Electronic Materials Letters, Vol. 7, No. 4 (2011), pp.

333-336
DOI: 10.1007/s13391-011-0420-4

Green Synthesis and Characterization of Se Nanoparticles and Nanorods

Huiyu Chen1,2,3,*, Ji-Beom Yoo3, Yaqing Liu1,2, and Guizhe Zhao1,2

1
Research Center for Engineering Technology of Polymeric Composites of Shanxi Province, North University of
China, Taiyuan 030051, People’s Republic of China
2
College of Materials Science and Engineering, North University of China, Taiyuan 030051,
People’s Republic of China
3
School of Materials Science & Engineering (BK21), Sungkyunkwan University, Suwon 440746,
Republic of Korea
(received date: 26 July, 2011 / accepted date: 31 August, 2011)

Selenium nanoparticles and nanorods were successfully prepared in a mixed solvent of ethylene glycol and
water at a relatively low temperature of 85°C. No other surfactant or template was employed, and glucose
was used as a green and mild reducing reagent in the current synthesis. The volume ratio of ethylene glycol
to water played an important role for controlling the shapes of selenium products. The obtained selenium
samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), high-resolution
transmission electron microscopy (HRTEM), Raman spectra, and UV-vis absorption spectra. The evolution
process from amorphous selenium to a trigonal phase complied with a “solid-solution-solid” formation mech-
anism. HRTEM and SAED results indicate that the trigonal selenium nanorods grow along the [001] direction.
This method might provide an environmentally-friendly and low cost route for the synthesis of other related
nanomaterials with controlled morphologies.
Keywords: solution synthesis, nanoparticles, nanorods, selenium

1. INTRODUCTION ered to be more promising due to its low cost, ease of

In the past decade, nanosized materials have attracted a
great deal of attention due to the fact that they have different
properties from their corresponding bulk counterparts.[1-3] It
is widely accepted that the properties of nanomaterials have
a close relationship with their morphology, size, size distri-
[4, 5]
bution, crystallinity, and so on. Therefore, control over
the morphology and size of inorganic materials at micro- and
nano-scale level is an important goal. In particular, one-
dimensional (1D) nanostructures such as nanorods, nanow-
ires, and nanobelts have been the focus of intensive research
owing to their unique physical and chemical properties as
well as fascinating potential applications in electronic and
[6,7]
photonic nanodevices. To date, a variety of synthetic
methodologies including electrodeposition,[8] template-
assisted (anodic aluminum oxide, porous membranes, and
[6]
surfactant) and template-free synthesis, a solution phase
[9] [10-12]
route. and chemical vapor deposition (CVD) methods
have been developed for the fabrication of 1D nanostruc-
tures. Among them, the solution phase approach is consid-
*Corresponding author: hychen09@sina.com
©KIM and Springer
handling, and high yield production.
Elemental selenium is an important indirect gap semicon-
ductor with excellent photoelectrical and semiconducting
properties. It has a relatively low melting point (~490 K),
high photoconductivity (~8 × 104 S cm−1), many allotropic
forms (amorphous, monoclinic, and trigonal), and high reac-
tivity toward other chemicals, allowing its conversion into a
[13] [14]
series of functional materials such as CdSe, ZnSe, and
[15]
Ag2Se. Selenium has been widely used in the field of solar
cells, rectifiers, and xerography.[16,17] Recently, several ap-
proaches have been employed to prepare selenium nano-
structures with controllable morphologies. Typically, sele-
nium nanoparticles are synthesized by reducing a selenious
acid solution with ascorbic acid in the presence of polysac-
[18]
charides, or prepared by pulsed laser deposition (PLD)
using a YAG laser with a power of 532 nm.[19] Xia and
coworkers employed solution refluxing or sonochemical
techniques to produce t-Se nanowires by the reaction of
[20, 21]
selenium acid with excess hydrazine. Komarneni et
al reported that the synthesis of selenium nanobelts was
successfully achieved via a hydrothermal route at 160 for
15 h,[22] and Se nanobelts were also obtained by a thermal
evaporation method at 600°C.[23] Most of these methods
require expensive instruments, high temperature or long
334 H. Chen et al.: Green Synthesis and Characterization of Se Nanoparticles and Nanorods
Fig. 1. SEM images and size distribution diagrams of Se nanoparticles synthesized in an EG/H2O mixed solution at 85°C for 45 min. The dos-
ages of glucose were (a) 1 g, (b) 2 g, (c) 4 g, and (d) 8 g.
reaction time. In addition, some toxic reagents were also
used for the synthesis of Se products. The development of a
simple, efficient, and environmentally-friendly route for the
preparation of Se nanostructures is thus a key area of study.
In this work, amorphous selenium (α-Se) nanoparticles
and trigonal selenium (t-Se) nanorods were prepared at 85°C
using ethylene glycol (EG) and water as a mixed solvent.
Glucose acts as a mild and environment-benign reducing
agent, and no surfactant or template was employed during
the synthetic process. The volume ratio of EG to water was
found to play a key role in the variation of the selenium mor-
phology. The reaction for the synthesis of Se nanostructures
in this work can be expressed as follows:
Na2SeO3 + 2C6H12O6 → Se + 2C6H11O7Na + H2O
2. EXPERIMENTAL
All chemical reagents were purchased from Sigma-Ald-
rich and used as received without further purification. In a
typical synthesis, 1.02 g of Na2SeO3 and various amount of
glucose were dissolved in 70 mL of ethylene glycol (EG)
and 15 mL of H2O mixed solution, and the beaker holding
the reactants was then sealed and put in an oven previously
set to a temperature of 85°C. After the reaction proceeded
for 45 min, 1, and 1.5 h, the beaker was removed and the
samples were collected and rinsed with DI water several
times. Finally, the Se samples were dispersed in DI water
and stored in dark. Controlled experiments were carried out
by changing the dosage of glucose and the volume ratio of
EG to water, respectively, while keeping the other synthetic
parameters constant.
Powder X-ray diffraction (XRD) measurements were per-
formed on a Bruker D8 focus diffractometer with a Cu Kα
radiation source (λ = 0.15406 nm) in the 2θ ranging from 20
to 80°. Scanning electron microscopy (SEM) images were
taken by a JEOL JSM6700F field emission scanning elec-
tron microscope. High resolution transmission electron
Electron. Mater. Lett. Vol. 7, No. 4 (2011)
microscopy (HRTEM) images and the corresponding
selected area electron diffraction (SAED) patterns were
taken with a JEOL JEM2100F transmission electron micro-
scope performed at an accelerating voltage of 200 kV. The
−1
Raman spectra were measured from 100 to 800 cm at room
+
temperature using the 514-nm line of Ar laser with a power
level of 30 mW (RM1000-Invia, Renishaw). The UV-vis
absorption spectra were recorded on a Shimadzu UV-3600
spectrophotometer.
3. RESULTS AND DISCUSSION
The color of the solution changed to brick red when the
reaction proceeded for 45 min, and the samples were col-
lected at this stage for all various characterizations. Fig. 1
shows SEM images of Se samples synthesized with different
amounts of glucose. All the products possess a large quantity
of nanoparticles with a perfect spherical shape and clean sur-
face. The average size of Se nanoparticles is about 320 nm
when 1 g glucose was used in the system (Fig. 1(a)). The
reaction rate was accelerated when the dosage of glucose
was increased, and larger Se nanoparticles were therefore
obtained in a given reaction time. For the current synthesis,
the mean size of Se nanoparticles gradually increased to
480 nm when 8 g of glucose was employed (Fig. 1(d)).
Fig. 2 Shows the XRD pattern and the related digital cam-
era image of the sample prepared with 8 g of glucose. There
was no sharp peak in the XRD pattern, indicating that the Se
product synthesized under these conditions was amorphous.
Also, the brick red color is the characteristic color of α-Se.
The color of the solution changed to dark red when the
reaction time was prolonged to 1 h. The sample was com-
posed of larger particles with average size of 0.85 µm
(Fig. 3(a)-(b)), and a minute amount of particles possess a
rough surface. For the XRD pattern shown in Fig. 3(c), all
the peaks could be indexed to the trigonal phase of selenium
(JCPDS card No. 06-0362) and no other peaks of impurities
were detected. The digital camera image in the inset reveals
 H. Chen et al.: Green Synthesis and Characterization of Se Nanoparticles and Nanorods
Fig. 2. XRD pattern and digital camera image (in the inset) of the
sample prepared at 85°C for 45 min with 8 g glucose as the reducing
reagent.
Fig. 3. SEM image (a) and size distribution diagram (b) of Se sample
synthesized at 85°C for 1 h with 2 g of glucose, (c) XRD pattern of
the corresponding sample and the digital camera image in the inset,
(d) SEM image of Se product obtained at 85°C for 1.5 h.
that the resultant Se is dark red, the characteristic color of
trigonal selenium. The formation process from α-Se parti-
cles to t-Se complied with a “solid-solution-solid” formation
mechanism on the basis of the observed experimental phe-
nomena. The brick red color indicating the appearance of α-
Se in the solution gradually became lighter and then almost
disappeared, with the solution becoming dark red. The
observed phenomena were in good agreement with those of
a reported work.[24] During the entire process, the originally
generated á-Se nanoparticles dissolved to produce highly
reactive Se atoms, which re-crystallized and formed more
stable crystalline t-Se nuclei when the concentration of these
free selenium atoms was sufficiently high. In the subsequent
growth stage, these t-Se nuclei grew into larger t-Se parti-
cles, because the viscosity of the mixed solvent was so high
that it limited the nuclei movement. When we prolonged the
reaction time to 1.5 h, surprisingly, some particles coexisted
Electron. Mater. Lett. Vol. 7, No. 4 (2011)
335
Fig. 4. SEM image (a) and Raman spectrum (b) of t-Se nanorods syn-
thesized with 30 mL of EG and 55 mL of water as a mixed solvent, (c)
HRTEM image and (d) SAED pattern of an arbitrary t-Se nanorod.
with some rods as the dominant final product (Fig. 3(d)).
The formation mechanism for selenium rods in the present
synthetic system requires further investigation and related
work is currently underway.
Selenium nanorods could be prepared on a large scale
when the mixed solvent of EG and water was employed with
dosages of 30 mL and 55 mL, respectively. As seen in the
SEM image displayed in Fig. 4a, a large quantity of Se nan-
orods with length of 10~15 µm and diameter ranging from
200 to 500 nm could be synthesized. These Se nanorods
were characterized by XRD (not shown here) and the Raman
spectrum (Fig. 4(b)), and the results demonstrated that the
selenium nanorods were in a trigonal phase with high purity.
−1
A strong peak located at 234 cm can be observed in the
Raman spectrum, which is a characteristic signature of trigo-
nal selenium and can be assigned to the stretching vibration
−1
of helical selenium chains (A1 mode). The peak at 140 cm
corresponds to the transverse optical phonon mode (E
−1
mode), and two other weak peaks at 443 and 460 cm can
be attributed to the second-order spectra of t-Se. The sele-
nium nanorods were further characterized by high-resolution
TEM (HRTEM), and a typical HRTEM image captured
from an arbitrary Se nanorod is shown in Fig. 4(c). The
fringe spacing of the crystal planes perpendicular to the long
axis direction of the nanorod is about 0.50 nm, which is
close to the (001) lattice spacing of t-Se. The corresponding
selected area electron diffraction (SAED) pattern exhibits
discrete spots and indicates a well-crystallized single crystal
(Fig. 4d), which can be well indexed to trigonal selenium
[1-10]
along the zone axis. Both the HRTEM and SAED results
indicate that the t-selenium nanorods have a preferential
[001] growth direction along their long axis.
The UV-vis absorption spectrum was also used to charac-
terize the obtained t-Se nanorods. As shown in Figure 5, the
336 H. Chen et al.: Green Synthesis and Characterization of Se Nanoparticles and Nanorods
Fig. 5. UV-vis absorption spectrum of the obtained t-Se nanorods.
t-Se nanorods prepared at room temperature show one weak
peak at 347 nm and two strong peaks centered at 462 and
586 nm; these peaks are close to the absorption peaks at 346,
450, and 570 nm for t-Se nanowires obtained in C12EO10
[25]
micelles. As previously reported, the optical property of
Se nanomaterials varied according to the size and micro-
structure of the materials, and thus could be tuned by chang-
ing the synthetic conditions.[22] The peaks above 530 nm can
be solely attributed to interchain interactions perpendicular
[26]
to the c axis within a given t-Se crystal. Therefore, the
position of the low-energy peak at high wavelength may pro-
vide instructive information for the interchain interactions as
well as the degree of crystal perfection.
4. CONCLUSIONS
In summary, amorphous selenium nanoparticles and trigo-
nal selenium nanorods were successfully prepared at a low
temperature of 85°C using glucose as a reducing reagent. A
mixed solvent of ethylene glycol and water was employed,
and the volume ratio of ethylene glycol to water was found
to play a key role for controlling the morphology of the
resultant selenium samples. HRTEM and SAED results indi-
cate that the Se nanorods grow along the [001] direction. The
evolution process from amorphous selenium to trigonal sele-
nium complied with a “solid-solution-solid” formation
mechanism. Amorphous selenium nanoparticles were pro-
duced initially and then transformed into crystal seeds for the
subsequent growth of t-Se. The presently reported green
chemical approach may be extended to fabricate other nano-
materials with controllable shapes.
ACKNOWLEDGEMENTS
The financial support from Youthful Science Foundation
of North University of China and from the BK21 Project of
Electron. Mater. Lett. Vol. 7, No. 4 (2011)
School of Advanced Materials Science & Engineering is
gratefully acknowledged.
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