Professional Documents
Culture Documents
electron microscope
This article has been downloaded from IOPscience. Please scroll down to see the full text article.
(http://iopscience.iop.org/0957-4484/18/33/335604)
View the table of contents for this issue, or go to the journal homepage for more
Download details:
IP Address: 152.15.236.17
The article was downloaded on 18/08/2013 at 09:00
E-mail: yacaman@che.utexas.edu
Figure 1. Low-resolution TEM images of the NaBiO3 sample (a) at the initial point of irradiation and (b) after 30 min of irradiation.
Inset: corresponding SAED pattern.
2. Experimental procedure
2
Nanotechnology 18 (2007) 335604 S Sepulveda-Guzman et al
Figure 3. TEM images of the NaBiO3 sample (a) after 5 min of irradiation and (b) after 10 min of irradiation.
3
Nanotechnology 18 (2007) 335604 S Sepulveda-Guzman et al
Figure 5. HRTEM image of an isolated bismuth particle. Inset: FFT Figure 7. Bright-field TEM image of irradiated sample after 45 min
of the image. of irradiation. Arrows indicate the resulting structures after the
coalescence between the particles: (a) agglomerate and (b) snake-like
structure.
size increased to ∼6 nm, the motion became slower and
more stable to the observation conditions. At this moment,
a high-resolution TEM (HRTEM) image of a single particle minutes of irradiation and is related to smaller particles, the
was recorded (figure 5). The characteristic lattice fringes coalescence involves the diffusion of an entire particle which
of the rhombohedral structure of bismuth were observed and collides with other particles. During coalescence, adjacent
measured as 0.23 and 0.33 nm accordingly. In addition, a fast particles first form an agglomerate and then merge into a
Fourier transform (FFT) was conducted on the image, and the single particle. As a result of the bulk transport and extended
spots in the corresponding FFT were indexed to the (1 2 2), coalescence of several nanoparticles in the sample, snake-like
(1 1 0), and (0 1 2) diffraction planes, with a lattice spacing structures were finally observed (figure 7). This diffusion
of 1.43 Å, 2.26 Å, and 3.27 Å, respectively (figure 4 inset). mechanism is most likely caused by continuous irradiation and
These values are in agreement with the simulated diffraction the weak interaction between the particles and the support.
pattern of the rhombic structure of the bismuth [1 1 1] zone This mechanism is in agreement with recent studies which
axis. In a previous work, Oshima et al [20] observed a have shown that electron-beam irradiation can trigger the
transition from rhombohedral to cubic structure in 6–7 nm coalescence of nanoparticles, even those highly stabilized by a
diameter Bi particles under an electron beam; however, in capping agent. The process depends on several factors, such
our case, no structural transition was observed. Instead of as the sensitivity of the passivating ligands to the electron
a structural transition a coalescence process was observed beam, the support characteristics, the size of the nanoparticles,
during the irradiation of the Bi nanoparticles (figure 6). Unlike and the irradiation dose [22]. On the other hand, Kim et al
the Ostwald ripening process, which occurs during the early [23] reported the synthesis of gold nanoparticles by electron-
Figure 6. (a) HRTEM image of Bi particles after 30 min of irradiation. (b) Magnification of selected area. Inset: FFT of the image.
4
Nanotechnology 18 (2007) 335604 S Sepulveda-Guzman et al
Figure 8. (a) High-angle annular dark-field (HAADF) image of the synthesized bismuth nanoparticles and (b) composition profile of C, O and
Bi extracted from the line-scan microanalysis of one nanoparticle.
beam irradiation and found that the particle size can be partly from the irradiated sample. The induced reduction in the
controlled by the accelerating voltage. According to previous TEM by the desorption of oxygen atoms under electron
studies done in the field, it is clear that several parameters, irradiation has been observed in other materials, such as V2 O5
such as temperature, electron dose, accelerating voltage, time and NiO–MgO, resulting in the formation of VO and Ni
and precursor particle size, should influence the growth and metal, respectively [17, 26]. A more detailed explanation
morphology of the bismuth nanoparticles synthesized through of the mechanism of formation is needed; nevertheless, the
electron-beam irradiation. synthesis of Bi nanoparticles under electron irradiation is
Although there are well-known aspects of the electron highly interesting for nanotechnology purposes, and could find
irradiation effects discussed in the literature, such as applications in areas like electron-beam nanolithography and
adsorption, desorption, diffusion and dissociation, each system might also serve as an example for the synthesis of other
has particular considerations. The complete mechanism of the semiconductor nanoparticles.
reduction of NaBiO3 by electron-beam irradiation is still not
fully understood. However, we believe it could include the 4. Conclusions
ionization of the sodium bismuthate, i.e., the electron beam
breaks the bonding between the elements under the observation Bismuth metal nanoparticles were easily synthesized by
conditions in the TEM (200 kV). Similar ionization has been the electron irradiation of a bismuth precursor (NaBiO3 )
observed during the oxidation of Fe4 N and InP in an ultrahigh- under observable conditions (200 kV) in a TEM. In situ
characterization was used to study the reduction of the NaBiO3
vacuum (UHV) chamber [16, 24, 25]. Nevertheless, in our
and the growth mechanism of the Bi nanoparticles. The
case, as the irradiation continues the collisions between the
decrease of oxygen peak in the EDS spectrum suggests that
electrons and the bismuthate sample result in the formation
the reduction of Bi5+ results from the desorption of oxygen
of Bi metal and simultaneous desorption of oxygen atoms.
ions under electron irradiation. The Bi particles showed a
Thus the oxygen is lost to the vacuum, particularly in the
rhombohedral structure which is common in bulk bismuth. The
area where the transformation takes place completely. This particles size could be controlled by the irradiation time. In
is further supported by the absence of an oxygen peak in addition, the bismuth particles were unstable under the electron
the EDS spectrum acquired from an isolated Bi nanoparticle beam and showed a diffusion–collision process during the last
formed after 30 min (37 nC cm−2 ) of irradiation (figure 2(b)). irradiation period.
However, in order to rule out any noise signal effect and
to verify the accuracy of the EDS, a line-scan microanalysis
Acknowledgments
was done on a single bismuth nanoparticle comparing both
the bismuth and oxygen signal to that of carbon, which is
The authors want to thank ICNAM of the University Of Texas
used as a reference (figure 8). The results revealed that the
Austin, the Welch Foundation and NSF materials division, and
bismuth signal is originated by the bright particle seen on the Industrias Penoles for financial support. S Sepulveda-Guzman
image. As expected, the intensity increases at the centre of acknowledges the support received from CIQA-Mexico.
the particle. In contrast, the intensity of the oxygen signal
is considerably lower than that of Bi and the intensity is not
limited to the particle boundaries, whereas the intensity of the References
carbon signal fluctuates around an average value, indicating [1] Jose-Yacaman M, Rendon L, Arenas J and Serra-Puche M C
that the sensitivity of the acquisition was constant throughout 1996 Science 273 223
the process. These results confirm the desorption of oxygen [2] Majetich S A and Jin Y 1999 Science 284 470
5
Nanotechnology 18 (2007) 335604 S Sepulveda-Guzman et al
[3] Persson K, Jansson K and Järås S G 2007 J. Catal. 245 401 [16] Liu Z Q, Hashimoto H, Sukedai E, Song M, Mitsuishi K and
[4] Wang Y and Xia Y 2004 Nano Lett. 4 2047 Furuya K 2003 Phys. Rev. Lett. 90 255504
[5] Goia C, Matijevic E and Goia D V 2005 J. Mater. Res. 20 1507 [17] Su D S, Wieske M, Beckman E, Blume A, Mestl G and
[6] Li Y, Wang J, Deng Z, Wu Y, Sun X, Yu D and Yang P 2001 Schlögl R 2001 Catal. Lett. 75 81
J. Am. Chem. Soc. 123 9904 [18] Kim S H, Choi Y-S, Kang K and Yang S I 2007 J. Alloys
[7] Wang J, Wang X, Peng Q and Li Y 2004 Inorg. Chem. 43 7552 Compounds 427 330
[8] Wang Y W, Hong B H and Kim K S 2005 J. Phys. Chem. B [19] JCPDS International Centre for Diffraction Data 2003 PDF
109 7067 85-1330; PCPDFWIN v. 2.4
[9] Fu R, Xu S, Lu Y-N and Zhu J-J 2005 Cryst. Growth Des. [20] Oshima Y, Takayanagi K and Hirayama H 1997 Z. Phys. D
5 1379 40 534
[10] Wrul A, Hyslop M, Brown S A, Hall B D and Monot R 2001 [21] Roosen A R and Carter W C 1998 Physica A 261 232
Eur. Phys. J. D 16 205 [22] Chen Y, Palmer R E and Wilcoxon J P 2006 Langmuir
[11] Sun X, Zhang Z and Dresselhaus M S 1999 Appl. Phys. Lett. 22 2851
74 4005 [23] Kim J-U, Cha S-H, Shin K, Jho J Y and Lee J-C 2005 J. Am.
[12] Zhang Z, Sun X, Dresselhaus M S, Ying J Y and Heremans J P Chem. Soc. 127 9962
1998 Appl. Phys. Lett. 73 1589 [24] Bouslama M, Lounis Z, Ghaffour M, Ghamnia M and
[13] Yamamoto T, Hirayama T, Fulkunaga K and Ikuhara Y 2004 Jardin C 2002 Vacuum 65 185
Nanotechnology 15 1324 [25] Liu Z Q, Hashimoto H, Song M, Mitsuishi K and
[14] Nagase T and Umakoshi Y 2003 Mater. Sci. Eng. A 343 13 Furuya K 2004 Acta Mater. 52 1669
[15] Troiani H E, Camacho-Bragado A, Armendariz V, [26] Davies P K and Mackinnon I D R 1986 J. Am. Ceram. Soc.
GardeaTorresday J L and Jose-Yacaman M 2003 Chem. 69 C-124
Mater. 15 1029