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.
KeywordsNanochain Chemical vapor reaction Growth mechanism Optical property
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.
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