Green and controlled synthesis of single family magic-size cadmium

selenide nanocrystals by the use of cyclo-hexeno-1,2,3-selenadiazole an

organoselenium compound
Rupinder K. Beri and Pawan K. Khanna
*
Received 24th December 2009, Accepted 24th February 2010
DOI: 10.1039/b927290a
Single family magic-size CdSe nanocrystals (MSNCs) have been obtained by reasonably low
temperature thermolysis of cyclo-hexeno-1,2,3-selenadiazole i.e. an organoselenium precursor. The
reaction of selenium precursor with metal salt at temperatures between 100 and 150

C leads to
formation of stabilized magic-size nano-clusters showing sharp and persistent absorption peaks at
371 nmand 392 nm. The present approach is without the use of generally employed toxic reagents thus
making the method virtually green. The photoluminescence (PL) emission spectrumshows two features
rst a band-gap emission at 405 nm and second a broad-band emission from 430 to 680 nm. The
X-ray diffraction (XRD) measurements indicate the formation of zinc-blende (cubic) crystal structure.
The detailed characterization by X-ray photoelectron spectroscopy (XPS), Energy dispersion X-ray
analysis (EDX), Transmission electron microscopy (TEM), Selected area electron diffraction (SAED)
and Infrared spectroscopy (IR) is described.
1. Introduction
The applications of IIVI semiconductor quantum dots (2 to
10 nm) in diverse elds such as electronics,
1
opto-electronics,
2
biosensors and imaging
3
and solar cells
4
have ensured
a continued interest in the area. Amongst the IIVI semi-
conductors CdSe is considered to be front runner as its optical
properties are tunable into the entire visible light spectrum.
Tuning of optical behaviour of the quantumdots arises primarily
due to small particle sizes, underlying fundamental properties of
quantum connement and high volume to mass ratios. The
synthetic methodologies for obtaining mono-disperse materials
have been perfected and the correlation of properties (particu-
larly optical) to shape and size are also well understood in terms
of quantum connement effects in three spatial dimensions.
5
Though CdSe quantum dots are most well understood in
comparison to other semiconductor quantum dots, a lot remains
to be claried when it comes to CdSe below 2 nm. In this lower
size domain are encountered the ultra-small nanocrystals (1 to
2 nm) popularly termed as magic-size nanocrystals. Magic-size
nanocrystals may have several nomenclatures and the termi-
nology magic-size and/or magic-number nanocrystals or
nanoclusters (MSNCs) have been used by different authors.
69
MSNCs are considered to be thermodynamically stabilized
structures or ensembles with specic number of atoms formed
during the inorganic polymerization process.
10
They are
proposed to contain no more than one-unit cell of the bulk
crystal and closed-shell congurations as opposed to quantum
dots which do not contain closed-shell structure. The thermo-
dynamic stabilization of MSNCs on account of possible
difference of geometry and/or composition compared to
quantum dots translates into their possessing unique spectral
properties different from those of quantum dots and opens up
newer avenues for application. For example, the absorption
peaks for quantumdots are slightly broad, and are systematically
red-shifted with respect to particle size but the emissions are
narrowand size-tunable.
11
For the MSNCs on the other hand the
absorptions appear sharp, discrete and normally at xed posi-
tions whereas the emissions appear broad
8
though the method of
synthesis greatly inuences this property and exceptions to this
behaviour have been reported recently
9
where only sharp-emis-
sions were observed.
Broad-emitting magic-size nanocrystals offer applications in
the area of white-light emitting diodes (LEDs) and the prospects
of replacing conventional incandescent and uorescent lighting
by intrinsically combining the red, blue and green or orange
colours produced due to inherent surface-defect sites.
8
In addi-
tion they offer the advantages of energy efciency, long-life,
durability and design exibility like any other LED.
12
Clusters of IIVI semiconductors were reported as early as
1984.
13
The 10 A

thiophenolate-capped CdS clusters were

observed to have sharp absorption peaks. CdSe clusters spanning
a size of 12 nm and displaying cage structures were reported in
1996.
14
Clusters reported by Ptateschek et al.
15
displayed sharp
HOMOLUMO absorption peaks at xed wavelengths. The
absorption at 410 nm was assigned to a cluster with Koch-
pyramid structure and lateral length 1.7 nmbased on small-angle
X-ray scattering (SAXS). Homologous series of CdSe clusters by
Soloviev et al.
6
showed sharp absorptions and two types of
emission bands in the photoluminescence (PL) spectra; narrow
band gap PL and the broad and large red shifted deep trap
PL. Transient formation of magic-size nanocrystals have been
reported by Peng and Peng
7
during the high temperature
synthesis of CdSe quantum dots. Stable CdSe clusters (CdSe)
33
and (CdSe)
34
were observed in mass spectrum by Kasuya et al.
16
Nanoscience Laboratory, Centre for Materials for Electronics
Technology(C-MET), Pune, 411008, India. E-mail: pkkhanna@cmet.
gov.in; pawankhanna2002@yahoo.co.in; Fax: +91-20-25898085; Tel:
+91-20-25899273
2762 | CrystEngComm, 2010, 12, 27622768 This journal is The Royal Society of Chemistry 2010
PAPER www.rsc.org/crystengcomm | CrystEngComm
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and were found to grow in preference to other compositions.
Based on rst-principle calculations corecage structure was
proposed with puckered (CdSe)
28
cages with (CdSe)
56
cores.
They were proposed to have a diameter of 1.5 nmby atomic force
microscopy and displayed sharp excitonic peak at 415 nm and
smaller peaks at 382 nm and 352 nm. Magic-size nanocrystals
reported by Bowers et. al.
8
showed sharp band-edge absorption
at 414 nm corresponding to size of 1.5 nm. The emission spectra
lacked the sharp band gap PL but displayed broad deep-trap PL.
Similarly, families of magic-sizes of CdSe have been reported
recently by Ouyang et al.
9
which possess only sharp band-gap
emissions. These have been reported to exist along with regular
quantum dots and have been assigned size on the basis of the
absorptions and diffused ordered NMR spectroscopy. In
another study the structureproperty relationship for CdSe
cluster upto sizes of 2 nm has been carried out and it has been
reported
17
that for sizes greater than or equal to (CdSe)
14
, sharp
spectra are observed, because the PL due to excitons (which is
inherently sharp) is predominant. On the other hand broad
spectra are observed for sizes smaller than (CdSe)
14
. It can be
inferred from the examples cited above on stable CdSe clusters
that the absorption bands in all the cases are characteristic
occurring at isolated positions but the emission bands are far
from characteristic. There is also a certain difculty with regard
to assigning the crystal structure as either zinc-blende or wurt-
zite. However, recently researchers
18
have assigned them to be
tentatively wurtzite albeit by the use of phosphine ligands and by
adopting high temperature pyrolytical methods.
Other methods for obtaining magic-size nanocrystals have
described the use of etchants wherein larger crystals grown have
been etched to smaller ones by using amines.
19
However, magic-
crystals formed without the use of etchants have also been repor-
ted.
20,21
Low temperature organometallic preparations have also
yielded magic-crystals both by injection
22
and non-injection
methods.
9
Lowtemperature inverse wateroil micellular have been
reported.
16
Most of the organometallic methods still advocate the
use of phosphine reagents such as trioctylphosphine (TOP)/TOP-
oxide, amines such as hexadecylamine (HDA) for etching or
otherwise, and the use of 1-octadecene for preparation of nano-
crystals withsuperior optical properties. Theywarrant extreme care
while handling due to high toxicities of reagents and are also dif-
cult toreproduce due tocomplexity of procedures which sometimes
require quenching of reactions within seconds for obtaining parti-
cles of sizes <2 nm.
22
The fatty acids, especially oleic acid have also
been used to encapsulate the CdSe magic-size nanocrystals.
However, the particles obtained by this method do not possess
broad/white emission.
9
The taskof the synthetic chemist is tricky by
this method as isolating exclusively one type of magic-size nano-
crystals by suppressing the formationof multiple type or families of
magic-crystals along with quantum dot appears difcult.
The fundamental scientic understanding of magic-size
nanocrystals as apparent from the above cited examples is still in
the infancy stage and it is therefore imperative that more studies
of these classes of compounds become available so as to harness
their full technological potential. The complexity of synthetic
procedures may remain as one of the stumbling blocks in
providing materials consistently or in better yields and there
remains an ongoing need to devise newer methods which address
the above lacunae.
We realize that 1,2,3-selenadiazoles have potential as Se-
precursors to take metal selenide nanoparticles synthesis into the
green zone because they can completely eliminate the usage of
TOP, other phosphorus containing reagents or amines.
23
The
choice of these organoselenium reagents also offers several
distinct advantages. First, they are easily prepared from the
corresponding alkyl/aryl semicarbazones via single step.
24
Second, reasonably low temperature decomposition of these
compounds facilitates an easy elimination of reactive selenium
25
thus offering scope to carry out the synthesis at low temperature
(compared to the cases where TOP : Se is used) which is a key
factor for the formation of magic-size CdSe nanocrystals. Third,
it also facilitates an easy monitoring process. Fourth, the use of
inert atmosphere is not an absolute necessity. We report herein
the precise formation of magic-size CdSe nanocrystals using
cyclo-hexeno-1,2,3-selenadiazole and describe their detailed
characterization.
2. Experimental details
2.1 General
All solvents and chemicals were of reagent grade and were used
as received. The starting materials, cyclo-hexeno-1,2,3-selena-
diazoles, were prepared as described in the literature
24
and
puried by column chromatography. All manipulations were
carried out using standard airless procedures.
2.2 Monitoring and characterization
Aliquotes of reaction mixture were taken out at regular intervals
and used to study the growth of CdSe MSNCs. The isolation was
carried out on a small scale as follows: samples were prepared by
rst precipitating freshly prepared nanocrystals out of their
coordinating solvents with ethanol or methanol. The resulting
solids were centrifuged on a R-23 Centrifuge Machine (Remi,
India Ltd), dried in the oven (60

C, 68 hours) and used for
analysis either as solids or re-dispersed in toluene. UV-Vis
absorption spectra were recorded on a JASCO V-570UV/VIS/
NIR spectrophotometer at room temperature. Solutions were
placed into quartz cuvettes and scanned over 200800 nm
wavelength range.
Photoluminescence (PL) measurements of solutions were
recorded using HITACHI F-2500 uorescence spectrophotom-
eter. The samples were excited between 300 and 500 nm and
emissions monitored between 350 and 800 nm. The quantum
yield was calculated following previously reported method.
26
Powder X-ray diffraction patterns were measured using Cu-Ka
(l 1.5406 A

) radiation on Mini Flex Rigaku X-ray diffrac-

tometer. X-Ray photoelectron spectra (XPS) were recorded with
a 9 channeltron CLAM4 analyzer under a vacuum better than 1
10
8
Torr, using Mg-Ka radiation with a constant pass
90 energy of 50 eV. Low and high resolution Transmission
Electron Microscopy (TEM) images were taken on a Technai
G-20 transmission electron microscope with an acceleration
voltage of 200 kV. Randomly oriented nanocrystals on the TEM
substrate were obtained by using diluted solution of the nano-
crystals. FT-IR spectra were recorded as KBr disc on
Perkin Elmer FT-IR 2000 spectrophotometer in the range of
4004000 cm
1
.
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2.3 Preparation of magic-size CdSe using oleic acid and
diphenyl ether (DPE)
In a typical experiment oleic acid (17 ml, 53.5 mmol) was heated
to 150

C in a 250 ml ask under argon atmosphere. To this was
added cadmium acetate (3.14 g, 11.75 mmol) and stirred for
5 min for dissolution followed by the addition of diphenyl ether
(45 ml) at 150

C. Following the drop in temperature the reaction

was re-heated for 15 min for it to re-attain 150

C. Cyclo-
hexeno-1,2,3-selenadiazole (1 g, 5.35 mmol) dissolved in 5 ml of
DPE was added to the above via syringe. Colour change from
yellow to deep orange was noticed and the reaction was moni-
tored by UV-Vis spectroscopy using aliquots. The reaction was
heated for a maximum of 6 hours after which heating was
stopped and the reaction mixture was cooled to 60

C.
Isolation and purication. Ethanol (50 ml) was added and
orange-yellow precipitates thus obtained were centrifuged. The
solid was separated by decantation, washed with ethanol (50 ml)
and re-centrifuged. The process was repeated 23 times. The free
owing solids obtained after ltration were dried at 60

C. Yield:
1.8 g (capped CdSe with organics).
3. Results and discussion
When cadmium acetate and oleic acid are heated together in
diphenyl ether in the temperature between 100 and 150

C and
further with cyclo-hexeno-1,2,3-selenadiazole dissolved in the
same solvent reacted (Scheme 1), the solution darkens from pale-
yellow to orange indicating the formation of CdSe nanocrystals.
The thermolysis of the selenadiazole provides reactive selenium
and/or 1,4-diselenine
25
that reacts with the cadmium oleate
generated in situ by the reaction of cadmium acetate and oleic
acid. Either of the above decomposition products of 1,2,3-sele-
nadiazole may form an intermediate single-source precursor
complex with cadmium oleate which decomposes to form magic-
size CdSe nano-crystals under the dened conditions outlined
herein.
The use of large excess of oleic acid proves an effective cap or
surfactant for obtaining particles below 2 nm. The use of
diphenyl ether as solvent ensures easy work-up and temperature
homogeneity throughout the reaction ask. The reaction
produces CdSe magic-size nanocrystals at temperatures
(#150

C). The type of the particle obtained is found to be
greatly dependent on the temperature at which the reaction is
carried out apart from ratio of reactants used.
3.1 Optical spectral features
Formation of magic-size clusters was monitored by UV-Vis
spectroscopy (Fig. 1A) using aliquots taken out during the
synthesis. Within minutes of the addition of the Se-precursor two
well-dened absorptions appear at 371 nm and 392 nm. With
time these peaks become sharper but persist at the same position.
The doublets have been assigned to electronic transitions 1S(e)
1S
3/2
(h); 1S(e)2S
3/2
(h) with energy separation of 180 meV
between the two transitions.
27
The size assignment based on peak
at 392 nm as per reported observations
9
is 1.5 nm. The pho-
toluminescence (PL) emission spectrum (Fig. 1B) shows two
features rst a sharp peak at 405 nm (3.06 eV) assigned as band
gap emission and second a broad band (430 to 680 nm)
assigned as the deep trap emission based on the behaviour of
semiconductor nanoclusters.
6
The band gap emission is narrow;
FWHM 30 nm and is only slightly Stokes shifted (13 nm)
fromthe absorption value. The band gap is the rst electronically
allowed transition and it involves the metal and chalcogen atoms.
The deep trap emission is, however, substantially red shifted
from the absorption onset (typically by 0.5 eV). The large Stokes
shift of this luminescence band indicates that the equilibrium
geometry in the excited state is distorted from the ground state
due to radiative recombination of localized surface trapped
charge carriers (arising due to surface defects).
Further it has been reported
8
that long lifetime of this state
(deep trap) is due to alternate energy dissipation modes
(via coupling of vibrational modes of ligand to surface atoms
when they are of comparable size) or collision relaxation makes it
appear broad. The fact that no absorption can be detected in the
spectral region of the PL, clearly indicates that this emission
electronic transition is forbidden. These features are consistent
with deep-trap emission in nanoclusters where HOMOLUMO
gap involves forbidden transitions of surface states.
6
It is interesting to note that reported work on magic-size CdSe
grown pyrolytically,
8
do not show band-edge PL and families of
CdSe magic-size NCs synthesized by a non-injection method do
not show deep-trap PL
9
whereas the nanocrystals obtained in the
Scheme 1 Formation of CdSe MSNCs using 1,2,3-selenadiazoles.
Fig. 1 Room temperature optical spectra: (A) UV-Vis absorption
showing evolution of magic-size CdSe and (B) superimposed UV-Vis and
photoluminescence (l
ex
350 nm) of magic-size CdSe.
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present synthesis show both PL emissions i.e. sharp as well as
broad. Our samples show white-light emission (Fig. 2) as well as
less balanced yellow light emission from different samples
depending on relative intensity ratios of band-gap PL and deep
trap PL. The quantum efciency of >10% from our measure-
ment
26
using anthracene as reference seems to be very attractive
as against the reported efciency of 15%.
9
3.2 Effect of varying ratios of reactants and surfactant on
optical properties
It is well established that for the nucleation and growth of the
nanocrystal, temperature is one of the critical factors which
determines optimal growth conditions as well as product yield.
To study this, the preparation of CdSe by the use of cyclo-hex-
eno-1,2,3-selenadiazoles was carried out at different tempera-
tures ranging from 100

C to 250

C. Based on the TGA it was
found that 150

C is the optimum decomposition temperature of
the selenadiazole. It was found that in general lower tempera-
tures are more suitable for the formation of MSNCs. However,
at a particular temperature, the ratios in which reactants and
surfactants or capping agents are employed, can be used as
efcient parameters for exercising control over the type of
particle obtained. The results of carrying out the reaction at
150

C are summarised in Table 1. For a ratio of 1 : 1 : 20 of
selenadiazole (selenium source) to cadmium acetate (metal
source) to oleic acid (surfactant) mixtures of quantum dots and
MSNCs are produced. For either lower capping agent ratio (1 :
1 : 10) or high metal source ratio i.e. (1 : 2 : 20) or (1 : 2 : 10)
magic-size nanocrystals are produced exclusively and reliably.
Temperatures lower than 150

C results in incomplete reaction
with MSNCs being the only product, however, reactions at
180

C lead to formation of quantum dots.
29
Large excesses of
oleic acid with respect to cadmium acetate may lead to complete
conversion of cadmium acetate to cadmium-oleate which may
decompose at high temperatures to release Cd ions. Similarly, the
selenadiazole also decomposes at high temperature to release
highly reactive Se. When the ratio of cadmium precursor to
selenium precursor is more than unity then an excess of Cd ions
may be responsible for stabilizing the magic-size nuclei formed.
When this ratio of cadmium : selenium is 2 : 1 then it might just
be sufcient to prevent the dissociation of magic-size nuclei to
form regular quantum dots. At the same time maintaining the
temperature of 150

C is a critical factor that ensures formation
of thermodynamically controlled stable nuclei but prevents their
growth to regular quantum dots. If, however, the oleic acid is not
in large excess then the incomplete displacement of acetate from
cadmium salt may lead to the formation of an intermediate
species Cd(OOCCH
3
)
x
(OOC(CH
2
)
n
CH
3
)
2x
which may not
release Cd ions readily leading to an Se-rich environment which
may again be responsible for stabilizing the magic-nuclei. The
effect may be related perhaps to differences of feed rates of
reactive Se and Cd which may in-turn be related to the rate of
decomposition of precursors. Surfaces enriched in Cd or Se or
other such defects may perhaps be leading to unique photo-
physical properties which show good consistency when obtained
by different methods (Fig. 3). It is further observed that the
cadmium rich environment leads to slight red-shift in the emis-
sion maximum of the MSNCs. The Cd-rich environment may
cause further defects in the nanocrystals thus creating additional
deep trap states resulting in the red-shifts.
Fig. 2 White light emission from (A) magic size CdSe and (B) solvent
alone.
Table 1 Effect of varying ratios of reactants and surfactant on forma-
tion of magic-size CdSe at 150

C in diphenyl ether
Ratios of reactants
Product obtained Selenadiazole Cadmium acetate Oleic acid
1 1 20 Quantum dots + MSNCs
1 1 10 MSNCs
1 2 20 MSNCs
1 2 10 MSNCs
Fig. 3 Formation of magic-size CdSe at 150

C using different ratios of
selenium source, cadmium source and surfactant: (A) absorption spectra
and (B) emission spectra.
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3.3 XRD diffraction
The X-ray diffraction pattern (Fig. 4A) indicates cubic structure
of CdSe.
28
The ve main diffraction peaks identied as (111),
(200), (220), (311) and (400) show that the conformation is
convincingly, essentially zinc-blende. Interesting differences are
observed in the intensity of peaks in comparison to CdSe
quantum dots
29
obtained by similar choice of reagents but at
higher temperatures. The intensity of (220) is enhanced at the
expense of the (111) and (331) planes. We suspect that this could
be due to orientation or elongation along (220) due to forma-
tion of distorted structures as a result of the closed-shell
conguration. Further, diffraction peaks (102) and (103) char-
acteristic for wurtzite (hexagonal) are clearly absent. Our
observations comply with theoretical calculations
30
and experi-
mental observations
31
on several Cd(S/Se) cluster sizes where it
was predicted that stable CdSe clusters exist with a zinc blende
conformation rather than the wurtzite structure. The XRD
observations from different batches are consistent (Fig. 4B) and
can be used reliably to differentiate our magic-size nanocrystals
from quantum dots.
3.4 XPS
The elemental composition and surface properties can be best
understood by XPS analysis. The binding energy value of 54.9 eV
corresponds to Se 3d. (Fig. 5A). There is no evidence of oxidation
due to absence of additional peak for SeO
2
indicating the effec-
tive capping due to the use of oleic acid.
In addition the 3d doublet with binding energies 405.6 eV (Cd
3d
5
) and 412.4 eV(Cd 3d
3
) match with expected binding energies
32
for CdObondformationshowing the chemisorption and binding
of oleic acid to Cd via carboxylate. (Fig. 5B). The symmetric
feature of the O 1s peak at 532 eV indicates the presence of two
symmetric oxygen atoms in the carboxylate (COO

) moiety.
(Fig. 5C). This is further indicated by the FTIR spectra.
3.5 IR
To understand the adsorption mechanism of oleic acid on the
surface of CdSe nanoparticles, the FTIR spectra (Fig. 6) were
Fig. 4 (A) Comparison of powder X-ray diffraction of CdSe: (a) Qdots
and (b) MSNCs showing zinc-blende crystallites; (B) MSNCs formed at
150

C using different ratio surfactants.
Fig. 5 XPS spectra of magic-size CdSe (A) Se 3d (core level) (B) Cd 3d
(core level) and (C) O 1s (core level).
2766 | CrystEngComm, 2010, 12, 27622768 This journal is The Royal Society of Chemistry 2010
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studied. All samples of MSNCs showed identical spectra with
3% cm
1
variation in the peak positions. The major peaks were
assigned on the basis of typical IR spectrum of pure oleic acid
33
given in parenthesis. The broad feature between 3405 and
3390 cm
1
(3500 and 2500 cm
1
) was undoubtedly due to the
OH stretch of the carboxylic acid. The two sharp bands at 2917
(2925) cm
1
and 2850 (2854) cm
1
can be attributed to the
asymmetric and symmetric CH
2
, stretch, respectively and are
shifted to lower frequency compared to oleic acid indicating that
the hydrocarbon particles in the monolayer surrounding the
CdSe particles are in close-packed crystalline state. The C]O
stretch observed in IR spectrum of oleic acid alone (1700
1730 cm
1
) is absent in the CdSe particles. Instead well dened
bands 1528 cm
1
(s) characteristic of the asymmetric n
as
and
1435, 1405 cm
1
(COO

) characteristic of the symmetric n

s
(COO

) stretch are observed. This shows that the oleic acid is

chemisorbed as a carboxylate onto the CdSe quantum dots.
Further the wavenumber separation D of 120 cm
1
seems to
indicate chelating bidentate mode of interaction of carboxylate
with metal atom rather than monodentate or bridging bidentate.
The observation of both OH stretch and C]O stretch of oleic
acid indicates that the adsorption of oleic acid is not conned to
single mode and/or monolayer. Both protonated and deproto-
nated oleic acid (via bidentate mode) seem to be present akin to
a CdSe cluster capped with oleic acid. The protonated oleic acid
may be interacting weakly via its double bond. The bands in the
region 682 cm
1
and 719 cm
1
can be assigned out of plane OH
bend and CH
2
rocking and are again shifted to lower frequency
compared to oleic acid. The rocking frequency of different
samples shows maximum deviation. The FTIR data together
with XPS is strongly indicative of the bidendate mode of bonding
of carboxylate group to metal in which both oxygens are
equivalent rather than monodendate bond with inequivalent
oxygen atoms. In that case the IR spectrum would have dis-
played strong band at 17001730 cm
1
and the O1s XP spectrum
would have shown another peak around 532 eV. Whereas sele-
nadiazoles are known to decompose thermally to produce
alkynes or a 1,4-diselenin compounds
25
the absence of IR bands
in the region 1500 cm
1
indicate that there is no surface capping
of alkyne or contamination of the diselenin in the nal product.
3.6 TEM
Though the use of TEMfor identication of particles below2 nm
is challenging, the TEM micrographs (Fig. 7A) of dried and re-
dispersed CdSe were collected and the gure showed onion like
patterns at certain places with certain degree of elongation which
is also indicated by XRD (220 plane) analysis. Further the
HRTEM (Fig. 7B) clearly shows the existence of lattice fringes
and sub nm scale particles in the atomic planes which may be
point defects. The concentric rings in the selected area electron
diffraction (SAED) are considered due to zinc blende crystal
structure and the presence of these rings conrm that the mate-
rial is highly crystalline.
Conclusions
Organoselenium compounds such as 1,2,3-selenadiazoles can
function as low temperature sources of reactive selenium for the
preparation of metal selenide (CdSe) nanocrystals. Fine tuning
the process by maintaining moderate temperatures (100150

C)
and varying the ratios in which reactants and capping agents are
used gives thermodynamically stabilized magic-size CdSe
nanocrystals. The above results have led us to dene the differ-
entiating conditions which lead exclusively to formation of
magic-size nanocrystals. The process can be easily scaled up to
give gram quantities of material. The above results further
demonstrate a method which gives exclusively zinc-blende
nanocrystals with the avoidance of TOP or similar phosphorus
ligands. The emission properties of these particles (12 nm) (on
the basis of UV-absorptions) are dominated by surface
phenomenon which produces the broad emissions due to surface
defects. IR and XPS indicate that the oleic acid carboxylate
seems to be binding via a bidentate mode. The powder XRD
shows that the material is clearly zinc-blende (cubic). Visualiza-
tion of the particles by TEM showed the material is highly
crystalline. We are currently exploring the utility of this method
for the preparation of other metal selenide nanocrystals.
Fig. 6 Comparison of FTIR spectra of magic-size CdSe formed at
150

C using different ratios of reactants.
Fig. 7 (A) TEM with inset selected area electron diffraction (SAED) of
magic-size CdSe formed at 150

Cusing the ratio of 1 : 2 : 10 of Se source :

Cd source : oleic acid; (B) HRTEM lattice imaging with inset lattice
fringes.
This journal is The Royal Society of Chemistry 2010 CrystEngComm, 2010, 12, 27622768 | 2767
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Acknowledgements
This work was supported by DST Govt. of India (Grant no. SR/
S1/PC-17/2006). We thank Executive Director C-MET, Dr AK
Viswanath, Dr CVVV Satyanarayana for fruitful discussion and
Prof. BRMehta for permission to use TEMand HRTEMfacility
of Unit on Nanoscience and Nanotechnology Initiative at IIT
Delhi (Project No. SR/S5/NM-22/2004) of DST Govt. of India.
Notes and references
1 K. S. Leschkies, R. Divakar, J. Basu, E. Enache-Pommer,
J. E. Boercker, C. B. Carter, U. R. Kortshagen, D. J. Norris and
E. S. Aydil, Nano Lett., 2007, 7, 17931798.
2 M. Achermann, M. A. Petruska, D. D. Koleske, M. H. Crawford and
V. I. Klimov, Nano Lett., 2006, 6, 13961400.
3 R. C. Somers, M. G. Bawendi and D. G. Nocera, Chem. Soc. Rev.,
2007, 36, 579591; A. Robe, E. Pic, H. Lassalle, L. Bezdetnaya,
F. Guillemin and F. Marchal, BMC Cancer, 2008, 8, 111.
4 I. Robel, V. Subramanian, M. Kuno and P. V. Kamat, J. Am. Chem.
Soc., 2006, 128, 23852393; P. V. Kamat, J. Phys. Chem. C, 2008, 112,
1873718753; R. D. Schaller and V. I. Klimov, Phys. Rev. Lett., 2004,
92, 186601.
5 L. Manna, E. C. Scher and A. P. Alivisatos, J. Am. Chem. Soc., 2000,
122, 1270012706; C. Burda, X. Chen, R. Narayanan and
M. A. El-Sayed, Chem. Rev., 2005, 105, 10251102.
6 V. N. Soloviev, A. Eichhofer, D. Fenske and U. Banin, J. Am. Chem.
Soc., 2000, 122, 26732674; V. N. Soloviev, A. Eichhofer, D. Fenske
and U. Banin, J. Am. Chem. Soc., 2001, 123, 23542364.
7 Z. A. Peng and X. Peng, J. Am. Chem. Soc., 2002, 124, 33433353.
8 M. J. Bowers, J. R. McBride and S. J. Rosenthal, J. Am. Chem. Soc.,
2005, 127, 1537815379.
9 J. Ouyang, B. Zaman, F. Yan, D. Johnston, G. Li, X. Wu, D. Leek,
C. I. Ratcliffe, J. A. Ripmeester and K. Yu, J. Phys. Chem. C, 2008,
112, 1380513811.
10 N. Herron, A. Suna and Y. Wang, J. Chem. Soc., Dalton Trans., 1992,
23292335.
11 C. B. Murray, D. J. Norris and M. G. Bawendi, J. Am. Chem. Soc.,
1993, 115, 87068715.
12 V. L. Colvin, M. C. Schlamp and A. P. Aliviatos, Nature, 1994, 370,
354356.
13 I. G. Dance, A. Choy and M. L. Scudder, J. Am. Chem. Soc., 1984,
106, 62856295.
14 S. Behrens, M. Bettenhausen, A. C. Deveson, A. Eichhofer,
D. Fenske, A. Lohde and U. Woggon, Angew. Chem., Int. Ed.
Engl., 1996, 35, 2215.
15 V. Ptatschek, T. Schmidt, M. Lerch, G. Muller, L. Spanhel,
A. Emmerling, J. Fricke, A. H. Foitzik and E. Langer, Ber. Bunsen-
Ges. Phys. Chem., 1998, 102, 8595.
16 A. Kasuya, R. Sivamohan, Y. A. Barnakov, I. M. Dmitruk,
T. Nirasawa, V. R. Romanyuk, V. Kumar, S. V. Mamykin,
K. Tohji, B. Jeyadevan, K. Shinoda, T. Kudo, O. Terasaki, Z. Liu,
R. V. Belosludov, V. Sundararaja and Y. Kawazoe, Nat. Mater.,
2004, 3, 99102.
17 R. Jose, N. U. Zhanpeisov, H. Fukumura, Y. Baba and M. Ishikaw,
J. Am. Chem. Soc., 2006, 128, 629636.
18 J. R. McBride, T. C. Kippeny, S. J. Pennycook and S. J. Rosenthal,
Nano Lett., 2004, 4, 12791283.
19 C. Landes, M. Braun, C. Burda and M. A. El-Sayed, Nano Lett.,
2001, 1, 667670; C. Landes and M. A. El-Sayed, J. Phys. Chem. A,
2002, 106, 76217627; X. Chen, A. C. S. Samia, Y. Lou and
C. Burda, J. Am. Chem. Soc., 2005, 127, 43724375.
20 L. Qu, W. W. Yu and X. Peng, Nano Lett., 2004, 4, 465469.
21 S. Kudera, M. Zanella, C. Giannini, A. Rizzo, Y. Li, G. Gigli,
R. Cingolani, G. Ciccarella, W. Spahl, W. J. Parak and L. Manna,
Adv. Mater., 2007, 19, 548552.
22 M. J. Bowers, J. R. Mcbride and S. J. Rosenthal, US Pat.
20 070 170 418, 17 October 2006.
23 R. K. Beri, P. More, B. G. Bharate and P. K. Khanna, Curr. Appl.
Phys., 2010, 10, 553556; P. K. Khanna, R. M. Gorte and
R. Gokhale, Mater. Lett., 2004, 53, 96669.
24 H. Meier and E. Voigt, Tetrahedron, 1972, 28, 187.
25 P. K. Khanna, C. P. Morley, R. M. Gorte, R. Gokhale,
V. V. V. S. Subbarao and C. V. V. Satyanarayana, Mater. Chem.
Phys., 2004, 83, 323327.
26 W. W. Yu, L. Qu, W. Guo and X. Peng, Chem. Mater., 2003, 15,
28542860.
27 D. J. Norris and M. G. Bawendi, Phys. Rev. B: Condens. Matter,
1996, 53, 1633816346.
28 L. Liu, Q. Peng and Y. Li, Inorg. Chem., 2008, 47, 50225028.
29 R. K. Beri and P. K. Khanna, Unpublished results.
30 K. Eichkorn and R. Ahlrichs, Chem. Phys. Lett., 1998, 288, 235.
31 Z. A. Peng and X. Peng, J. Am. Chem. Soc., 2001, 124, 33433353;
H. W. Kroto, J. R. Heath, S. C. OBrien, R. F. Curl and
R. E. Smalley, Nature, 1985, 318, 162163; T. Vossmeyer, G. Reck,
B. Schulz, E. T. K. Haupt and H. Weller, Science, 1995, 267, 1477.
32 J. E. Bowen Katari, V. L. Colvin and A. P. Alivisatos, J. Phys. Chem.,
1994, 98, 41094117.
33 N. Wu, L. Fu, M. Su, M. Aslam, K. C. Wong and V. P. Dravid, Nano
Lett., 2004, 4, 383386.
2768 | CrystEngComm, 2010, 12, 27622768 This journal is The Royal Society of Chemistry 2010
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