Materials Letters 64 (2010) 1037–1040

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Materials Letters
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / m a t l e t

The influence of the cadmium source on the shape of CdSe nanoparticles

N.N Maseko a, N. Revaprasadu a,⁎, V.S.R. Rajasekhar Pullabhotla a, R. Karthik b, P. O'Brien b
a
Department of Chemistry, Private bag X1001,University of Zululand, Kwa-Dlangezwa, 3886, South Africa
b
The School of Chemistry and Materials Science Center, The University of Manchester, Oxford Road, Manchester, M13 9PL, UK

a r t i c l e i n f o a b s t r a c t

Article history: Tri-n-octylphosphine oxide (TOPO) and hexadecylamine (HDA) capped CdSe nanoparticles in the shape of
Received 13 November 2009 spheres and rods have been synthesized employing a hybrid route involving solution chemistry and
Accepted 2 February 2010 thermolysis at high temperatures. The influence of the cadmium source on the shape of the nanoparticles
Available online 11 February 2010
was studied. When cadmium chloride is used spherical particles are formed, however when cadmium
carbonate is used rod shaped TOPO and HDA CdSe particles are observed. The absorption and
Keywords:
photoluminescence of the CdSe nanorods are also reported.
CdSe nanoparticles
Cd source
© 2010 Elsevier B.V. All rights reserved.
Hexadecylamine (HDA)
Tri-octylphosphine (TOP)
Tri-octylphosphine oxide (TOPO)

1. Introduction
During the past decade there have been considerable work
undertaken in the area of nanomaterials synthesis. The demand for
high quality semiconductor nanomaterials has increased exponen-
tially due to the applications of these materials in biological labels [1]
photovoltaic and light emitting devices [2,3] and lasers [4]. Concur-
rent with the growth in synthetic methods for nanomaterials is the
emphasis on finding greener synthetic routes. Some of the important
properties that need not be compromised in designing newer greener
routes, include reasonable crystallinity, achievement of desirable
particle sizes over the largest possible range, desired surface
passivation, increased luminescence and a high degree of mono-
dispersity in size and shape.
Chemically grown CdSe nanoparticles are probably the most
extensively investigated colloidal II–VI semiconductor nanoparticles
because its band gap can be tuned across the visible spectrum by
variation of its particle size [5]. Bawendi and co-workers pioneered
the use of precursors to synthesize passivated nanoparticles at high
temperatures. In their popularly cited paper, CdSe nanoparticles were
synthesized by injecting a solution containing dimethyl cadmium and
trioctylphosphine selenide (TOPSe) into hot tri-n-octylphosphine
oxide (TOPO) [6]. This route and adaptations thereof has been
extensively used to synthesize CdSe nanoparticles for the study of
their fundamental properties [7,8]. The method allows for the kinetic
control, where parameters such as reaction temperature and
precursor concentration control the final morphology and size of
⁎ Corresponding author.
E-mail address: nrevapra@pan.uzulu.ac.za (N. Revaprasadu).
the particles. The toxic and pyrophoric nature of dimethyl cadmium at
elevated temperatures resulted in the search for alternative routes. A
modification of the Bawendi route was reported by Peng and Peng,
where CdO replaced dimethyl cadmium as the precursor [9]. The
authors have done extensive work on the shape control of CdSe
nanoparticles by varying key reaction parameters such as tempera-
ture, precursor concentration and capping groups [9–11]. Recently the
synthesis of CdSe nanoparticles in olive oil, eliminating the use of
phosphine has also been identified as a cheaper, cleaner route to
easily up scalable nanoparticles [12,13].We have recently reported a
new, safe, inexpensive and facile non-organometallic synthetic route
to organically soluble CdSe nanoparticles [14]. In this paper we report
the synthesis of TOPO and HDA capped CdSe nanoparticles using this
hybrid method employing both solution chemistry and thermolysis at
high temperature. We have investigated the effect of the cadmium
source on the shape of the nanoparticles by using different cadmium
salts. Very briefly this method involves the reduction of selenium
powder to produce selenide ions (Se2−), followed by the addition of
cadmium ions (Cd2+) and finally thermolysis in TOPO or HDA. The
source of the Cd2+ ions was varied by using different cadmium salts.
2. Experimental
2.1. Synthesis of CdSe nanoparticles
In a typical room temperature reaction, selenium powder was
reduced to selenide ion by adding 0.32 mmol of selenium powder to
20.0 mL of HPLC grade water in a three neck flask. A solution of
sodium borohydride (NaBH4) was added to the flask contents and the
flask was purged with nitrogen flow to create an inert atmosphere.
The reduction reaction was carried out for 2 h with continuous

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doi:10.1016/j.matlet.2010.02.002
1038 N.N. Maseko et al. / Materials Letters 64 (2010) 1037–1040
stirring. A 0.32 mmol solution of cadmium salt (CdCl2, CdSO4 and
CdCO3) was added to the reduced selenide ion solution. A light yellow
to brown coloured solution was obtained depending on the cadmium
source used. Stirring was continued for 5 min, followed by the
addition of excess methanol to flocculate the CdSe particles. The
resulting precipitate was isolated by centrifugation and dispersed in
15.0 mL of TOP. The resultant CdSe-TOP mixture was then injected
into 6.0 g of TOPO (pre-heated to 230 °C) or HDA (pre-heated to
160 °C). After injection a drop (20–30 °C) in the temperature was
observed. The temperature was then stabilized at the injection
temperature and the reaction was allowed to proceed for one hour.
After cooling, excess methanol was added to flocculate the nanopar-
ticles. The flocculate was separated from the supernatant by
centrifugation and the excess methanol was removed under vacuum
to give TOPO or HDA-capped CdSe nanoparticles. The resultant
particles were dissolved in toluene to give an optically reddish brown
solution of nanoparticles for characterization.
2.2. Characterization
A Perkin Elmer Lambda 20 UV–Vis Spectrophotometer was used to
carry out optical measurements in the 200–800 nm wavelength range
at room temperature. For TEM analysis samples were placed in quartz
cuvettes (1 cm path length). Photoluminescence (PL) spectra were
recorded on a Perkin Elmer LS 55 luminescence spectrometer with
Xenon lamp over 200–800 nm range. Samples were prepared by
placing a drop of dilute solution of nanoparticles on Formvar-coated
grids (150 mesh). The samples were allowed to dry completely at
room temperature and viewed using a JEOL 1010 TEM. Viewing was
done at an accelerating voltage of 100 kV and images captured
digitally using a Megaview III camera, stored and measured using Soft
Imaging Systems iTEM software.
3. Results and discussion
Colloidal CdSe nanoparticles in the shape of spheres or rods were
synthesized by the reduction of selenium powder using NaBH4 as the
reducing reagent to give an oxygen free selenide ion (NaHSe)
followed by the addition of the cadmium salt. The reduction is due
to the presence of an active hydride in NaBH4, which also activates the
reaction between the selenide ion and CdCl2. The occurrence of the
reaction is confirmed by the change in the colour of the reaction
solution from colourless to bright-yellow after the addition of the
cadmium salt. The resultant CdSe particles were then dispersed in tri-
n-octylphosphine (TOP) and injected into HDA or TOPO which serves
as the coordinating solvent. The reaction scheme (Fig. 1) shows the
synthesis of HDA and TOPO capped CdSe nanorods when cadmium
carbonate is used as the cadmium source.
Fig. 1. Scheme showing synthesis of TOPO and HDA capped CdSe nanorods.
The surface ligand dynamics on the surface of CdSe nanoparticles
has an influence on the choice of temperature for the reactions carried
out in high boiling point solvents. Low temperatures favour slower
growth rates. Therefore higher temperatures have been used and the
solvents chosen are correlated to their boiling points [15]. The
coordinating solvent is important because surface passivation of the
nanocrystals by organic molecules has been shown to control the
growth rate, particle size, luminescence efficiency, stability and
solubility. In this study, TOPO and HDA were used as the coordinating
solvents because they give higher surface passivation due to greater
coverage of the co-ordinating unsaturated Cd at the surface by the
ligands [6]. The stability of the TOPO capped particles is due to the
high affinity of TOPO for Cd2+ and it's bulky nature also provides
increased steric hindrance [16]. In contrast HDA, a primary amine is a
slightly weaker base than TOPO, with less steric hindrance, high
electron donating ability and high capping density as a result of its
small stereochemical interference [17,18].
Fig. 2 shows the TEM image of TOPO capped CdSe nanoparticles
using CdCl2, CdSO4 and CdCO3 as cadmium sources. The CdSe
nanoparticles synthesized using CdCl2 and CdSO4 were spherical with
average particle sizes of 5.13 nm± 0.53 nm and 8.98 nm± 1.29 nm
respectively. However there is a distinct change in particle shape when
CdCO3 is used as the cadmium source. Rod shaped CdSe particles with an
average length of 35.34± 6.17 nm and breadth of 10.79± 1.58 nm are
visible in the TEM image. A similar trend is observed when TOPO is
replaced by HDA.
We have reported the synthesis of spherical hexadecylamine
capped CdSe nanoparticles using cadmium chloride as the cadmium
source [14]. In this study HDA capped CdSe particles in the shape
of rods, bipods and tripods are observed (Fig. 3) when the chloride
is replaced by the corresponding carbonate salt. There are short
and long rods present, with average lengths of 20.74 ± 3.10 nm and
35.05 ± 3.19 nm respectively. The absorption spectra for the TOPO
and HDA capped CdSe nanorods are shown in Fig. 4. The TOPO capped
CdSe nanoparticles exhibit a band edge at 628 nm (1.73 eV) with a
distinct excitonic peak at 570 nm and an absorption shoulder at
488 nm. The photoluminescence (PL) spectrum shows a narrow
emission curve with the maximum at 584 nm and a full width at half
maximum (FWHM) of 50 nm. The absorption band edge of the HDA
capped CdSe nanoparticles is observed at 608 nm. The corresponding
PL spectrum shows a narrow emission curve with the emission
maximum at 593 nm and a FWHM of 46 nm.
A plausible explanation for the evolution of particle shape with
variation of cadmium salts is that the reaction of the soluble salts,
chloride and sulfate with the selenide proceeds to completion before
thermolyis in the solvent. The resultant fully formed CdSe particles are
decomposed and grow into thermodynamically stable spherical
particles. The carbonate salt does not dissolve completely in solution
resulting in a suspension of the cadmium carbonate. As a result only a
 N.N. Maseko et al. / Materials Letters 64 (2010) 1037–1040
Fig. 2. TOPO capped CdSe nanoparticles prepared with (a) CdCl2 (b) CdSO4 and
(c) CdCO3.
shell of CdSe is formed in addition to the selenium and carbonate
source. After injection into the hot solvent the carbonate and the CdSe
is decomposed under kinetically controlled growth resulting in
anisotropically shaped particles such as rods, bipods and tripods.
Fig. 3. HDA capped CdSe nanoparticles prepared with CdCO3.
1039
Fig. 4. Absorption (I) and PL spectrum (II) of (a) TOPO and (b) HDA capped CdSe
nanorods.
4. Conclusion
We have reported the synthesis of organically capped CdSe
nanoparticles by a method employing the use of reduced selenium
and a cadmium salt. The shape of TOPO and HDA capped CdSe
nanoparticles is influenced by the cadmium source. Cadmium chloride
and sulphate produce spherical particles whereas cadmium carbonate
gives rod shaped particles.
Acknowledgements
The authors are grateful to the National Research Foundation
(NRF) and Department of Science and Technology (DST) South Africa
for financial support. The authors also thank Dr James Wesley-Smith
from the Electron Microscopy Unit, University of KwaZulu-Natal for
electron microscopy measurements.
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