an outstanding wide-gap semiconducting materials [5–8], have exhibited great applications in composite materials, optical circuits, light-emitting diodes, field-emission devices, and hydrogen storage [9–12]. These properties make SiC a promising candidate for various applications in nanoscale photoelectronic device . As known to all, some intrinsic properties are directly connected with the specific morphologies, much effort has being devoted to the synthesis and applications of various 1D SiC nanostructures, and different types of SiC nanostructures have been synthesized and reported in present literatures [14–23]. Incentived by the development of novel 1D SiC nanostructure to pursuit its unique property, a simple chemical vapor reaction (CVR) approach combined with nanoporous AAO template for SiC crystal growth control was successfully developed. Herein, the SiC nanostructures were obtained via the chemical vapor process between the C (vapor) pyrolyzed from the C 3 H 6 and SiO (vapor) generated by a solid–solid reaction between milled Si-SiO 2 ; therefore, the process was called after chemical Vapor Reaction (CVR). The CVR approach has been well revealed for the synthesis of SiC nanostructures due to the inherent advantages of simple process, low cost, lower temperature, catalyst free and high purity quotient .
Just recently, we have successfully synthesized periodic composite SiC/SiO2 beaded nanostructures (SiC nanowires and SiO2 nanospheres) on carbon substrate via the CVR approach . Wei et al. . have synthesized 1D SiC/SiO2 nanochain heterojunctions are composed of 3C-SiC strings and SiO2 beads via microwave method; however, the chained homogeneous nanostructure of single-crystalline SiC has not been reported erenow. In this paper, the nanostructures of the product are constructed by spheres of 25–30 nm and conjoint wires of 15–20 nm in diameters.  is the typically preferred growth direction with high density of stacking faults. Moreover, the as-gained nanostructures may have great application in improving the properties of the nano-composite materials due to the strong adhesion between the contoured surface nanowires and matrix comparing to the smooth-surface nanowires . Synthesis, characterizations, the corresponding Raman spectroscopy and photoluminescence measurement are also reported and discussed in this paper. A SA-VS growth mechanism is further proposed to interpret the growth mechanism of the uniform single-crystalline SiC nanochains.
The nanoporous AAO template was prepared by a two-step aluminum anodic oxidation process. Prior to anodizing, the high-purity aluminum thin sheets were annealed at 450°C for 2 h, rinsed in distilled water, then electro-polished to achieve a smooth surface. Subsequently, the samples were anodized in 0.3 M oxalic acid (40 V, 17°C, 4–5 h, Al sheet as an anode). First, the anodized layer was removed by etching in a mixture of phosphoric acid and chromic acid at 60°C for 8–10 h. Second, the samples rinsed in distilled water and oxalic acid was anodized again in 0.3 M oxalic acid (40 V, 16°C, 7–9 h, Al sheet as an anode). After the anodizing, the unwanted aluminum matrix was dissolved in HgCl2 solution at room temperature. Finally, the template was rinsed with distilled water and immersed in 5% phosphoric acid for about 20–40 min at 32°C to adjust the pore diameter and remove the barrier layer at the bottom of nanoholes.
Typical CVR processes were carried out as follows: First, the AAO template was put at the bottom of the homemade reaction chamber and supported by a piece of carbon cloth. The mixture of Si and SiO 2 powder (molar ration 1:1) was placed over the AAO template, and a piece of carbon cloth was inserted between the template and the mixture powder. Another piece of carbon cloth was situated over the powder.
Then the chamber was placed into a vertical furnace, before heating, the furnace was purged 2–3 times with high-purity argon (Ar) using a rotary vacuum pump, the temperature of furnace was increased to 1,230°C from room temperature at a mean speed of 450–500°C.h-1 held the top temperature for 10-15 min. Meanwhile, the steady flow of C3H6 at 0.1–0.2 sccm from the bottom of the graphite reaction chamber was started and maintained it for 5–10 min. Finally, the power was switched off and the furnace was cooled to room temperature.
The synthesized AAO template and SiC nanochains were characterized by a JEOL JSM-6 FESEM equipped with elemental EDX equipment. Further detailed structural information was obtained by a JEOL-2010 HRTEM and SAED. XRD pattern was recorded by a Rigaku D/max-2,400 X-ray diffractometer. Raman spectra were measured by a Renishaw 2,000 micro-Raman spectrometer. Photoluminescence spectra were performed in a Hitachi F-4500 fluorescence spectrophotometer.
Results and Discussion
Compared with the SiC nanowire arrays in our former work [], we supposed that the position of the AAO template and the reaction time have palyed important roles in determining the morphology of the products. The nanoarrays can be synthesized just during short reaction time and the low reaction rate; moreover, the AAO template must be placed over the milled powders, and the detailed growth mechanism has been depicted in the relevant paper. The SiC/SiO 2 composite nanostructures [] were synthesized without using any template or catalyst and two-stage vapor–solid growth mechanism was proposed. The first stage is the formation of the SiC nanowires within stacking faults, and the second stage is the formation of the SiO 2 spheres at the faults position. Moreover, the distribution of the gas over the carbon substrate is uniform, and the substrate could not limit the concentration of the reactant.
In summary, a simple CVR approach assisted by the nanoporous AAO template is successfully developed to form the single-crystalline β-SiC nanochains using Si-SiO2 powder and C3H6 gas as raw materials. The as-obtained nanostructures with spheres of 25–30 nm and conjunct wires of 15–20 nm in diameters typically possess novel chained homogeneous nanostructure which is different from the products have been reported. A SA-VS growth mechanism is proposed to interpret the formation of the SiC nanochain. This approach could also be applied to synthesize nanochains of the other materials. Raman and PL characterizations confirm the unique optical properties which mean the products may hold great application in functional nano-devices.
The work reported here was supported by the National Natural Science Foundation of China under Grant No.50972063, 50572041, the Natural Science Foundation of Shandong Province under Grant No. Y2007F64, the Science and Research Development Plan of Education Department in Shandong Province under Grant No. J06A02, the Tackling Key Program of Science and Technology in Shandong Province under Grant No. 2006GG2203014, the Application Foundation Research Program of Qingdao under Grant No. 09-1-3-27-jch and also the Key Technology Major Research Plan in Qingdao under Grant No. 09-1-4-21-gx. We express our grateful thanks to them for their financial support.
- Gudiksen MS, Lauhon LJ, Wang JF, Smith DC, Lieber CM: Nature. 2002, 415: 617. 10.1038/415617aView ArticleGoogle Scholar
- Xia Y, Yang P, Sun Y, Wu Y, Mayers B, Gates B, Yin Y, Kim F, Yan H: Adv Mater. 2003, 15: 353. 10.1002/adma.200390087View ArticleGoogle Scholar
- Kong XY, Ding Y, Yang R, Wang ZL: Science. 2004, 303: 1348. 10.1126/science.1092356View ArticleGoogle Scholar
- Hao YF, Meng GW, Wang ZL, Ye CH, Zhang LD: Nano Lett. 2006, 6: 1650. 10.1021/nl060695nView ArticleGoogle Scholar
- Madelung O: Intrinsic Properties of Group II-V and I-VI Compounds; Landolt-Bornstein New Series, Group III. Volume 22. Springer, Berlin; 1987.Google Scholar
- Wang ZL, Dai ZR, Gao RP, Bai ZG: Appl Phys Lett. 2000, 77: 3349. 10.1063/1.1327281View ArticleGoogle Scholar
- Duan XF, Huang Y, Cui Y, Wang J, Lieber CM: Nature. 2001, 409: 66. 10.1038/35051047View ArticleGoogle Scholar
- Soueidan M, Ferro G, Kim-Hak O, Habka N, Soulière V, Nsouli B: Cryst Growth Des. 2008, 8: 1051. 10.1021/cg701146mView ArticleGoogle Scholar
- Yang W, Araki H, Tang C, Thaveethavorn S, Kohyama A, Suzuki H, Noda T: Adv Mater. 2005, 17: 1519. 10.1002/adma.200500104View ArticleGoogle Scholar
- Niu JJ, Wang NJ: J Phys Chem B. 2007, 111: 4368. 10.1021/jp070682dView ArticleGoogle Scholar
- Han XD, Zhang YF, Zheng K, Zhang XN, Zhang Z, Hao YJ, Guo XY, Yuan J, Wang ZL: Nano Lett. 2007, 7: 27. 10.1021/nl0627689View ArticleGoogle Scholar
- Lithoxoos GP, Samios J: Nano Lett. 2006, 6: 8.Google Scholar
- Feng DH, Jia TQ, Li XX, Xu ZZ, Chen J, Deng SZ, Wu ZS, Xu NS: Solid State Commun. 2003, 128: 295. 10.1016/j.ssc.2003.08.025View ArticleGoogle Scholar
- Gundiah G, Madhav GV, Govindaraj A, Seikh MM, Rao CN: J Mater Chem. 2002, 12: 1606. 10.1039/b200161fView ArticleGoogle Scholar
- Ye HH, Titchenal N, Gogotsi Y, Ko F: Adv Mater. 2005, 17: 1531. 10.1002/adma.200500094View ArticleGoogle Scholar
- Xi GC, Peng YY, Wang SM, Li TW, Yu WC, Qian YT: J Phys Chem B. 2004, 108: 20102. 10.1021/jp0462153View ArticleGoogle Scholar
- Pei LZ, Tang YH, Zhao XQ, Chen YW, Guo C: J Appl Phys. 2006, 100: 046105. 10.1063/1.2335606View ArticleGoogle Scholar
- Yang WY, Miao HZ, Xie ZP, Zhang L, An LN: Chem Phys Lett. 2004, 383: 441. 10.1016/j.cplett.2003.11.031View ArticleGoogle Scholar
- Wu RB, Li BS, Gao MX, Chen JJ, Zhu QM, Pan Y: Nanotechnology. 2008, 19: 335602. 10.1088/0957-4484/19/33/335602View ArticleGoogle Scholar
- Gao FM, Yang WY, Wang HT, Fan Y, Xie ZP, An LN: Cryst Growth Des. 2008, 8: 1461. 10.1021/cg701227nView ArticleGoogle Scholar
- Wang HT, Xie ZP, Yang WY, Fang JY, An LN: Cryst Growth Des. 2008, 8: 3893. 10.1021/cg8002756View ArticleGoogle Scholar
- Yang YY, Meng GW, Liu XY, Zhang LD, Hu Z, He CY, Hu YM: J Phys Chem C. 2008, 112: 20126. 10.1021/jp809359vView ArticleGoogle Scholar
- Zhang XN, Chen YQ, Xie ZP, Yang WY: J Phys Chem C. 2010, 114: 8251. 10.1021/jp101067fView ArticleGoogle Scholar
- Li ZJ, Zhang JL, Meng AL, Guo JZ: J Phys Chem B. 2006, 110: 22382. 10.1021/jp063565bView ArticleGoogle Scholar
- Li ZJ, Gao WD, Meng AL, Geng ZD, Gao L: J Phys Chem C. 2009, 113: 91. 10.1021/jp806346dView ArticleGoogle Scholar
- Wei GD, Qin WP, Zheng KZ, Zhang DS, Sun JB, Lin JJ, Kim Ryongjin, Wang GF, Zhu PF, Wang LL: Cryst Growth Des. 2009, 9: 1431. 10.1021/cg800845hView ArticleGoogle Scholar
- Wang DH, Xu D, Wang Q, Hao YJ, Jin GQ, Guo XY, Tu KN: Nanotechnology. 2008, 19: 215602. 10.1088/0957-4484/19/21/215602View ArticleGoogle Scholar
- Koumoto K, Takeda S, Pai CH: J Am Ceram Soc. 1989, 72: 1985. 10.1111/j.1151-2916.1989.tb06014.xView ArticleGoogle Scholar
- Chen XL, Li JY, Lan YC, Cao YG: Modern Phys Lett B. 2001, 15: 27. 10.1142/S0217984901001495View ArticleGoogle Scholar
- Meng AL, Li ZJ, Zhang JL, Gao L, Li HJ: J Cryst Growth. 2007, 308: 263. 10.1016/j.jcrysgro.2007.08.022View ArticleGoogle Scholar
- Fu QG, Li HJ, Shi XH: Mater Chem Phys. 2006, 100: 108. 10.1016/j.matchemphys.2005.12.014View ArticleGoogle Scholar
- Olego D, Cardona M: Phys Rev B. 1982, 25: 3889. 10.1103/PhysRevB.25.3889View ArticleGoogle Scholar
- Feng ZC, Mascarenhas AJ, Choyke WJ, Powell JA: J Appl Phys. 1998, 64: 3176. 10.1063/1.341533View ArticleGoogle Scholar
- Cambaz GZ, Yushin GN, Gogotsi Y, Lutsenko VG: Nano Lett. 2006, 6: 548. 10.1021/nl051858vView ArticleGoogle Scholar
- Wu RB, Yang GY, Gao MX, Li BS, Chen JJ, Zhai R, Pan Y: Cryst Growth Des. 2009, 9: 100. 10.1021/cg701101jView ArticleGoogle Scholar
- Wu RB, Pan Y, Yang GY, Gao MX, Wu LL, Chen JJ, Zhai R, Lin J: J Phys Chem C. 2007, 111: 6233. 10.1021/jp070115qView ArticleGoogle Scholar
- Xi GC, Liu YK, Liu XY, Wang XQ, Qian YT: J Phys Chem B. 2006, 110: 14172. 10.1021/jp0617468View ArticleGoogle Scholar
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