Synthesis and Characterization of a Size Series of Extremely Small Thiol-Stabilized CdSe
Nanocrystals
Andrey L. Rogach,
†,‡
Andreas Kornowski,
†
Mingyuan Gao,
§
Alexander Eychmu1 ller,*
,†
and
Horst Weller
†
Institut fu¨r Physikalische Chemie, UniVersita¨t Hamburg, 20146 Hamburg, Germany, and
Max-Planck-Institut fu¨r Kolloid- und Grenzfla¨chenforschung, 12489 Berlin, Germany
ReceiVed: December 31, 1998; In Final Form: March 11, 1999
As an expansion to the wet chemical route for the preparation of quantum-sized II-VI semiconductor materials,
a series of thiol-capped crystalline CdSe nanoparticles has been synthesized in aqueous solution using mercapto-
alcohols (2-mercaptoethanol, 1-thioglycerol), and mercapto acids (thioglycolic acid, thiolactic acid) as stabilizers.
The smaller (app. 1.4-2.2 nm diameter) CdSe particles were obtained using thioalcohols as capping agents;
the use of thioacids as stabilizers produced larger (2.1-3.2 nm diameter) CdSe particles. CdSe nanoparticles
were separated from the crude solutions as redissolvable powder samples with narrow size distributions using
a size-selective fractionation and have been characterized by UV-vis absorption and photoluminescence
spectroscopy, X-ray diffraction, high-resolution transmission electron microscopy, and energy-dispersive X-ray
analysis. A calculation of the HOMO-LUMO gap of CdSe particles as a function of their size has been done
using an extended effective mass approximation.
Introduction
A number of exciting size- and surface-dependent properties
of nanometer-sized semiconductor particles,
1
which lie between
molecular and bulk forms of matter, have stimulated an
exponential development of nanochemistry and nanophysics in
the past decade which is currently being realized in nanotech-
nology.
2
Extensive research has been done in the synthesis and
characterization of colloidal II-VI semiconductor nanoparticles.
An important landmark in the development of wet chemical
routes for cadmium chalcogenide nanocrystals was, together
with the nonaqueous TOP/TOPO (trioctyl phosphine /trioctyl
phosphine oxide) technique,
3
the use of different thiols as
stabilizing agents in aqueous solution.
4-6
A monodisperse size
series of thioalcohol-stabilized CdS
7
and CdTe
8
nanoparticles
with extremely small sizes (1-3 nm size range) was synthesized
in aqueous solutions and was obtained in the gram scale as
redissolvable nanocrystalline powders or as crystals of nano-
clusters (superstructures).
9,10
To complete the series of thiol-
stabilized cadmium chalcogenide nanocrystals synthesized by
a wet chemical route in aqueous solution, CdSe nanoparticles
were synthesized. The basic spectroscopic and structural
characterizations of thiol-capped CdSe nanoparticles are pre-
sented, reserving a more detailed study of some selected CdSe
samples for future investigations.
Experiment
Chemicals. All chemicals used were of analytical grade or
of the highest purity available. They were obtained from Sigma,
Merck, Aldrich, Alfa, and Fluka and used as received. The
solution of 0.05 M NaHSe was prepared following the synthesis
route of NaHTe solution described previously.
8
Under a N
2
atmosphere, 100 mL of 0.05 M NaOH solution was titrated with
H
2
Se (generated by the reaction of Al
2
Se
3
with 10% H
2
SO
4
).
Al
2
Se
3
was used in a 1.7-fold excess to the calculated quantity.
After titration, the solution was bubbled with N
2
for 30 min to
remove any traces of H
2
Se present in the solution. The solution
of NaHSe can be stored under nitrogen for some days but in
this case was used directly after preparation.
Apparatus. Room-temperature UV-vis absorption spectra
were obtained with a Perkin-Elmer Lambda 40 UV-vis
spectrophotometer. Photoluminescence measurements were
performed at room temperature using a FluoroMax-2 spectro-
fluorimeter (Instruments SA). X-ray powder diffraction (XRD)
spectra were taken on a Philips X’Pert diffractometer (Cu KR
radiation, variable entrance slit, Bragg-Brentano geometry,
secondary monochromator). Samples for these measurements
were prepared by placing finely dispersed powders of CdSe
nanoparticles on standard PVC supports. High-resolution trans-
mission electron microscopy (HRTEM) and energy-dispersive
X-ray analysis (EDX) were performed on a Phillips CM-300
microscope operating at 300 kV. TEM samples were prepared
by dropping diluted aqueous solutions of CdSe nanoparticles
onto 400-mesh carbon-coated copper grids with the excess
solvent immediately evaporated.
Results and Discussion
Synthesis of CdSe Nanoparticles. Aqueous colloidal solu-
tions of CdSe nanoparticles have been synthesized through the
addition of freshly prepared oxygen-free NaHSe solutions to
N
2
-saturated Cd(ClO
4
)
2
‚6H
2
O solutions at pH 11.2 in the
presence of different thiols as stabilizing agents. The CdSe
particle size was controlled by the type of stabilizer and through
postpreparative size-selective precipitation. As has been shown
in our previous studies,
7,8
thioalcohols (2-mercaptoethanol and
1-thioglycerol) are effective size-regulating and stabilizing
* Corresponding author. E-mail: eychmuel@chemie.uni-hamburg.de.
Fax: +49-40 428383452.
†
Universita¨t Hamburg.
‡
Permanent address: Physico-Chemical Research Institute, Belarussian
State University, 220050 Minsk, Belarus.
§
Max-Planck-Institut.
3065J. Phys. Chem. B 1999, 103, 3065-3069
10.1021/jp984833b CCC: $18.00 © 1999 American Chemical Society
Published on Web 04/03/1999
agents for cadmium chalcogenide nanoparticles. In addition,
thioglycolic and thiolactic acids were also used as stabilizers
for CdSe nanoparticles as reported by Gao et al.
11
A solution of 1.97 g (4.70 mmol) of Cd(ClO
4
)
2
‚6H
2
O and
11.54 mmol of the stabilizer (RSH) in 250 mL of demineralized
water was adjusted to pH 11.2 with 1 M NaOH. The solution
was placed in a three-necked flask fitted with a septum and
valves and was deaerated with N
2
bubbling for 30 min. Under
vigorous stirring, 44 mL (2.2 mmol) of the freshly prepared
oxygen-free 0.05 M NaHSe solution was injected. The initial
molar ratio Cd
2+
/Se
2-
/RSH was therefore app. 1:0.5:2.4, which
were the same conditions used for the preparation of thiol-
stabilized CdS
7
and CdTe
8
nanoclusters.
The addition of NaHSe produced bright-yellow, transparent
colloids stable toward oxidation under air. Solutions were
refluxed for different times (up to 12 h), and aliquots were
removed at regular intervals (15-30 min) with absorption
spectra taken to monitor the growth of the clusters. The
development of absorption spectra of thioalcohol-stabilized CdSe
nanoparticles with time resembles that of thioalcohol-stabilized
CdS and CdTe nanoparticles.
7,8
Addition of the NaHSe solution
caused the appearance of absorption shoulders or maxima in
the UV region and unstructured absorption features at longer
wavelengths. The heating of the solutions led to an increase of
absorption between 330 and 400 nm at the expense of the short-
wavelength bands. New absorption maxima appeared at specific
wavelengths, suggesting the formation of some thermodynami-
cally favorable cluster structures. A prolonged refluxing (up to
12 h) caused a continuous red shift of the absorption edge up
to 450 nm which was not accompanied with a formation of
new pronounced absorption maxima. Particle growth occurred
continuously at this stage via Ostwald ripening.
In contrast, no or only very weakly pronounced absorption
maxima were observed at the initial stage of the synthesis of
CdSe nanoparticles in the presence of thioacids, and the
absorption edge which appeared after addition of NaHSe
solution lay in the visible spectral range. During the heating of
the solution, the particle growth proceeded about 5 times faster
than for thioalcohol-stabilized CdSe and larger CdSe particles
were formed. A prolonged refluxing (up to 12 h) of the solutions
of thioacid-stabilized CdSe nanoparticles caused a red shift of
the absorption edge up to 530-540 nm due to continuous
growth of the particles.
Isolation of CdSe Nanoparticle Fractions: Absorption and
Photoluminescence of the Particles. Absorption spectra of the
crude colloidal solutions represented a mixture of CdSe nano-
particles with different sizes. The method of size-selective
precipitation
12
was used to isolate the samples of CdSe
nanoparticles with different sizes and narrow size distributions
from crude solutions. They were concentrated down to app. 30
mL using a rotary evaporator, and 2-propanol was added
dropwise until turbidity occurred. The solutions were stirred
for 2-3 h, and the precipitate and supernatant were separated
through centrifugation.
Figure 1 shows sets of absorption spectra of mercaptoethanol
and thioglycolic acid stabilized CdSe nanoparticles with different
sizes separated from the corresponding crude solutions. The
narrowing of the size distribution of the particles led to a better
resolution of the 1s-1s electronic transitions. As expected for
quantum-sized particles, the position of the first electronic
transition was shifted to higher photon energies and became
more pronounced with decreasing particle size in accordance
with the size quantization effect.
1
Higher electronic transitions
were also clearly resolved for the smallest CdSe nanoparticles
(Figure 1).
Figure 1. Absorption spectra of the isolated fractions of CdSe
nanoparticles capped with 2-mercaptoethanol (a) and thioglycolic acid
(b).
Figure 2. Powder X-ray diffractograms of the isolated fractions of
CdSe nanoparticles. The particle size decreases from top to bottom;
particle sizes obtained from Bragg and Scherrer equations are shown.
The line spectra give the bulk CdSe reflections (top, wurzite hexagonal;
bottom, zinc blende cubic).
3066 J. Phys. Chem. B, Vol. 103, No. 16, 1999 Letters
Both thioalcohol- and thioacid-stabilized CdSe nanoparticles
showed a broad photoluminescence band with a room temper-
ature photoluminescence quantum yield of less than 0.1%
(referenced by Rhodamin 6G) and a maximum which shifted
strongly toward longer wavelengths in comparison with the
absorption edge. This kind of photoluminescence which has been
ascribed to an emission from deep surface traps was also
observed for a series of thioalcohol-capped CdS clusters.
13
The
photoluminescence maxima of thioalcohol-stabilized CdSe
particles were located at about 600 nm and were further shifted
toward the near IR for thioacid-stabilized ones.
Structural Characterization of CdSe Nanoparticles. Small-
and wide-angle powder X-ray diffractometry has been performed
on the powders of isolated fractions of CdSe nanoparticles.
Figure 2 shows X-ray diffraction patterns of some selected
fractions of CdSe nanoparticles capped with different stabilizers.
The diffractograms confirmed the crystallinity of the CdSe
nanoparticles. The positions of the reflection peaks matched the
cubic modification of CdSe (zinc blende phase) better than the
hexagonal one. Note that the cubic modification has also been
found to be more preferable for thiol-capped CdS and CdTe
nanocrystals
7,8
synthesized in aqueous solution at moderate
temperatures as opposed to the hexagonal phase for cadmium
chalcogenides obtained through the high-temperature TOP/
TOPO technique.
3
Alkoxysilane-stabilized CdSe nanocrystals
exhibited cubic zinc blende structure.
14
Modeling of the
experimentally observed XRD spectra using the hexagonal
modification of CdSe with the presence of stacking faults along
the (002) axis has been performed by Murray et al.,
3
possibly
fitting our data for the smaller CdSe nanoparticles better than
the cubic modification. An extensive structural characterization
of thiol-stabilized CdSe nanoparticles will be left for future
investigations.
The broadness of the diffraction peaks of CdSe nanoparticles
shown in Figure 2 increased gradually with a decrease of particle
size. The mean nanocrystal sizes obtained from the full width
at half-maximum intensity of the (111) zinc blende reflection
according to the Scherrer equation are depicted in Figure 2. A
reflection maximum appeared also in the small-angle region of
the X-ray diffraction patterns due to the periodicity of their
arrangement. The appearance of such a peak provides further
confirmation for the narrow size distribution of the particles.
The peak angle maxima can be converted to the nearest neighbor
distances of the nanoparticles in the powdered samples by using
the Bragg equation. These distances can be used as a measure
of the mean particle size as has been discussed in refs 7 and 8.
The calculated values are depicted in Figure 2 and are in
surprisingly good agreement with the ones obtained from the
Scherrer equation.
Figure 3 shows a typical HRTEM overview image of CdSe
nanoparticles (here thioglycerol-stabilized CdSe particles with
the excitonic maximum in the absorption spectrum at ca. 375
nm) together with a single CdSe particle and its corresponding
fast Fourier transform (FFT). The existence of lattice planes on
the HRTEM image further confirmed the crystallinity of CdSe
nanoparticles. The average sizes estimated from HRTEM
micrographs were generally larger than those obtained from
XRD patterns, a trend already observed for thiol-stabilized CdS
Figure 3. HRTEM overview image of thioglycerol-stabilized CdSe nanoparticles together with a single CdSe particle and its corresponding FFT.
Letters J. Phys. Chem. B, Vol. 103, No. 16, 1999 3067
clusters with comparable sizes.
7
We note here that electron
microscopy in this regime of extremely small sizes may lead
to an overestimation of the contribution of larger particles of
the given size distribution. Additionally, Rietveld analysis of
the XRD spectra reveals larger particle sizes than those obtained
through Braggs and Scherrers equations
15
and thus converging
to the particle sizes estimated from the TEM images.
EDX measurements on CdSe nanocrystals indicated the
presence of Cd, Se, and S with the atomic ratio of S/Se
increasing with decreasing of the particle sizes. This correlates
with the increase of the surface-to-volume ratio when particles
become smaller, which corresponds to a larger amount of
stabilizing thiol molecules (and S atoms) on the particle surface
relative to the number of Se atoms in the particle core.
Calculation of the 1s-1s Electronic Transition of CdSe
Nanoparticles. Calculation of the HOMO-LUMO gap of CdSe
nanoparticles as a function of their size (treated as spheres) has
been done using an extended theoretical approach described in
detail in ref 16. The extension of the common effective mass
approximation included the implementation of the Coulomb
interaction and finite potential walls at the particle boundaries
in water as the surrounding dielectric medium. The physical
parameters put into the model were E
g,CdSe
) 1.7 eV,
17
the
effective masses m
e,H
2
O
) m
h,H
2
O
) 1, m
e,CdSe
) 0.11, m
h,CdSe
) 0.44, and the high-frequency dielectric constants
H
2
O
) 1.78,
CdSe
) 5.8.
18
The results of the calculation of the 1s-1s transition energy
in CdSe nanoparticles as a function of particle size are shown
in Figure 4 together with experimental values derived from XRD
patterns for some fractions of CdSe nanoparticles. Two regions
for HOMO-LUMO transition energies were obtained from the
absorption spectra of CdSe particles and, accordingly, two size
regions are depicted on Figure 4; CdSe nanoparticle sizes from
1.4 to app. 2.2 nm were achieved using thioalcohols and from
app. 2.1 to 3.2 nm using thioacids as stabilizing agents. CdSe
particle sizes obtained from the theoretical curve in Figure 4
are in reasonable agreement with the experimentally determined
values.
Summary
Some characteristics of the series of thiol-stabilized CdSe
nanoparticles with different sizes are summarized in Table 1.
All particles were in the size quantization regime in comparison
with bulk CdSe. Second electronic transitions were clearly
resolved for the smallest CdSe nanoparticles. The size-dependent
shift of the CdSe particle band gap energies calculated by a
finite depth potential well model in the framework of the
effective mass approximation was in a reasonable agreement
with the experimentally observed change in the absorption
spectra of CdSe nanoparticles with size.
CdSe nanoparticles were crystalline and preferentially adopted
the cubic zinc blende CdSe phase. Although not favorable for
bulk CdSe,
19
the zinc blende phase appears to be observed for
thiol-capped CdS, CdSe, and CdTe nanoclusters synthesized in
aqueous solution at moderate temperature. Photoluminescence
of CdSe nanoparticles originated from deep surface traps and
was practically independent of particle size.
A detailed structural study of the series of CdSe nanoparticles
presented here, in particular a confirmation of the structure of
the smallest CdSe clusters with well-defined absorption features,
is the aim of future investigations.
Acknowledgment. We thank J. Ludwig from the Miner-
alogisch-Petrographisches Institut, Universita¨t Hamburg for
XRD measurements, and Dr. M. Harrison for carefully reading
the manuscript. Financial support was provided by the Volk-
swagen Foundation, Hannover. M.G. was supported by the
Alexander von Humboldt Foundation.
References and Notes
(1) For reviews, see, e.g.: Brus, L. E. Appl. Phys. A. 1991, 53, 465.
Wang, Y.; Herron, N. J. Phys. Chem. 1991, 95, 525. Banyai, L.; Koch, S.
W. Semiconductor Quantum Dots; World Scientific: Singapore, 1993.
Weller, H. Angew. Chem., Int. Ed. Engl. 1993, 32, 41. Weller, H. AdV.
Mater. 1993, 5, 88. Alivisatos, A. P. J. Phys. Chem. 1996, 100, 13226.
Woggon, U. Optical Properties of Semiconductor Quantum Dots. Springer-
Verlag: Berlin, 1997. Gaponenko, S. V. Optical Properties of Semiconduc-
tor Nanocrystals. Cambridge University Press: Cambridge, 1998.
(2) See, e.g.: Klein, D. L.; Roth, R.; Lim, A. K. L.; Alivisatos, A. P.;
McEuen, P. L. Nature 1997, 389, 699. Feldheim, D. L.; Keating, C. D.
Chem. Soc. ReV. 1998, 28, 1. Colvin, V. L.; Schlamp, M. C.; Alivisatos,
A. P. Nature 1994, 370, 354. Dabbousi, B. O.; Bawendi, M. G.; Onitsuka,
O.; Rubner, M. F. Appl. Phys. Lett. 1995, 66, 1316.
(3) Murray, C. B.; Norris, D. J.; Bawendi, M. G. J. Am. Chem. Soc.
1993, 115, 8706.
(4) Rajh, T.; Micic, O. I.; Nozik, A. J. J. Phys. Chem. 1993, 97, 11999.
(5) Lee, G. S. H.; Craig, D. C.; Ma, I.; Scudder, M. L.; Bailey, T. D.;
Dance, I. G. J. Am. Chem. Soc. 1988, 110, 4863.
(6) Herron, N.; Calabrese, J. C.; Farneth, W. E.; Wang, Y. Science
1993, 259, 1426.
(7) Vossmeyer, T.; Katsikas, L.; Giersig, M.; Popovic, I. G.; Diesner,
K.; Chemseddine, A.; Eychmu¨ller, A.; Weller, H. J. Phys. Chem. 1994,
98, 7665.
(8) Rogach, A. L.; Katsikas, L.; Kornowski, A.; Su, D.; Eychmu¨ller,
A.; Weller, H. Ber. Bunsen-Ges. Phys. Chem. 1996, 100, 1772; 1997, 101,
1668.
(9) Vossmeyer, T.; Reck, G.; Katsikas, L.; Haupt, E. T. K.; Schulz,
B.; Weller, H. Science 1995, 267, 1476.
(10) Vossmeyer, T.; Reck, G.; Schulz, B.; Katsikas, L.; Weller, H. J.
Am. Chem. Soc. 1995, 117, 12881.
TABLE 1: Comparison of Size, Electronic Transition Energies, Crystal Structure, and Photoluminescence Behavior of CdSe
Nanoparticles Capped with Different Stabilizers
stabilizer 2-mercaptoethanol 1-thioglycerol thioglycolic acid
crystal structure cubic CdSe (zinc blende) cubic CdSe (zinc blende) cubic CdSe (zinc blende)
photoluminescence trapped trapped trapped
1s-1s electronic transition, nm 360-450 360-450 450-530
diameter, nm 1.4-2.2 1.4-2.2 2.1-3.2
Figure 4. Calculated energy of the first electronic transition as a
function of the CdSe nanoparticle size together with experimental values
for some fractions of CdSe nanoparticles. Two regions of the particle
sizes are depicted for two types of stabilizers.
3068 J. Phys. Chem. B, Vol. 103, No. 16, 1999 Letters
(11) Gao, M.; Richter, B.; Kirstein, S. AdV. Mater. 1997, 9, 802.
(12) Chemseddine, A.; Weller, H. Ber. Bunsen-Ges. Phys. Chem. 1993,
97, 636.
(13) Vossmeyer, T. Dissertation. TU Berlin, 1995.
(14) Ptatschek, V.; Schreder, B.; Herz, K.; Hilbert, U.; Ossau, W.;
Schottner, G.; Raha¨user, O.; Bischof, T.; Lermann, G.; Materny, A.; Kiefer,
W.; Bacher, G.; Forchel, A.; Su, D.; Giersig, M.; Mu¨ller, G.; Spanhel, L.
J. Phys. Chem. B 1997, 101, 8898.
(15) Rockenberger, J. Dissertation. University of Hamburg, 1998.
(16) Schooss, D.; Mews, A.; Eychmu¨ller, A.; Weller, H. Phys. ReV.B
1994, 49, 17072.
(17) The value E
g,CdSe
) 1.7 eV was obtained by extrapolation of the
value E
g,CdSe
) 1.9 eV (cubic CdSe, 4 K, ref 18) to room temperature.
(18) Landolt-Bo¨rnstein, Numerical Data and Functional Relationship
in Science and Technology, New Series; Springer-Verlag: Berlin, 1982;
Group III, Vol. 17, Part b, Section 3.11.
(19) Sidgwick, N. V., Ed. The Chemical Elements and their Compounds;
Oxford University Press: London, 1952; Vol. 1, p 271.
Letters J. Phys. Chem. B, Vol. 103, No. 16, 1999 3069
