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In situ formation of bismuth nanoparticles through electron-beam irradiation in a transmission

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2007 Nanotechnology 18 335604


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Nanotechnology 18 (2007) 335604 (6pp) doi:10.1088/0957-4484/18/33/335604

In situ formation of bismuth nanoparticles

through electron-beam irradiation in a
transmission electron microscope
S Sepulveda-Guzman, N Elizondo-Villarreal, D Ferrer,
A Torres-Castro, X Gao, J P Zhou and M Jose-Yacaman1
Chemical Engineering Department and The Texas Materials Institute, The University of Texas
at Austin, Austin, TX 78712, USA

E-mail: yacaman@che.utexas.edu

Received 1 May 2007, in final form 12 June 2007

Published 25 July 2007
Online at stacks.iop.org/Nano/18/335604
In this work, bismuth nanoparticles were synthesized when a precursor,
sodium bismuthate, was exposed to an electron beam at room temperature in
a transmission electron microscope (TEM). The irradiation effects were
investigated in situ using selected-area electron diffraction, high-resolution
transmission electron microscopy and x-ray energy dispersive spectroscopy.
After the electron irradiation, bismuth nanoparticles with a rhombohedral
structure and diameter of 6 nm were observed. The average particle size
increased with the irradiation time. The electron-induced reduction is
attributed to the desorption of oxygen ions. This method offers a one-step
route to synthesize bismuth nanoparticles using electron irradiation, and the
particle size can be controlled by the irradiation time.

1. Introduction nanoparticles a potential material for optical and optoelectronic

Considerable research has been focused on the synthesis As the new nanostructures have been mainly studied
of uniform metal nanoparticles due to their potential use by transmission electron microscopy, important research into
as pigments, recording materials and catalysts [1–3]. A electron irradiation effects on the nanostructures has been con-
great number of bismuth submicron structures have been ducted using novel in situ characterization techniques. Ya-
obtained using wet chemical methods, such as the precipitation mamoto et al [13], reported the modification of the conduc-
process [4, 5]. However, over the past years, bismuth tivity in an insulating BaTiO3 using electron holographic stud-
nanostructures have attracted great attention due to their very ies of irradiated sample in a transmission electron microscope
interesting properties. Nanotubes, nanowires and nanobelts (TEM). The stability and the crystallization of amorphous al-
have been synthesized using hydrothermal processes [6, 7]. loys by electron irradiation have also been studied in situ [14].
In addition, bismuth nanoparticles and nanoplates have In a different approach, the mechanism of formation of carbon
been synthesized by the solution-phase technique using onion-like structures by electron irradiation of Pt, Al or Au
different reducing agents [8, 9], whereas clusters of bismuth nanoparticles deposited on a ultra-thin carbon film has been
nanoparticles were prepared by inert-gas aggregation by Wrul elucidated [15]. Little attention has been paid, however, to
et al [10]. Many of the resulting nanostructured materials studying the electron-stimulated oxidation and/or reduction in
have several advantages when compared with bulk bismuth. the high-vacuum system of the electron microscope. Liu et al
For instance, bismuth nanowires could have thermoelectrical [16] observed the oxidation of Fe4 N(001) to Fe3 O4 in a TEM
properties [11], and recent studies suggest that a semimetal– and attributed this process to absorption of residual oxygen un-
semiconductor transition occurs in bismuth nanostructures as der electron irradiation in the microscope. On the other hand,
the crystallite size decreases [11, 12]. This makes bismuth the reduction of orthorhombic V2 O5 to cubic VO by electron
irradiation was studied by spectroscopic techniques in an an-
1 Author to whom any correspondence should be addressed.
alytical TEM [17]. Very recently, the synthesis of bismuth

0957-4484/07/335604+06$30.00 1 © 2007 IOP Publishing Ltd Printed in the UK

Nanotechnology 18 (2007) 335604 S Sepulveda-Guzman et al

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.

nanoparticles by the reduction of BiCl3 under electron-beam

irradiation in a TEM was reported [18]. However, a pretreat-
ment involving harsh reaction conditions is required before the
electron irradiation of the sample. In addition, a high dose and
a high accelerating voltage (400 kV) are needed. In this work,
we report an easier route to synthesize bismuth nanoparticles
by electron-stimulated reduction of sodium bismuthate without
pretreatments and using considerably lower irradiation condi-
tions. The phase transition, the effect of irradiation time and
the formation mechanism of the metal nanoparticles were in-
vestigated in situ using selected-area electron diffraction, high-
resolution transmission electron microscopy, and x-ray energy
dispersive spectroscopy.

2. Experimental procedure

Sodium bismuthate (NaBiO3 ) was purchased from Aldrich and

used without further purification. The sodium bismuthate was
powdered and placed over a carbon-film copper grid. The
experiments were carried out in a FEI Tecnai G20 TEM and a
JEOL 2010F (200 kV) TEM equipped with field emission gun
(FEG) and an ultrahigh-resolution observation system. The
observation was carried out under an accelerating voltage of Figure 2. (a) EDS spectrum acquired from the NaBiO3 sample at the
200 kV, at a column vacuum pressure of 10−9 Torr and a initial point of irradiation and (b) EDS spectrum acquired from an
beam current density of 14 pA cm−2 . Selected-area electron isolated particle formed after irradiation.
diffraction (SAED), x-ray energy dispersive spectroscopy
(EDS) and TEM images were recorded in situ at room
temperature. in the corresponding TEM image at this stage. However,
when the sample was irradiated for 30 min small particles and
3. Results and discussion crystalline clusters developed (figure 1(b)), along with several
diffraction spots randomly distributed in the corresponding
The initial state of the NaBiO3 was analysed using SAED SAED pattern (figure 1(b) inset). Both the cluster size and the
to define the diffraction pattern of the sample before the brightness of the diffraction spots increased with the irradiation
irradiation process. Figure 1 shows the TEM images and time. The resulting crystalline structure is related to metallic
the corresponding SAED patterns of the NaBiO3 sample Bi with rhombohedral structure, similar to bulk Bi. The
at the beginning and after irradiation. The SAED pattern reciprocal distances of the stronger reflections observed in
shows only a characteristic ring without any diffraction spots the SEAD were measured and correspond to the diffraction
(figure 1(a) inset), which indicates the amorphous state of indices (0 0 6), (2 0 8), (0 1 8), and (1 0 10) of the
the NaBiO3 sample. In addition, no clusters were observed rhombohedral structure of bismuth, according to the JCPDS

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.

database [19]. Some diffraction spots are weaker and were

not identified; however, they could be related to by-products,
such as sodium or bismuth salts. The bright-field (BF) images
and SAED clearly show the low stability of NaBiO3 under
electron irradiation and the induced reduction of Bi5+ ions
by electron irradiation. In order to study the change in
composition, the sample was analysed by EDS at different
stages during the irradiation process. The spectrum acquired at
the beginning of the experiment displays the peaks of Bi, Na,
and O (figure 2(a)), as well as those peaks related to the carbon
film (Cu and C). At this point, the semi-quantitative analysis
was consistent with the atomic composition of NaBiO3 . After
30 min of sample irradiation, the EDS spectrum of an
isolated particle shows that the bismuth to sodium ratio has
increased considerably, which indicates that the particle is
mainly composed of Bi (figure 2(b)). These results suggest that
besides the decomposition of the NaBiO3 under the electron-
beam irradiation and the phase transformation from Bi5+
to Bi0 in the sample, sodium and oxygen were segregated
or volatilized under the vacuum environment. Changes in
composition have been also observed in inorganic samples
under electron irradiation [16]. Figure 4. A series of bright-field TEM images of the sample exposed
The electron irradiation of the NaBiO3 and the to different electron irradiation doses. (a) 4.2 nC cm−2 ,
(b) 8.4 nC cm−2 , (c) 16.8 nC cm−2 and (d) 37 nC cm−2 .
nanoparticle formation were followed up by observation at
higher magnification. The effect of the irradiation time on
the particle size distribution is shown in figure 3. When the
sample was irradiated for 5 min, nanoparticles with an average large crystals by the Ostwald ripening process [21]. Figure 4
diameter of 4 nm were observed (figure 3(a)). The particles shows a series of BF images which illustrate the dynamics
showed different morphologies, ranging from spherical to of this process as a function of the irradiation dose. The
rhombohedral shape; the latter morphology has been reported smaller nanoparticles were progressively dissolved into the
for bismuth nanoparticles [10, 20]. After 10 min of irradiation, bigger ones resulting in rhombohedral-shaped particles after
the number of large particles increased to an average size of being exposed to an electron dose of 37 nC cm−2 . Since
6 nm diameter (figure 3(b)), and as the irradiation continued, the reaction was carried out in the solid state, the absence of
the particles coalesced, leading to irregularly shaped particles. capping organic molecules or stabilizers, which could prevent
After 60 min of irradiation time, significant broadening in the the continuous dissolving of the smaller particles into the
particle size distribution was observed. This process could be bigger ones, makes this process easier. Once the particles
explained as follows. The synthesis of the smallest bismuth were synthesized, their stability under the TEM is critical
nanoparticles occurred during the earlier minutes of irradiation. for all the potential applications. During the earlier reaction
Once formed, these nanoparticles acted as seeds and grew minutes, the particles were too small, and showed a rapid
into crystals. Some of these particles were able to grow into motion under the electron beam; however, when the particle

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
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.

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
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
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