Research article

Received: 13 August 2012, Revised: 26 December 2012, Accepted: 2 January 2013 Published online in Wiley Online Library

(wileyonlinelibrary.com) DOI 10.1002/bio.2491

Highly luminescent hybrid SiO2-coated CdTe

quantum dots: synthesis and properties
Ning Liu and Ping Yang*
ABSTRACT: Novel hybrid SiO2-coated CdTe quantum dots (QDs) were created using CdTe QDs coated with a hybrid SiO2
shell containing Cd2+ ions and a sulfur source via a sol–gel process in aqueous solution. Aqueous CdTe QDs with tunable
emitting color created through a reaction between cadmium chloride and sodium hydrogen telluride was used as cores for
the preparation of hybrid SiO2-coated CdTe QDs. In our experiments we found that the surface state of the cores and
preparation conditions that affect the formation of the hybrid SiO2 shell also greatly affect photoluminescence of the hybrid
SiO2-coated CdTe QDs. The generation of CdS-like clusters in the vicinity of the CdTe QDs, caused the quantum size effect of
the QDs to be greatly reduced, which changes photoluminescence properties of the hybrid QDs fundamentally. Namely, the
novel hybrid SiO2 shell played an important role in generating a series of specific optical properties. In addition, the novel
hybrid SiO2 shell can be created if no CdTe QD is added. In order to gain an insight into the inter structure of the hybrid
shell, we characterized the hybrid SiO2-coated CdTe QDs using X-ray diffraction analysis and discuss the formation
mechanism of such a hybrid structure. This work is significant because the novel hybrid SiO2-coated CdTe QDs with
its excellent properties can be used in many applications, such as biolabeling and optoelectronic devices. Copyright ©
2013 John Wiley & Sons, Ltd.

Supporting Information may be found in the online version of this article.

Keywords: Hybrid; Silica; Composite; CdTe QDs; Photoluminescence

Introduction passivate QD cores perfectly and minimize the structure defects

Novel materials based on semiconductor quantum dots (QDs)
have attracted much attention over the last two decades due
to their unique size-dependent behavior and their optical
properties, such as the high brightness, luminescent tunability
with one excitation wavelength and high stability against
photobleaching compared with organic dyes (1,2). The electronic
and optical properties of the QDs make them transitional
between bulk material and molecules (3,4). In particular, the
variation of band gap with size has attracted much attention. Be-
cause of the advantages of luminescent QDs, they have a broad
application in many fields, including fluorescent biomarkers
and informational electronics. The development of biocompat-
ible highly luminescent materials for cell staining and visualiza-
tion has been an interesting objective in cellular biology and
ultrasensitive immunoassay, because luminescent probes for
biomolecular labeling and recognition are of great importance
in the fields of chemistry, biology and medical sciences as well
as in biotechnology (5).
The luminescent properties of QDs depend strongly on their
surface structure. Improvement of the photoluminescence (PL)
properties of the QDs by surface modification is an important
research topic. Capping QDs with heterogeneously organic or
inorganic shells is an efficient strategy to optimize their PL
properties, such as robust photochemical stability, increased PL
efficiency and surface functionality, which are prerequisite for
QDs applications in many fields. So far, several strategies have
been reported for the synthesis of various core shell QDs,
as much as possible, a decreased lattice matching between
shells and core materials is required (12). Generally, proper shell
capping can increase the PL efficiency of the QDs up to 10-fold
due to the properties of the shell material.
Recently, increasing attention has been directed to the
coating of emitting QDs with a layer of transparent silica
because the SiO2 has a larger electronic band gap than most
semiconductor core materials and because the excellent SiO2
shell has a great many advantages, such as good mechanical
stability, chemical robustness, good biocompatibility. However,
the thick SiO2 shell on QDs can drastically reduce PL efficiency
and enlarge the size of QDs compared with the initial QDs,
which limit the application of QDs in many fields. For example,
Bawendi’s group found that incorporating luminescent CdSe/
ZnS QDs into a SiO2 shell around SiO2 beads reduced PL
efficiency from 38% to about 13% (13).
To achieve significant signal increases in ultrasensitive
bioanalysis and extend the functionality of QDs, we have synthe-
sized hybrid nanostructures because such structure may lead to
QDs with novel emitting properties. Few studies have focused
on QDs coated with a hybrid SiO2 shell with increased PL effi-
ciency as well as tunable and narrow PL spectra. Recently we
reported that hybrid SiO2-coated CdTe QDs could be created
* Correspondence to: Ping Yang, School of Material Science and Engineering,
University of Jinan, 250022, Jinan, People’s Republic of China. Email:
1

mse_yangp@ujn.edu.cn
such as CdTe/ZnS, CdSe/CdS, CdSe/ZnS, CdTe/CdSe, CdSe/ZnSe,
CdS/ZnS, ZnSe/ZnS, InP/ZnS and PbSe/PbS (6–11). Various shell School of Material Science and Engineering, University of Jinan, 250022,
materials powerfully influence the PL properties of QDs. To Jinan, People’s Republic of China

Luminescence 2013 Copyright © 2013 John Wiley & Sons, Ltd.


using a two-step synthesis process including a sol–gel reaction
and a facile reflux procedure and with a core CdTe QDs created
using H2Te gas as a precursor (14). This time, we prepared CdTe
QDs using sodium hydrogen telluride (NaHTe) solution prepared
by the reaction of Te powder and NaHB4 in air-free double-
distilled water, which was more environmentally friendly. Also,
the tremendous diversity on surface states of core QDs
affects the formation procedure and PL properties of the hybrid
SiO2-coated CdTe QDs, such as the red shift of spectra, PL peaks,
PL efficiency, and full-width at half-maximum (FWHM) of PL
spectra. We studied the effect of preparation conditions on PL
properties systematically, and the results indicate the PL peak
wavelength of the hybrid QDs depended strongly on the molar
ratio of thioglycollic acid (TGA)/Cd2+, appropriate tetraethyl
silicate (TEOS) concentration to achieve narrow PL spectra, and
NH4OH to produce hybrid QDs with a high PL efficiency. In
addition, two kinds of Cd2+ precursors were used to deposit a
hybrid SiO2 shell on CdTe QDs. We investigated the structure
of hybrid QDs systematically through X-ray diffraction (XRD).
The unique PL properties made the hybrid SiO2-coated CdTe
QDs a good candidate for applications in many fields.
The hybrid QDs displayed many advantages attributed to the
formation of CdS-like clusters near the QD silica layers during
reflux (15). In a previous study, we found the absence of an
interface between the QD and CdS-like clusters caused an
increase of PL efficiency compared with the initial CdTe QDs.
The CdS-like clusters near the QDs results in a red shift of the
PL peak. As these clusters were not chemically bonded to the
QD surface, the lattice constant mismatch between the core
and shell has no effect on the PL properties of the hybrid QDs
as well as the inhomogeneity of the total QD ensemble was
reduced, which led to narrowing of the PL spectrum. The PL
properties of hybrid QDs strongly depend on preparation condi-
tions; however, there have still not been any detailed studies on
preparation conditions. Therefore, a systematic study on prepa-
ration conditions is necessary. Furthermore, there are still many
other factors that have not been studied, such as growth
mechanisms and shell structures of the hybrid SiO2-coated
CdTe QDs.
Materials and methods
Materials
Tellurium powder (Te, 99%), cadmium chloride (CdCl2
2.5H2O)
(99%), cadmium perchlorate hexahydrate (Cd(ClO4)2
6H2O,
98%), TGA (90%), TEOS (28.4%) and sodium borohydride (NaBH4,
≥96%) were purchased from Shanghai Guo Yao Chemical
Reagent Company, http://www.gongchang.com/Sinopharm_
Chemical_Reagent_Co_Ltd_-company-4881673-DF4AAgUCVw/.
An ammonia solution (NH3
H2O) (25–28%) was supplied by
Laiyang Kangde Chemical Reagent Company, http://xiaopaojicj.cn.
gongchang.com/. Milli-Q water (r ~ 18 MΩ
cm) was used as a
solvent. All chemicals were of analytical grade or of the highest
purity available.
Preparation of thioglycollic acid -coated CdTe quantum dots
TGA-capped CdTe QDs with various emitting colors (from green
2
to red) in aqueous solutions were prepared using cadmium
chloride and NaHTe as described elsewhere (16). Seventy-six
milligrams of NaBH4 and 26 mg of Te powder were mixed in
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N. Liu and P. Yang
2 mL of pure water to prepare a fresh NaHTe solution at a
temperature of 60 C. CdCl2.2.5H2O (0.4 mmol) and TGA
(0.6 mmol) were dissolved in 25 mL of water to get a solution
of Cd2+ and TGA. The pH of the solution was adjusted to 11 using
a NaOH solution of 2.0 M. The fresh NaHTe solution was added to
the solution of Cd2+ and TGA under N2 flow. The mixture was then
refluxed to create CdTe QDs, and the CdTe QDs with various sizes
can be obtained by adjusting the reflux time.
Preparation of hybrid SiO2-coated CdTe quantum dots
The preparation of hybrid SiO2-coated CdTe QDs using a similar
two-step synthesis has been described in detail in our previous
work (14). To investigate the effect of precursors on PL
properties of hybrid SiO2-coated CdTe QDs, two kinds of Cd2+
precursors were used to prepare the solution of Cd2+ and TGA.
In step 1, the CdTe QDs were precipitated by 2-propanol and
then redispersed in aqueous solution of Cd2+ and TGA whose
pH was 10.5, adjusted using a NaOH solution of 1 M. Diluted
ammonia (10 wt%) and TEOS were added to the aqueous
solution containing Cd2+, TGA and CdTe QDs in a beaker and
then sealed to reduce the evaporation of ammonia. After stirring
for 3 h at room temperature, a thin SiO2 shell was created on the
surface of the CdTe QDs. In step 2, a reflux process under 100 C
was used to make the hybrid SiO2 shell created on the surface of
the CdTe QDs. To fabricate the hybrid QDs with a tunable PL
peak, reflux time was adjusted. For a purpose of systematic
experiments, the molar ratio of Cd2+ to TGA, the concentrations
of CdTe QDs, TEOS, NH4OH and TGA in solutions were adjusted.
Characterization
The absorption and PL spectra were recorded using conven-
tional spectrometers, Hitachi U-4100 and F-4600, respectively.
The PL efficiency of CdTe QDs was estimated by comparison
with rhodamine 6G in ethanol at room temperature, assuming
its PL efficiency as 95% (lex = 365 nm) (17,18). The powder XRD
patterns of samples were recorded with an X-ray powder
diffractometer (Bruker D8, http://www.bruker.com/cn/products/
x-ray-diffraction-and-elemental-analysis.html) using a Cu Ka tar-
get. The observation of transmission electron microscopy (TEM)
and PL lifetime measurement were carried out by using an
electron microscope (JEM-100CX, http://www.ndsu.edu/em_lab/
instrumentation/jeol_jem_100cx_ii/) and a time-correlated single-
photon-counting spectrofluorometer system (Fluorocube-01, JY-IBH,
Horiba, http://www.instrument.com.cn/netshow/SH100344/C167721.
htm#), respectively.
Results and discussion
Formation of hybrid SiO2-coated CdTe quantum dots
A two-step synthesis was used to create hybrid SiO2-coated
CdTe QDs. In step 1, colloidal CdTe QDs were coated with a
SiO2 layer containing TGA and Cd2+ ions in an alkaline condition
using ammonia as a catalyst via a modified Stöber method. A
sol–gel silica layer deposited on the CdTe QDs because of
the hydrolysis and condensation reactions of silicon alkoxide
(Si(OR)4) in aqueous solutions (19). Normally, the condensation
of SiO2 monomers in alkaline conditions results in the genera-
tion of silica particles. In our experiments, the condensation of
SiO2 monomers did not lead to the formation of SiO2 particles.
Luminescence 2013
Highly luminescent hybrid SiO2-coated CdTe quantum dots
This is ascribed to two reasons. One is the existence of TGA, Cd2+,
and other retained precursors. The other is that no ethanol is
present in the solutions. Because of the absence of ethanol, the
hydrolysis of TEOS is very slow. The nucleation of SiO2 did not
occur because the concentration of SiO2 monomers in solution
is low (20). Therefore, SiO2 monomers were deposited on CdTe
QDs to form a thin SiO2 layer with the TGA and Cd2+ ions in solu-
tion. In this case, the CdTe QDs were coated with a composite
SiO2 layer, which may change the surface state of the CdTe
QDs. When the CdTe QDs were redispersed in aqueous solution,
the TGA molecules were partly removed from the surface of the
CdTe QDs. Then, the Si-O- group generated by the hydrolysis
of TEOS linked to the Cd2+ ions on the surface of the CdTe QDs
via an electrostatic force. The deposition process of SiO2 mono-
mers on the CdTe QDs was performed as below and the TGA
was used as a stabilizer.
In step 2, a reflux process at 100 C resulted in a hybrid SiO2
containing CdS-like clusters deposited on CdTe QDs via a sol–
gel reaction. During reflux, the Cd2+ in solution link with the
mercapto group in the TGA and forms a TGA-Cd complex. At
the same time, CdS-like clusters were formed through Cd2+ ions
and S2– ions generated by the decomposition of TGA. Because of
the deposition of the Cd-TGA complex and SiO2 monomers and
the generation of the CdS-like clusters, the hybrid SiO2 shell on
CdTe QDs gradually thickened. Scheme 1 illustrates the
formation procedure of TGA-capped CdTe QDs coated by a
hybrid SiO2 shell. However, the thickness of the hybrid SiO2 shell
was limited and the amount of SiO2 in the hybrid shell did not
increase continuously. We found that the SiO2 monomers did
not play a key role during the formation of the hybrid shell as
we could get high-quality hybrid QDs without added TEOS. So
we presume the Cd-TGA complex and the CdS-like clusters
generated in the hybrid shell play central roles in the novel PL
properties of the hybrid QDs. However, the SiO2 monomers
can modify the QDs surface and reduce the surface defects,
which improves quality of the hybrid QDs.
PL properties of hybrid SiO2-coated CdTe quantum dots
Hybrid SiO2-coated CdTe QDs were first fabricated by using
CdCl2
2.5H2O as Cd precursor. Figure 1 shows the absorption
and PL spectra of the hybrid SiO2-coated CdTe QDs prepared
using CdTe cores with various emitting colors (539, 582, 606
and 620 nm). The results indicate that the hybrid SiO2-coated
CdTe QDs had narrow PL spectra, high PL efficiencies, and red-
shifted PL peaks compared with initial colloidal CdTe cores.
The hybrid QDs created using small CdTe QDs revealed a large
increase in PL efficiency and red-shift of PL spectra compared
with those hybrid QDs created using large CdTe QDs. This result
Scheme 1. Preparation procedure of thioglycollic acid (TGA)-capped CdTe quantum dots (QDs) coated by a hybrid SiO2 shell.
Luminescence 2013 Copyright © 2013 John Wiley & Sons, Ltd.
was ascribed to the great difference in the surface state of CdTe
cores with various emitting colors. Table 1 illustrates the prepa-
ration conditions and PL properties of hybrid SiO2-coated CdTe
QDs prepared using CdTe cores with various emitting colors.
The PL properties of CdTe cores are listed for comparison. For
example, the PL spectrum of hybrid QDs revealed a red shift of
60 nm after refluxing for 260 min when green-emitting CdTe
cores (core 1, 539 nm). In contrast, a red shift of 19 nm was
observed when red-emitting CdTe cores (core 4, 620 nm) were
used. This phenomenon is attributed to the small CdTe QDs
having many surface dangling bonds and defects, which
promoted deposition of a hybrid shell on the surface of CdTe
QDs. Such thin hybrid shells passivated the QD surface and
reduced the surface defects effectively. Large CdTe cores have
relatively low surface defects and high PL efficiency. In addition,
this phenomenon is ascribed to the limitation of band gap of
semiconductor core/shell QDs. A similar phenomenon was
observed in CdSe/ZnS core/shell QDs.
The PL variation of hybrid SiO2-coated CdTe QDs occurs
mainly in step 2, and Fig. 2 shows the absorption and PL
spectra of CdTe QDs before and after being coated with a thin
SiO2 layer using step 1. The result indicates a small blue shift
of the PL spectrum and an increased PL efficiency from 60% to
67% were observed after coating with a thin SiO2 layer. How-
ever, absorption spectra and the FWHM (52 nm) of PL spectra
almost remained unchanged. The increased PL efficiency is
ascribed that the passivation of thin SiO2 layer reduced the
surface defects effectively. Such a thin SiO2 layer is transparent
and does not cause a deterioration in the optical properties of
the QDs. This differs from traditional QDs coated with a pure
sol–gel SiO2 shell. In that case, the PL efficiency decreased and
PL spectra became broad. In addition, this demonstrates that a
subsequent reflux procedure plays an important role for the
growth of the hybrid SiO2 shell.
We investigated systematically the effect of preparation
conditions on PL properties, and Table 2 summarizes the prepa-
ration conditions and PL properties of hybrid SiO2-coated CdTe
QDs. The result indicates that PL properties of the hybrid QDs
depended strongly on reaction time, the molar ratio of Cd2+ to
TGA, the concentration of TEOS, NH4OH and TGA in solution as
well as the size of CdTe cores. It is known that the molar ratio
and concentration of TGA and Cd2+ in solutions affect the PL
properties of hybrid QDs greatly. The molar ratio and concentra-
tions of TGA and Cd2+ affected the amount of S2– in the solution;
meanwhile the PL efficiency of the samples increased dramati-
cally, and then decreased gradually according to the increment
of TGA/Cd2+ ratio. Also, when the molar ratio of TGA to Cd2+ in
solutions is less than 2, monothio-Cd complex formed in the
solution; when the TGA/Cd2+ ratio was >2, dithio-Cd complexes 3
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 N. Liu and P. Yang

Figure 1. Absorption and photoluminescence (PL) spectra of hybrid SiO2-coated CdTe quantum dots (QDs) prepared using CdTe QDs with different emitting colors (from
green to red, as shown in Table 1). (a) Samples a and b. (b) Samples c and d. (c) Samples f and g. (d) Samples h and i. The absorption and PL spectra of initial CdTe cores are
shown for comparison.

Table 1. PL properties of hybrid SiO2-coated CdTe quantum

dots using CdTe quantum dots with different emitting
wavelengths as cores

Sample PL peak FWHM PL efficiency Reflux time

(nm) (nm) (%) (min)
Core 1 539 52 37 N/A
a 599 49 46 260
b 611 51 51 720
Core 2 582 49 67 N/A
c 620 44 67 180
d 625 44 62 270
Core 3 606 52 60 N/A
Figure 2. Absorption and photoluminescence (PL) spectra of CdTe quantum dots
e 604 52 67 0 (QDs) before (solid line) and after (dotted line) coated with a thin SiO2 layer by step
f 622 47 47 100 1 using core 3 (shown in Table 1).
g 634 45 45 300
Core 4 620 51 70 N/A
h 639 47 77 300
i 657 48 65 1120 Additionally, a dithio-Cd complex had high stability compared
FWHM, full-width at half-maximum; PL, photoluminescence. with a monothio-Cd complex. In our experiments, the molar
ratio ranged from 1.5 to 3. Two kinds of TGA-Cd composites
therefore existed. As shown in Table 2, the PL peak position of
the hybrid QDs red-shifted with the increasing molar ratio of
formed in solution. The reaction between Cd2+ and TGA can be TGA/Cd2+. At this high ratio the amount of free TGA in solution
illustrated through equations (1) and (2) as follows (18). increased. Increased free TGA decomposed to generate more
S2– ions, which led to the growth of CdS-like clusters.
Cd2þ þ SR↔ðCd-SRÞþ (1) Furthermore, the concentration of TGA, TEOS and NH4OH also
4

play important roles for the formation of the hybrid SiO2 shell as
shown in Table 2. A high TEOS concentration (sample 2) resulted
ðCd-SRÞþ þ SR↔CdðSRÞ2 (2) in the hybrid SiO2-coated QDs with a relatively narrow PL

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Highly luminescent hybrid SiO2-coated CdTe quantum dots

Table 2. Preparation conditions and PL properties of hybrid SiO2-coated CdTe QDsa

Sample TEOS concentration TGA/Cd2+ molar NH4OH concentration TGA concentra- Reflux time PL peak wave- FWHM
(10–10 M) ratio (10–6 M) tion (M) (min) length (nm) (nm)
CdTe(a) N/A N/A N/A N/A N/A 528 37
1 5.58 1.5 0.11 0.01 30 566 40
2 8.93 1.5 0.11 0.01 30 574 37
3 4.46 1.8 0.03 0.005 120 579 43
4 4.46 1.8 0.03 0.0025 120 585 46
5 4.46 2 0.03 0.0025 200 590 46
6 8.93 2 0.11 0.005 360 600 57
7 4.46 2.5 0.03 0.0025 200 593 50
8 8.93 3 0.11 0.005 360 605 53
FWHM, full-width at half-maximum; PL, photoluminescence.
a
The PL properties of initial CdTe QDs are shown for comparison.

spectrum (small FWHM value), high PL efficiency and a largely
red-shifted PL peak compared with that in a small TEOS amount
(sample 1). Excess TEOS did not further change PL peak wave-
length of the hybrid QDs (see Supporting Information, Table S1
and Fig. S1). This indicates that the SiO2 matrix did not play a
role in the PL properties of the hybrid QDs.
It is well known that ammonia as a catalyst accelerates the
hydrolysis of TEOS (19). To investigate the effect of NH4OH on
PL properties, we studied the properties of the hybrid QDs
prepared with and without NH4OH in solution. For the prepara-
tion of sample 9, the CdTe QDs were redispersed in an
aqueous solution containing Cd2+, TGA and NH4OH. In contrast,
sample 10 was prepared using a solution only containing Cd2+
and TGA (without NH4OH). This means no TEOS was added
during the preparation of samples 9 and 10. We recorded the
evolution of the PL spectra of samples 9 and 10 with time.
Figure 3 shows the relationship among PL efficiency, FWHM of
PL spectra and PL peak wavelength of hybrid QDs during reflux.
The result indicates that sample 9 had a dramatic decrease in
FWHM of PL spectra (Fig. 3a) and high PL efficiency (up to
90%) accompanied by a red shift of the PL peak compared with
the initial colloidal CdTe QDs (Fig. 3d). In contrast, the FWHM of
PL spectra of sample 10 became broad with time (Fig. 3b) and PL
efficiency reduced quickly (Fig. 3c). The result indicates that the
NH4OH plays an important role in the formation of CdS-like
clusters in the shell matrix when other conditions were kept
the same. In the case of no TEOS added, red-shifted PL spectra
were also observed. In this case, CdS-like clusters dispersed in
an organic composite shell consisting of Cd2+ and TGA. There-
fore, the SiO2 monomers may not be as important during the
formation of the hybrid shell as previously thought, but it can
modify the surface of hybrid QDs effectively. We also studied
the effect of Cd2+ precursors on PL properties. According to
the experimental results, the precursors of Cd2+ have almost
no effect on the properties of hybrid QDs (see Supporting Infor-
mation, Figure S2 and Table S2). This recognizes that the anion
matched to the Cd2+ does not affect the PL properties of the
hybrid QDs in solution.
Sizes of hybrid SiO2-coated CdTe quantum dots
The tunable PL wavelength and high efficiency of the hybrid
SiO2-coated CdTe QDs differed significantly from those of CdTe
QDs with a pure SiO2 shell. The formation of a pure SiO2 shell
on the QDs leads to a drastic reduction in PL efficiency and an
increase of size compared with the initial QDs (13,21). To clarify
the origin of these spectral changes, we characterized hybrid
QDs using TEM. Figure 4 shows the TEM images of hybrid
SiO2-coated CdTe QDs shown in Table 3: (a) sample j; (b) sample
k; and (c) sample l. Table 3 illustrates the preparation conditions
and PL properties of hybrid SiO2-coated CdTe QDs (samples j, k
and l) and initial CdTe QDs (core 4).
The diameter of core 4 and sample j are 3.8 and 4.4 nm
respectively, which indicate that the thickness of the shell is less
that 1 nm, such a thin shell also benefits from retaining the PL
efficiency of the QDs. Samples j and k were prepared using the
same CdTe QDs (core 4) at different reflux times (330 min for
sample j and 770 min for sample k). However, the size of sample
j was smaller than that of sample k. In this case, the shell was
dissolved because of an excessively long reaction time. This
means the thickness of the QDs was limited and the amount
of SiO2 monomers organized in the shell did not increased con-
tinuously. However, the size of CdS-like clusters in the shell still
increased because sample k revealed a longer PL peak over a
long reflux time. In addition, samples k and l revealed the same
5

Figure 3. Relationship among (a,b) full-width at half-maximum (FWHM) of

diameter, but a different PL peak wavelength. These indicate
photoluminescence (PL) spectra, (c,d) PL efficiency and PL peak wavelength of hy- that the shell thickness did not play important role for the PL
brid CdTe quantum dots during reflux. spectra. The variation of PL properties depended strongly on

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 N. Liu and P. Yang

the size of CdS-like clusters in the shell instead of the shell
thickness.
PL lifetime of hybrid SiO2-coated CdTe quantum dots
Figure 5 shows the luminescence decay curves (measured on
the emission peak maximum, lex = 370 nm) of initial colloidal
solution of CdTe QDs and hybrid SiO2-coated CdTe QDs: (a)
samples m, n, o and p and core 2, and (b) sample o and core
4. Reproduced curves using the values shown in Table 4 are
plotted as thin white lines. For all samples, time-resolved
emission measurements were done at their peak wavelengths
in steady-state emission spectra. The decay curves can be fitted
to a biexponential model described by F(t) = A + B1 exp (–t/t1) +
B2 exp (–t/t2), where t1 and t2 represent the time constants and
B1 and B2 represent the amplitudes of the fast and slow compo-
nents, respectively. Average lifetime t is calculated using t = (B1
t12 + B2 t22) / (B1 t1 + B2 t2) (22). Table 4 illustrates the time
constants t1 and t2, components B1 and B2, average lifetime t,
and PL properties of CdTe QDs and hybrid SiO2-capped CdTe
QDs. It is noted that the fast component of the PL decay in the
initial CdTe QDs can be associated with an exciton recombina-
tion, while the slow component is known as originating from
the surface-related emission of CdTe QDs (23). The fast compo-
nent (B1) of PL decay for the hybrid QDs decreased compared
with that of CdTe QDs while the slow component (B2) increased.
Figure 5(a) reflects the law commendably. The PL lifetime of
semiconductor core-shell QDs depends strongly on their surface
state that is closely related to the composition, morphology
and thickness of the shell. According to calculations (24), this
successive increment is accompanied by an increase in the
radiative lifetime and a reduction in the non-radiative decay rate.
In addition, from Fig. 5(b), we could find that the average PL
decay lifetime of 26.80 ns for initial CdTe QDs (core 4) increased
further to 34.06 ns (sample o) after coating with a thin hybrid
shell on their surface through reflux process, even though
they own the same PL peak. Study of all the characterization
available together with calculations led us to conclude that the

Figure 4. Transmission electron microscopy images of CdTe quantum dots (core 4) and hybrid SiO2-coated CdTe quantum dots (j–l). (a) Core 4. (b) Sample j. (c) Sample k.
(d) Sample l. Mean diameters of core 4 and sample j were 3.8 and 4.4 nm, respectively. Mean diameter of samples k and l was 4.2 nm.

Table 3. Preparation conditions and PL properties of hybrid SiO2-coated CdTe QDs and initial CdTe QDsa

Sample TEOS concentration TGA/Cd2+ NH4OH concentration Diameter PL peak wavelength Reflux time
(10–10 M) molar ratio (10–6 M) (nm) (nm) (min)
Core 4 N/A N/A N/A 3.8 620 N/A
j 6.70 2 0.04 4.4 639 300
k 6.70 2 0.04 4.2 651 770
l 6.70 2 0.04 4.2 635 90
6

PL, photoluminescence; QDs, quantum dots.

a
The PL properties of initial CdTe QDs (core 4) are listed for comparison.

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Highly luminescent hybrid SiO2-coated CdTe quantum dots

Figure 5. Luminescence decay curves (measured on the emission peak maximum, lex = 370 nm) of initial colloidal solution of CdTe quantum dots and hybrid SiO2-coated
CdTe quantum dots. (a) Samples m, n, o and p and core 2. (b) Sample o and core 4. Reproduced curves using the values shown in Table 4 are plotted as thin white lines.

Table 4. Time constants t1 and t2, components B1 and B2, average lifetime t, and PL properties of CdTe QDs and hybrid SiO2-
capped CdTe QDsa

Sample B1 (%) t1 (ns) B2 (%) t2 (ns) t (ns) PL peak (nm) PL efficiency (%)
Core 2 55.02 13.03 44.98 32.01 25.70 582 67
m 51.29 18.23 48.71 38.99 32.14 613 64
n 47.09 18.94 52.91 40.37 34.06 620 67
Core 4 49.06 15.95 50.94 32.01 26.80 620 70
o 47.39 20.24 52.61 44.97 37.83 625 62
p 46.01 21.84 53.99 53.64 45.45 632 58
PL, photoluminescence; QDs, quantum dots.
a
The properties of initial CdTe QDs are listed for comparison.

phenomenon can be explained by the formation of CdS-like
clusters in the hybrid shell (1 nm or less in size) on the surface
of QDs during reflux (15).
The results in the current experiment do not exactly coincide
with our previous work. This is because we used Te powder
and NaBH4 instead of the Al2Te3 and H2SO4 to produce the pre-
cursor. This means the PL properties of the hybrid SiO2-coated
CdTe QDs strongly depend on the core’s surface state and
composition of the solution during reflux.
Crystal structure of hybrid SiO2-coated CdTe quantum dots
To study the composite and structure of the shell, we
investigated the crystallinities of the hybrid QDs using
powder XRD analysis. Figure 6 shows the XRD patterns of hybrid
SiO2-coated CdTe QDs: (a) before filtering; (b) after filtering; (c)
sample prepared using a TGA/Cd2+ molar ratio of 1.8 before
and after filtering; and (d) blank sample prepared without using
CdTe QDs. The TGA/Cd2+ ratios of the samples were adjusted
from 1.5 to 3. The standard diffraction peak positions of cubic
CdTe and cubic CdS are also shown for comparison.
We also synthesized hybrid SiO2-coated CdTe QDs under the
same conditions. The molar ratio of TGA/Cd2+ was adjusted
because the formation of the monomers and dimers of Cd2+
and TGA depended strongly on the ratio. The broad diffractive
peaks shown in Fig. 6 is typical from QDs. The initial CdTe QDs
show a cubic zinc blende structure, represented by the diffrac-
hybrid SiO2-coated CdTe QDs, which are intermediate between
the initial CdTe and the cubic CdS phase. This means that the
samples own a core-shell nanostructure similarly to previous
work (7). The difference of XRD patterns in Fig. 6(a) and 6(b) is
that many sharp peaks were observed in Fig. 6(a). This is mainly
ascribed to the CdS-like clusters generated during reflux. The
TGA/Cd2+ molar ratio is less than 2, and the monothio-Cd
complex is easily generated to create fibers. However, when
the molar ratio is increased to 2 and 3, the dithio-Cd complex
(Cd2+ connected with two or three ligands) dominate in solution,
which hinder the generation of composite fibers. After filtering,
three samples revealed almost the same XRD peaks as shown
in Fig. 6(b). Therefore, the molar ratio of TGA/Cd2+ did not affect
the crystal structure of the hybrid QDs. The samples using TGA/
Cd2+ ratios of 2 and 3 exhibited almost the same diffractive
peaks before and after filtering. This suggested that the sharp
diffractive peaks originate from the abundant composite
fibers, which have the same structure with the hybrid SiO2 shell
material, but the thin composite shell was too little to generate
the XRD signals.
We used the same method to prepare samples using a TGA/
Cd2+ molar ratio of 1.8 (XRD patterns are shown in Fig. 6c). We
found that the sharp diffractive peaks of composite fibers
appear synchronously with the three main diffraction peaks of
hybrid SiO2-coated CdTe QDs. Three diffractive peaks located
at 8.7 , 10.2 and 20.5 appeared in the small angle range, which
are the characteristic peaks of composite fibers. However, the
7

tive peaks at 23.8 , 39.3 and 46.4 while the CdS QDs diffractive peak 10.2 owns the strongest diffractive intensity, which was
peaks are at 26.5 , 44.0 , 52.1 and 30.7 . However, there are doubled to the peak at 20.5 , which indicated that the two peaks
three obvious diffractive peaks at 24.5 , 40.9 and 48.1 for are original from the same crystal facets. After filtering, these

Luminescence 2013 Copyright © 2013 John Wiley & Sons, Ltd. wileyonlinelibrary.com/journal/luminescence

Figure 6. X-ray diffraction patterns of hybrid SiO2-coated CdTe quantum dots. The TGA/Cd2+ ratio of the samples were adjusted from 1.5 to 3. (a) Before filtering. (b) After
filtering. (c) Sample prepared using TGA/Cd2+ molar ratio of 1.8 before and after filtering. (d) Blank sample prepared without using CdTe quantum dots. The standard dif-
fraction peak positions of cubic CdTe and cubic CdS are shown for comparison.
sharp peaks disappeared, which suggests that the excess
composite was removed. Because these characteristic peaks
cannot exactly be found in the standard XRD database, we
presume that the hybrid shell is a new kind of complex formed
by two or more composites. To demonstrate our hypothesis
further, we prepared blank samples without using CdTe QDs.
The XRD pattern is shown in Fig. 6(d). Except for the main diffrac-
tion peak positions of cubic CdS, the three main sharp diffractive
peaks also appeared. Experiments for blank samples revealed
similar phenomenon described above (see Supporting Informa-
tion, Fig. S3 and Table S3).
Conclusions
Novel hybrid SiO2-coated CdTe QDs were fabricated through a
two-step synthesis. This special core-shell structure gave the
QDs extraordinary properties, such as a narrowed PL spectrum,
red-shifted PL peak, and high PL efficiency (up to 90%). The
hybrid QD properties depend strongly on CdS-like clusters in
the hybrid shell near the CdTe cores and did not depend on
the thickness of the hybrid shell. The PL properties of the hybrid
QDs were also determined by the molar ratio and concentration
of Cd2+ to TGA, the concentration of TEOS, NH4OH and TGA
8
in solution, the size of the core and reaction time. The hybrid
QDs revealed a prolonged PL lifetime compared with initial
CdTe QDs due to the tremendous diversity in surface states
wileyonlinelibrary.com/journal/luminescence Copyright © 2013 John Wiley & Sons, Ltd.
N. Liu and P. Yang
of core QDs, even though they have the same PL peak wave-
length. Results in the current work differed markedly from those
in previous work. This is ascribed to the surface state of CdTe
QDs, which was determined by preparation conditions. Notably,
we used XRD to analyze the composite and structure of the
hybrid shell, which supplied very important evidence for our
hypothesis that the hybrid shell is a new kind of complex formed
by two or more composites containing Cd, TGA, NH4OH and
SiO2. The hybrid QDs would have unique applications to biolog-
ical and light-emitting devices due to their high PL efficiency,
tunable PL spectra and SiO2-contained functional shell.
SUPPORTING INFORMATION
Supporting Information may be found in the online version of
this article.
Acknowledgments
This work was supported in part by the Program for Taishan
Scholars, projects from National Natural Science Foundation of
China (21071061), and projects from Shandong Provincial
Natural Science Foundation, China (ZR2010EZ001) and
Outstanding Young Scientists Foundation Grant of Shandong
Province (BS2010CL004).
Luminescence 2013
Highly luminescent hybrid SiO2-coated CdTe quantum dots
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