The photoluminescence of CdSe nanocrystals

ABSTRACT
CdSe quantum dots had been synthesized with a hot injection method. It was shown that the addition of Pb ions in the
initial precursor solution changed the morphology of CdSe nanocrystals from slightly prolate ellipsoid to branched rod.
Photoluminescence (PL) of the branched nanocrystals showed rapid depression of emission intensity due to the staggered
band alignment due to zinc blende-wurzite polytypism. Low temperature PL spectrum also support that PL integrated
intensity is caused by non-radiative recombination process due to the dissociation of excitons.

Keywords: Nanocrystals, Photoluminescence, Semiconductors, Alloy, Quantum dot, CdSe

1. INTRODUCTION
Synthesis of II-VI semiconductor nanocrystals has been intensely pursued due to their importance in optoelectronic,
photovoltaic and biological applications [1-3]. Since hot injection synthesis of mono-dispersed spherical nanocrystals
using organometallic precursors was introduced by an MIT group [4], extensive works have been devoted to make
variation of their size and shape [5-7]. The size and shape of semiconductor nanocrystals play an important role to
determine their electronic and optic properties. In particular, anisotropic nanocrystal exhibit unique performance such as
enhanced solar cell efficiency, polarized luminescence, etc. Thus, anisotropic nanocrystals with variety of compositions
such as CdS, CdTe, CdSe, etc. were synthesized with hot injection method [5-8]. In particular, tetrapod-shaped CdTe
nanocrystals were synthesized with high shape selectivity and high size uniformity [6,8]. In constrast to this, CdSe
nanocrystals were relatively hard to synthesize with high shape selectivity, since the energy difference between the
wurzite and the zinc blende is too small to facilitate tetrapod-shaped crystals [5,7]. Recently, Asokan et al. reported
synthesis of CdSe tetrapods with high shape selectivity and high size uniformity. 9 Most of syntheses of anisotropic CdSe
nanocrystals involve special surfactants such as alkylphosphonic acid, quaternary ammonium salt compounds, etc. These
surfactant ligands preferentially bind to certain particle facets to reduce growth rate of these facets.
In addition, doping in semiconductor nanocrystals can adjust their optical and electronic properties [10,11]. For
example, doping foreign atoms can introduce characteristic luminescence peaks in photoluminescence spectra of
nanocrystals and reduce the lasing threshold of semiconductor nanocrystals [11]. Thus, works on doped nanocrystals are
mainly devoted to tune the optical and electronic properties of nanocrystals. To our knowledge, reports on the
morphological development of nanocrystal by doping are quite rare [12]. In this study, we report the effect of Pb 2+
addition on the photoluminescence of CdSe nanocrystals and their structure-property relationships were analyzed.

2. EXPERIMENTAL PROCEDURE
2.1 Synthesis of nanocrystals
CdSe nanocrystals were synthesized by injection of selenium precursor solution into hot Cd precursor solution
modified from the synthesis method for spherical CdSe nanocrystals [13]. The Cd precursor solution was synthesized by
dissolving 4mmol CdO to the mixture of 10mmol oleic acid and 20ml 1-octadecene (ODE). Sometimes, lead (II) acetate
hydrate was intentionally added instead of the same amount of CdO maintaining total concentration of metal salts.
Subsequently, the mixtures were heated to 150oC under N2 gas flow and metallic precursors were completely dissolved to
form clear solution of metal oleate (solution A). Separately, 8mmol selenium powders were dissolved in 7.71ml
trioctylphosphine (TOP) under dry N 2 atmosphere in the glove box and the selenium solution was swiftly injected to Cdbased precursor solution A at 225 oC. Aliquots were taken at different time interval after injection and rapidly cooled to
room temperature. Before further characterization, acetone was added to precipitate CdSe-based nanocrystals and the
precipitates were purified by repetition of centrifugation and re-dispersion to toluene. Overall reaction occurred in this
synthesis reaction can be written as (1 x)[Cd(A)n1] + x[Pb(A)n1] + Se(B)n2 Cd1xPbxSe + n1A + n2B, where A and B
corresponds to oleic acid and trioctylphosphine, respectively.

2.2 Characterization
Before further characterization, polar solvent such as acetone, methyl alcohol, etc. was added to precipitate Cd(Se,S)based NCs and the precipitates were purified by repetition of centrifugation and re-dispersion to n-hexane. The
luminescence quantum yield (QY) calculated from comparison with the luminescence intensity of organic dye such as
Rhodamine 6G dissolved in ethanol (QY=0.95). Samples for temperature dependent photoluminescence and Raman
spectroscopy was prepared by drop casting the nanocrystal solution on the Si substrate. Temperature dependence of
photoluminescence spectra were measured with double monochromator (SPEX 1403) excited with He-Cd laser
(=325nm) from 6K to 300K. X-ray diffraction profiles were obtained with Rigaku D-1200. Transmission electron
microscopy (TEM) using field emission TEM (JEOL)was applied to investigate the size and shape of grown
nanocrystals.

3. RESULTS AND DISCUSSION

Fig. 1 shows the optical absorption and fluorescence spectra of CdSe nanocrystals synthesized with various amount of
incorporated Pb ions. Addition of Pb ions during synthesis significantly quenches the fluorescence of CdSe nanocrystals.
That is, the photoluminescence (PL) spectral intensity of CdSe nanocrystals is noticeably reduced by addition of Pb ions
during their synthesis as shown in the inset of Fig. 1b. In particular, optical absorption spectra shows a clear redshift and
values of Stokes shift is increased from 4meV to 60meV with increasing amount of Pb ions.
The shape and size of these nanocrystals were further characterized by transmission electron microscope (TEM, JEOL
2100F). Fig. 2 shows TEM images of CdSe nanocrystals grown at 225 oC. Although the synthesis procedure used in this
study was based on the known synthesis route to spherical CdSe nanocrystals [13], slightly prolate ellipsoidal CdSe
nanocrystals were obtained from Pb-free precursor solution. In contrast to this, nanocrystals grown from the precursor
solution containing Pb2+ under the same growth condition showed branched morphology. In particular, longer
nanocrystals were synthesized from the precursor solution containing more Pb 2+ ions. The typical length of each arms in
branched nanocrystals was about 8nm for x=0.05 and 20nm for x=0.2 of Cd1-xPbxSe and diameter of each branch showed
no noticeable change. Thus, the aspect ratio of nanocrystals was increased with initial abundance of Pb ions in the
precursor solution. It is known that branched nanorods of II-VI semiconductors can be synthesized by controlling growth
rate and reaction kinetics. In particular, application of weak binding ligands such as oleic acid and high precursor
concentration were known to accelerate linear growth rate of nanocrystals [5,6]. Furthermore, the relatively low growth
temperature can contribute to form anisotropic growth [15]. Although a weak binding ligand and low growth temperature
condition were applied during the synthesis of nanocrystals in this study, only slightly prolate CdSe nanocrystals were
grown under Pb-free condition. In addition, the length of anisotropically grown nanocrystals was increased according to
the abundance of Pb in the precursor solution. Thus, Pb ions incorporated during the growth of nanocrystals played an
important role in anisotropic growth of CdSe nanocrystals. The high resolution TEM (HR-TEM) image of Pb-containing
nanocrystals presented in Fig. 3 showed highly entangled and branched morphology. Analysis of the lattice image
showed that the planar spacing along axis of nanorods is about 0.35nm, which corresponds to planar spacing of (002)
planes in the wurzite CdSe. Again, it was confirmed that CdSe crystals were preferentially grown along [002] direction.
The junction point of the two branches is composed of zinc blende phase as indicated by dotted circle in Fig. 3. Detailed
inspection of the HR-TEM image shows polytypic stacking faults. In CdSe, difference in formation energy of zinc

blende (ZB) and wurzite (WZ) phase is small and as a result of this, polytypic zinc blende/wurzite structure is not rare
[7]. Then, the cubic zinc blende phase and hexagonal wurzite phase are stacked alternatively along [001] axis. Since the
band structures of ZB and WZ is different, there are energy offset in the interface between ZB and WZ as illustrated in
Fig.3. Then, the staggered band alignment is expected for both conduction band offset and valence band offset. The
staggered band alignment usually induce spatial charge separation by exciton dissociation, since electrons move to ZB
region and holes move to WZ region. Then, the photogenerated holes and electrons are spatially separated and chance of
recombination of electrons and holes for luminescence is highly limited. In addition, the electron-hole recombination can
mainly be occurred at near the interface between ZB phase and WZ phase as a result of spatial charge separation.
Consequently, the PL intensity of Pb-containing CdSe nanocrystals are highly reduced and energy of luminescence is
reduced by sum of band offset of conduction band and valence band. That is, the Stokes shift of Pb-containing CdSe
nancrystals is highly exaggerated as shown in Fig. 1b.
Raman spectroscopy has been used to study the structure of nanocrystals. Specimen for Raman spectra were prepared
by dropping solution containing nanocrystals onto silicon wafer. After drying, Ar + laser (=514.5nm, power less than
10mW) was focused on a spot of 50m diameter in each sample and Raman spectra were collected with a triple Raman
spectrometer (SPEX-1430). Fig.4(a) showed a Raman spectrum of the nanocrystals grown at 225 oC. The first order
Raman band was identified at =206cm-1 for nanocrystals grown from Pb-free precursor solution for 90 seconds at
225oC and =207cm-1 for nanocrystals grown from Pb-containing precursor solution under the same growth condition.
The observed Raman spectra are highly asymmetric and shifted from the value of bulk CdSe (=210cm-1) [17,18]. The
asymmetric line shape of the Raman band is commonly observed in low dimensional nanostructures and can be fitted
well with two Lorentzian peak functions which is explained with two effects [18,19]. The more pronounced peak at
=206cm-1 can be assigned to be a CdSe longitudinal optical (LO) mode and the shoulder on the low frequency side of
LO mode is related to surface optical phonon (SO) mode [19,20]. The SO mode can be observed in the Raman scattering
process due to non-spherical geometry of nanocrystals and it is highly dependent on the aspect ratio of nanocrystals
[19,21]. As shown in Fig. 4(b), the frequency of SO mode for nanocrystals grown from Pb-containing precursor solution
shifted to high frequency. That is, the frequency of SO mode for nanocrystals grown from Pb-free precursor solution is
much lower than that for nanocrystals grown from Pb-containing precursor solution at the same growth conditions.
Lange et al. showed that Raman-active SO mode of CdSe nanorods is shifted to high frequency, as the aspect ratio

(length/diameter) increases [20]. Again, this indicated that the nanocrystals with high aspect ratio can be synthesized
from Pb-containing precursor solution.
The temperature dependent PL spectra often provides a detailed information on photoluminescence process. Fig. 5
shows temperature-dependent PL spectra of CdSe and Pb-containing CdSe nanocrystals. It is found that the PL intensity
is quenched with increasing temperature and such behavior can be well described by the equation expressed as:

I I o /(1 Ce ET / k BT )

(1)

where Io, C are fitting parameters and ET is thermal activation energy of photoluminescence. The calculated thermal
activation energy of the nanocrystals is 29meV and 10meV for CdSe and Pb-containing CdSe nanocrystals, respectively.
The exciton binding energy (EB) can be calculated from the parameters including dielectric constant (r) and effective
mass: r = 9.6 (cubic), 9.3 (hexagonal), me = 0.11 mo (cubic), 0.13 mo (hexagonal), mh = 0.45 mo. The obtained binding
energy of 13 meV and 15 meV for is order of magnitude in good agreement with the activation energy extracted
experimentally, affirming our belief that the quenching of the PL integrated intensity is caused by non-radiative
recombination process due to the dissociation of excitons.

4. SUMMARY
In this study, we report the effects of Pb 2+ addition on the photoluminescence of CdSe nanocrystals. The addition of Pb
ions in the initial precursor solution changed the morphology of CdSe nanocrystals from slightly prolate ellipsoid to
branched rod. The branched nanocrystals are mainly composed of alternatively stacked zinc blende and wurzite phase
grown along [002] direction. We detect shift of surface optical phonon modes in the Raman spectra as a result of
branched morphology of nanocrystals with high aspect ratio. Temperature dependent PL spectroscopy was applied to
analyze the PL process in the nanocrystals.

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Figure 1. (a) Luminescence of CdSe nanocrystals having different amount of Pb added and (b) optical spectroscopy of them.

Figure 2. TEM images of nanocrystals grown at 225oC with various initial molar abundance of Pb, x=Pb/(Cd+Pb). Peak indices in the
XRD pattern were assigned according to wurzite CdSe.

Figure 3. High resolution TEM images for nanocrystals grown from Cd 0.8Pb0.2Se precursor solution. Area encircled with dotted line is
in zinc blende structure.

Figure 4. Raman spectra of the nanocrystals grown at 225 oC from (a) Pb-free precursor solution and (b) solution containing Pb with
x=0.2.

Figure 5. Temperature dependence of photoluminescence spectra for (a) CdSe and (b) (Cd,Pb)Se(x=0.2) nanocrystals grown at 225 oC.
(c) Temperature dependence of the integrated PL intensity for the samples and results of fitting with eq(1).