PHYSICS, CHEMISTRY AND APPLICATION OF NANOSTRUCTURES, 2011

NEW ASPECTS IN THE HOT INJECTION SYNTHESIS TO

PROVIDE LARGE SCALE HIGH QUALITY QUANTUM DOTS
C. WAURISCH, L. LIEBSCHER, E. SPERLING, S. G. HICKEY, A. EYCHMLLER
Physical Chemistry, TU Dresden, Bergstrae 66b, 01062 Dresden, Germany
c.waurisch@chemie.tu-dresden.de
The quasi seeded growth approach is investigated as a possibility to optimize hot
injection methods in order to provide high quality CdSe and PbSe quantum dots. This
technique is reported here as a novel means by which up-scaling may be implemented.

1. Introduction
Colloidal semiconductor nanoparticles exhibit unique optical and (opto-)
electrochemical properties and thus are the subject of many areas of research
including chemistry, physics and material science. These so called quantum dots
(QDs) find applications as materials in solar cells, light emitting diodes,
thermoelectric devices as well as lithium ion batteries, which requires materials
of high quality with well adjusted properties and, in particular for industrial
implementation, production in large quantities.
The hot injection method is a widely employed, laboratory based, organometallic approach for the production of high quality QDs. This synthetic route
involves a rapid injection of a precursor solution into a hot solution of high
boiling coordinating components to affect a homogeneous nucleation event
which is followed by the subsequent growth at lower temperatures.1 The
precursor injection leads to monomer formation and, due to their
supersaturation, nuclei are formed. After lowering the reaction temperature the
energy barrier for nucleation cannot be overcome and the growth process is
favored while further nucleation is suppressed. When the precise reaction
conditions have been determined it is possible to separate nucleation and growth
which is crucial to control the size distribution of the particles and thus to obtain
high quality material.
The seeded growth method is a modification of the hot injection procedure
where nuclei are introduced into the reaction and thus heterogeneous nucleation
results. A special case of this approach is the quasi seeded growth, wherein
nuclei of a different material are formed in situ and subsequently a cation
exchange occurs whereupon the required seeds are formed and the overall
process is simplified to the growth of the particles (see Figure 1).2 Whilst in the

bulk the exchange reaction is kinetically hindered, in the nanoparticular size

regime it is thermodynamically favored.3

Figure 1. Mechanism of the quasi seeded growth approach.

In this work the hot injection syntheses conditions by which high quality
CdSe and PbSe nanoparticles may be obtained are optimized via the quasi
seeded growth approach. Different precursors and precursor concentrations for
the quasi seed formation are investigated and with the optimized protocols an
up-scaling is presented by increasing the apparatus dimensions as well as the
precursor concentrations.
2. Experimental
The standard nanocrystal syntheses were performed following modified
procedures of J. J. Li et al.4 for CdSe and from M. Nagel et al.5 for PbSe.
CdSe nanocrystals: A mixture of 0.4 mmol of CdO, 2 mmol of oleic acid in
9.5 g of 1-octadecene was heated to 100C under vacuum for 30 min and further
under Ar to 300C until a clear, colourless solution was obtained. Subsequently
the solution is cooled to 100C, 5 mmol of n-trioctylphosphine oxide and
8 mmol of hexadecylamine added and again kept at 100C under vacuum for
30 min. After heating to 270C under Ar, a mixture of 0.4 mmol of Se in
4.5 mmol n-trioctylphosphine and 1.5 g 1-octadecene was swiftly injected.
PbSe nanocrystals: Typically, a mixture of 2 mmol lead acetate trihydrate,
4.7 mmol oleic acid, 10 mL diphenylether and 9 mmol n-trioctylphosphine
(TOP) was heated under vacuum for 1 h at 90C and a further hour at 100C
under N2, before the Se-precursor solution made from 2 ml (1 M) Se in TOP,
0.5 ml (1.2 M) diphenylphosphine in TOP and 13.5 mmol TOP was injected.
Quasi seeded growth approach: As quasi seeds M. V. Kovalenko et al.2
propose SnSe for the synthesis of PbSe nanocrystals. As a highly reactive
species bis[bis(trimethylsilyl)amino]tin(II) is used. This precursor is added (5 %

with regard to the second cation) to both reaction solutions before injection of
the anion precursor.
3. Results and discussion
As can be seen from Figure 2, several features in the absorption spectra related
to the different excitonic transitions are more pronounced, for example the 1Se1Sh transition of the PbSe, compared to the normal hot injection procedure.
Significant changes in the full width at half maxima of interband transition
peaks provide an indication of the quality of the quantum dots, especially that of
the particle size distribution.

Figure 2. Absorption spectra of CdSe and PbSe

QDs prepared via the normal hot injection (hi) and
the quasi seeded growth approach (qsg).

Figure 3. Absorption spectra of PbSe QDs

prepared via the quasi seeded growth
approach with different quasi seed precursors.

In Figure 3 absorption spectra are shown which derive from different quasi
seed precursors used in the synthesis of PbSe QDs. Only the highly reactive
tin silylamide yields the pronounced absorption features although the silylamide
ligand itself is known to stabilize undercoordinated metals and thus increase the
particle quality.6
To demonstrate that the quasi seeded growth method could be employed as
an up-scaling protocol, the flask volume was increased by a factor of 2 while at
the same time the precursor concentrations were increased by a factor of 10.
Figure 4 shows the optical spectra of the resulting CdSe nanocrystals. Similar to
the results of the small scale syntheses the absorption features are more
pronounced in the quasi seeded growth approach. While the normal hot injection
method yields a broad size distribution, the cation exchange mediated synthesis
results in a better separation of nucleation and growth and thus the size
distribution is much smaller (cp. Emission spectra Fig. 4).

Figure 4. Absorption (left) and emission (right) spectra of the up-scaled approach to provide CdSe
nanocrystals via the standard hot injection (hi) as well as the quasi seeded growth method (qsg).

4. Conclusion
We report the quasi seeded growth route as a special
case of the hot injection method. It has been
successfully adapted to the optimization of two
syntheses providing CdSe and PbSe QDs. Further we
have demonstrated this approach as a novel means to
achieve the up-scaling of the laboratory standardized
protocols. It is envisioned that this methodology may
be applied to the syntheses of difficult to access QD
materials and to the up-scaling of the synthesis of
other QD protocols.

Figure 5. HR TEM image of

PbSe nanocrystals prepared
via the quasi seeded growth
approach

Acknowledgments
The authors are grateful to the Deutsche Forschungsgemeinschaft (DFG) for
financial support through the Priority Program SPP1313 and the Research
Training Group GRK1401.
References
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M. Nagel et al., Z. Phys. Chem. 221, 427 (2007)
M. Yarema et al., J. Am. Chem. Soc. 132, 15158 (2010)