NANO LETTERS

Electrochemical Synthesis and Characterization of Magnetic Nanoparticles on Carbon Nanowall Templates

Bingjun Yang
Department of Physics, National UniVersity of Singapore, 10 Kent Ridge Crescent, Singapore 119260 and Data Storage Institute, 5 Engineering DriVe 1, Singapore 117608

2002 Vol. 2, No. 7 751-754

Yihong Wu*
Department of Electrical and Computer Engineering, National UniVersity of Singapore, 4 Engineering DriVe 3, Singapore 117576 and Data Storage Institute, 5 Engineering DriVe 1, Singapore 117608

Baoyu Zong
Data Storage Institute, 5 Engineering DriVe 1, Singapore 117608

Zexiang Shen
Department of Physics, National UniVersity of Singapore, Singapore 119260
Received April 7, 2002

ABSTRACT
Magnetic nanoparticles (Ni, CoNiFe) with diameters ranging from 30 to 200 nm were synthesized by electrodeposition using carbon nanowalls as templates. A series of experiments have been carried out to study the formation mechanism of nanoparticles. It was found that the formation of nanoparticles instead of continuous films was attributed to two key factors, i.e., the uneven current density distribution on the nanowall surfaces and the pulsed current supply with alternate polarities. The as-grown nanocomposite structures were characterized using energydispersive X-ray analysis, scanning electron microscopy, and magnetic measurement using a vibrating sample magnetometer. These types of nanostructures may have potential applications in batteries, supercapacitors, catalysts, and biomedical devices.

Recently, we have successfully grown two-dimensional carbon nanosheets (dubbed carbon nanowalls) using microwave plasma enhanced chemical vapor deposition.1-3 The large surface area of such kind of carbon nanostructures makes them promising alternatives for applications that require the use of mesoporous carbon materials.4-14 To this end, soon after the finding of the carbon nanowalls, we have carried out a series of experiments to form a class of nanostructured materials using carbon nanowalls as the templates.15 These materials include ZnO, TiO2, SiOx, AlOx, SiNx, Fe, Ni, NiFe, NiCoFe, Cu, and Au. The growth mechanism of these nanostructures, however, was unknown. In this letter, we focus on magnetic nanoparticles and discuss their formation mechanism using electrodeposition on carbon nanowalls. The motivation for growing magnetic nanopar* Corresponding author. E-mail: elewuyh@nus.edu.sg. 10.1021/nl025572r CCC: $22.00 Published on Web 05/21/2002 2002 American Chemical Society

ticles on carbon nanowalls is two-fold: (i) many applications, such as batteries, use carbon/transition metal composite materials as the source materials and (ii) magnetic nanoparticles are widely studied for both fundamental research and technological applications in data storage. For the latter case, although the magnetic nanostructures can also be fabricated using other top-down approaches, such as e-beam lithography, those techniques are generally slow and costly. The templating technique to be discussed in this paper is attractive because it allows the formation of large-area nanostructures in a relatively short time period and without the need of expensive equipment. The carbon nanowalls were prepared on Cu substrates (typically 1 cm 1 cm in size) using a microwave plasma enhanced chemical vapor deposition system. The growth of carbon nanowalls has been described in detail in refs 1-3. Shown in Figure 1 are two typical scanning electron

Table 1: Parameters Used for the First Series of Experiments

J1 (mA/cm2) -100 -75 -50 -25 -12.5 0 etching time (s) 3 3 3 3 3 3 J2 (mA/cm2) 125 125 125 125 125 125 deposition time (s) 15 15 15 15 15 15

Figure 1. SEM images of carbon nanowalls on the Cu substrate: (A) is taken at a tilt angle of 10 degree; (B) is taken at a tilt angle of 15 degree. Scale bar: (A) 1 m and (B) 100 nm.

Table 2: Parameters Used for the Second Series of Experiments

J1 (mA/cm2) -100 -75 -50 -25 -12.5 etching time (s) 8 6 4 2 1 J2 (mA/cm2) 125 100 75 50 25 deposition time (s) 40 30 20 10 5

Figure 2. The current density profile for one cycle of the deposition and etching process.

microscopy (SEM) images of carbon nanowalls at different magnifications. As can be seen from the figures, the nanowalls have a lateral dimension in the micron range and a thickness of several nanometers. The electrodeposition of magnetic nanoparticles was carried out with a potentiostat/ galvanostat (EG&G M273A) system. The plating solutions were a mixture of (Ni, Fe, Co)SO47H2O, (Ni, Fe, Co)Cl26H2O, H3BO3, and saccharine with a pH value in the range of 2.5-3.5. The electrolyte temperature was maintained by water circulation at a thermostated temperature of 40 C. A nickel plate (6 cm 6 cm in size) was used as the cathode and a stirrer was employed to maintain a uniform chemical concentration in the electrolyte. The EG&G system provides a square-wave of bipolar pulses, and the duration of each polarity can be programmed and controlled by a computer. The electrodeposition process can be divided into two main cycles. During the positive voltage cycle deposition takes place, while etching occurs during the negative voltage cycle. Figure 2 shows the typical current density profile for one cycle of deposition and etching process. In the first series of experiments, all the parameters were fixed except for the etching current density, which was varied from 0 to -100 mA/cm2. In the second series of experiments, all the parameters were varied proportionally within a certain range of each parameter. The detailed parameters are listed in Tables 1 and 2, respectively. After the deposition was completed, the as-deposited materials were characterized using scanning electron microscopy and energy-dispersive X-ray analysis (EDX). The magnetic properties of the particles were examined using a vibrating sample magnetometer (VSM). Figure 3 shows the typical SEM images of magnetic particles formed on carbon nanowalls. The particular sample
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Figure 3. Typical SEM images of magnetic nanoparticles deposited on the carbon nanowalls. Scale bar: (A) and (B)1 m, (C) and (D) 100 nm.

was fabricated using a 15 s of deposition time at a current density of about 75 mA/cm2 and a 3 s etch time at a current density of -25 mA/cm2. As can be seen from (A) and (B), the magnetic nanoparticles are formed quite uniformly on the carbon nanowalls and the nucleation sites are concentrated on the carbon nanowall surfaces instead of the empty space surrounded by the carbon nanowalls. Some of nanoparticles were also deposited on the upper edge of carbon nanowalls. This is demonstrated very clearly by the high magnification image shown in (C). This might be attributed to the large current density on the upper edge of carbon nanowalls. Image (D) shows the nanoparticles formed on the inner walls of the carbon nanostructures, which were peeled off from the substrates using a tweezers after the electrodeposition was completed. It shows very clearly that the magnetic nanoparticles were formed not only at the upper portion of the nanowalls but also at other portions near the roots of the nanowalls. Although we had foreseen that noncontinuous films would be formed on the nanowall templates even before we started the electroplating experiments, we did not expect the asdeposited materials to exhibit such well-defined spherical
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Figure 4. SEM images of magnetic materials deposited on the carbon nanowalls with varying etching current densities. The current density of etching cycle for (A), (B), (C), (D), (E), and (F) was -100 mA/cm2, -75 mA/cm2, -50 mA/cm2, -25 mA/cm2, -12.5 mA/cm2 and 0, respectively. Scale bar: 100 nm.

Figure 6. SEM images of different size magnetic nanoparticles deposited on the carbon nanowalls. (A) Deposition (etching) duration: 30 s (6 s), deposition (etching) current density: 100 mA/ cm2 (-75 mA/cm2); (B) Deposition (etching) duration: 20 s (4 s), deposition (etching) current density: 75 mA/cm2 (-50 mA/cm2); (C) Deposition (etching) duration: 10 s (2 s), deposition (etching) current density: 50 mA/cm2 (-25 mA/cm2); (D) Deposition (etching) duration: 5 s (1 s), deposition (etching) current density: 25 mA/cm2 (-12.5 mA/cm2). Scale bar: 100 nm.

Figure 5. Schematic illustration of the formation process of magnetic particles.

shapes. A question naturally arose: what could be the mechanism responsible for the formation of well-rounded nanoparticles? Intuitively there are two possible reasons: (1) the defects on the carbon nanowall surfaces make some spots more conductive than other areas that serve as the nucleation sites; (2) the etch immediately after the short deposition further sharpens the edges and finally leads to the formation of a spherical shape. To test this hypothesis the first series of experiments have been carried out. Figure 4 shows the SEM images of the magnetic nanoparticles that were electrodeposited with all other parameters fixed except for the current density for the etching cycle, which was varied from -100 mA/cm2 to 0. As can be seen from (A) to (D), with the current density of the etching cycle decreasing, the shape of the nanoparticles became less spherical and the nucleation of most of the magnetic nanoparticles elongated more in one direction than in others to form an oval structure. When the current density of the etching cycle was further reduced, as can be seen in Figure 4 (E), the nanoparticles started to touch each other. Finally a quasi-continuous film was formed on the carbon nanowalls when the current density of the etching cycle was reduced to 0 (Figure 4(F)). The results were somewhat expected and can be understood as follows with the help of the cartoons shown in Figure 5. After the first cycle of deposition, the as-deposited materials most probably would have a shape shown in (a). At this stage, when a negative current was applied, the etching would take place at almost a constant rate over the entire structure, or a little bit faster at the edge of the particles due to the higher current density at the corners. In either case, this would form a structure shown in (c). The deposition cycle immediately after this resulted in an even-higher deposition rate at the center than that at the edges due to the better electrical conductivity of metals as
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Figure 7. Typical M-H curves of electrodeposited CoNiFe nanoparticles on carbon nanowalls.

compared to the carbons. The repetition of these deposition and etching processes would finally lead to the formation of spherical particles. Now we turn to the factors that determine the size of the spherical particles. Intuitively it is not difficult to imagine that the particle size will decrease when both the deposition and etching times were reduced proportionally. However, when the deposition and etching times were reduced, it would be difficult to control the deposition and etching processes had the current density not been reduced proportionally. Based on this consideration, the second series of experiments were carried out by reducing all the parameters proportionally as shown in Table 2. Figure 6 shows the SEM images of the particles formed at different parameter combinations. It can be seen that the sizes of nanoparticles gradually decreased from 200 to 30 nm from (A) to (D). At the same time, the nanoparticles tended to become smoother when their sizes became smaller. The EDX measurement confirmed the presence of magnetic elements and carbon. The composition of the CoNiFe particles were measured to be 34.43 wt % Co, 41.59 wt %
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Ni, and 23.98 wt % Fe. Figure 7 shows the typical hysteresis curves of the CoNiFe samples in both the substrate surface direction and its normal direction. The curves in both directions exhibit typical characteristics of nanomagnetic arrays.16 The curve along the nanowalls direction is more highly sheared as compared to that in the sample surface direction, suggesting a strong magnetostatic interaction in the wall directions. This is understandable because the nanospheres are closely packed on the walls, whereas the distance between the nanospheres in the sample surface direction is relatively large, which is determined by the spacing between the walls. In summary, magnetic nanoparticles with well-defined shapes have been successfully fabricated on carbon nanowalls. It was found that a short etching step immediately after a certain duration of deposition is critical for the formation of nanoparticles that otherwise would form quasicontinuous films. The exploration on the application of this type of novel composite structures is currently underway. Acknowledgment. B.J. acknowledges the graduate scholarship provided by the Agency for Science, Technology & Research of Singapore. References
(1) Wu, Y. H.; Chong, T. C. paper presented at the MRS 2001 Spring

Meeting, abstract No. W8.3, San Francisco, CA, April 16-20, 2001. (2) Wu, Y. H.; Qiao, P. W.; Chong, T. C.; Shen, Z. X. AdV. Mater. 2002, 14, 64. (3) Wu, Y. H.; Yang, B. J. Nano Lett. 2002, 2, 355. (4) Joo, S. H.; Choi, S. J.; Oh, I.; Kwak, J.; Liu, Z.; Terasaki, O.; Ryoo, R. Nature 2001, 412, 169. (5) Frackowiak, E.; Beguin, F. Carbon 2001, 39, 937. (6) Jurewicz, K.; Delpeux, S.; Bertagna, V.; Beguin, F.; Frackowiak, E. Chem. Phys. Lett. 2001, 347, 1-3, 36. (7) Niu, C.; Sichel, E. K.; Hoch, R.; Moy, D.; Tennet, H. Appl. Phys. Lett. 1997, 70, 1480. (8) Frackowiak, E.; Metenier, K.; Bertagna, V.; Beguin, F. Appl. Phys. Lett. 2000, 77, 2421. (9) Frackowiak, E.; Jurewicz, K.; Delpeux, S.; Beguin, F. J. Power Sources, 2001, 97-98, 822. (10) Sun, M.; Zangari, G.; Shamsuzzoha, M.; Metzger, R. M. Appl. Phys. Lett. 2001, 78, 2964. (11) Blackburn, J. M.; Long, D. P.; Cabanas, A.; Watkins, J. J. Science 2001, 294, 141. (12) Chen, Y.; Shaw, D. T.; Bai, X. D.; Wang, E. G.; Lund, C.; Lu, W. M.; Chung, D. D. L. Appl. Phys. Lett. 2001, 78, 2128. (13) An, K. H.; Kim, W. S.; Park, Y. S.; Moon, J.-M.; Bae, D. J.; Lim, S. C.; Lee, Y. S.; Lee, Y. H. AdV. Funct. Mater. 2001, 11, 387. (14) Diederich, L.; Barborini, E.; Piseri, P.; Podesta, A.; Milani, P. Appl. ` Phys. Lett. 1999, 75, 2662. (15) Wu, Y. H.; Yang, B. J.; Han, G. C.; Zong, B. Y.; Ni, H. Q.; Luo, P.; Chong, T. C.; Low, T. S.; Shen, Z. X. AdV. Funct. Mater., accepted. (16) Kazakova, O.; Hanson, M.; Blomquist, P.; Wappling, R. J. Appl. Phys. 2001, 90, 2440.

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