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Optical Materials xxx (2008) xxx–xxx

Contents lists available at ScienceDirect

Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Synthesis and photoluminescence of water-soluble Mn:ZnS/ZnS core/shell

quantum dots using nucleation-doping strategy
Qi Xiao *, Chong Xiao
School of Resources Processing and Bioengineering, Central South University, Changsha 410083, China

a r t i c l e i n f o a b s t r a c t

Article history: The water-soluble Mn:ZnS/ZnS (core/shell) quantum dots were synthesized through nucleation-doping
Received 14 April 2008 strategy in aqueous solutions in air, and characterized by X-ray diffraction (XRD), transmission electron
Received in revised form 13 June 2008 microscopy (TEM), and photoluminescence (PL) spectra. It was found that the Mn2+ 4T1 ? 6A1 emission
Accepted 18 June 2008
intensity of Mn:ZnS d-dots significantly increased with the increase of Mn2+ concentration, and showed
Available online xxxx
a maximum when Mn2+ doping content was 1.0%. If Mn2+ concentration continued to increase, namely
more than 1.0%, the Mn2+ 4T1 ? 6A1 emission intensity would decrease. By the growth of an additional
Keywords:
ZnS shell on Mn:ZnS d-dots, the emission intensity of Mn2+ in Mn:ZnS/ZnS core/shell d-dots were
Mn:ZnS/ZnS (core/shell) quantum dots
Nucleation-doping strategy
enhanced due to the elimination of the surface defects. Mn:ZnS/ZnS (core/shell) d-dots were not at all
Water-soluble air sensitive, while Mn:ZnS d-dots were strongly air sensitive.
Photoluminescence Ó 2008 Elsevier B.V. All rights reserved.

1. Introduction metallic method [17], chemical precipitation method [18], micro-

Semiconductor quantum dots, or quantum dots (q-dots), with
CdSe ones as the workhorse, have been widely explored as biomed-
ical labeling reagents since 1998 [1–4]. However, the small-ensem-
ble Stokes shift of intrinsic q-dot emitters made self-quenching. In
addition, experimental results indicated that any leakage of cad-
mium from the quantum dots would be toxic and fatal to a biolog-
ical system [5], and cadmium-containing products were eventually
environmentally problematic. Recently, Peng et al. [6–8] reported
that doped quantum dots (d-dots) (e.g., Mn:ZnSe d-dots) could
not only replace cadmium in CdSe quantum dots with zinc, but
also overcome a couple of intrinsic disadvantages of undoped
quantum dots (q-dots) emitters, that is, strong self-quenching
caused by their small ensemble stokes shift (energy difference be-
tween absorption spectrum and emission band) [9,10] and sensi-
tivity to thermal, chemical, and photochemical disturbances
[11,12]. Mn2+-doped ZnS quantum dots have been extensively
investigated for use in various applications other than biomedical
labeling, such as displays, sensors, and lasers [13–15]. In addition,
the luminescent lifetime of Mn2+-doped ZnS quantum dots was ca.
1 ms. Such a long lifetime made the luminescence from the nano-
crystal readily distinguishable from the background luminescence.
Therefore, Mn2+-doped ZnS quantum dots could be potential candi-
dates as fluorescent labeling agents, especially in biology [16].
Many approaches have been explored for the preparation of
Mn2+-doped ZnS quantum dots (Mn:ZnS d-dots), including organo-
* Corresponding author. Tel.: +86 731 8830543; fax: +86 731 8879815.
E-mail address: xiaoqi88@mail.csu.edu.cn (Q. Xiao).
emulsion technique [19], reverse micelle method [20], etc. The
traditional synthesis strategies of Mn:ZnS d-dots were based on a
reaction system with both dopant ions and competitive host ions
in it, which was difficult to control and optimize. To meet this chal-
lenge, Peng et al. [6–8] recently developed a new synthetic strat-
egy, nucleation-doping, to prepare Mn:ZnSe d-dots through
organometallic routes. The key feature of the nucleation-doping
strategy was decoupling the doping from nucleation, which al-
lowed for the growth of d-dots in a controllable fashion, thus yield-
ing d-dots with pure dopant emission at a high efficiency. To be a
suitable bio-labeling agent, the quantum dots should have high
luminescent efficiency, water-solubilization, and biocompatibility.
Water-soluble semiconductor quantum dots could be obtained
mainly by two different methods. The first way was to replace
the surface-capping molecules on the particles prepared by the
TOPO (trioctylphosphine oxide) method with water-soluble thiols
[21]. However, after the substitution of the surface-capping mole-
cules by hydrophilic molecules, the nanoparticle photolumines-
cence decreased markedly [21]. The second method was to
directly synthesize semiconductor quantum dots in aqueous solu-
tion using water-soluble stabilizers [22]. The second method be-
came a popular recipe for making water-soluble nanoparticles.
Therefore, a facile aqueous nucleation-doping strategy to obtain
water-soluble Mn:ZnS d-dots were highly desired.
On the other hand, the passivation of surface was of crucial
importance for the applications of semiconductor quantum dots.
In order to get a better passivation, inorganically passivated (or
core/shell structured) quantum dots have been developed and
shown dramatically enhanced properties [23]. Photoenhanced

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doi:10.1016/j.optmat.2008.06.010

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luminescence was observed in ZnS/CdS/ZnS quantum well [24], (k = 0.15418 nm). Transmission electron microscopy (TEM) images
ZnS:Mn/ZnS nanoparticles [20], ZnS:Mn/ZnO nanophosphors [25], were obtained using a JEM 3010 high-resolution transmission elec-
and ZnS:Mn/Zn(OH)2 nanocrystal [26], etc. Especially, formation of tron microscope. UV–Vis absorption spectra were recorded with a
ZnS:Mn2+/ZnS core/shell nanocrystals resulted in obvious enhance- UV–Vis scanning spectrophotometer (Shimadzu UV-2450). The
ment in the PL intensity with respect to that of bare ZnS:Mn2+ nano- photoluminescence (PL) spectra of the samples in solid form were
crystals due to the good match between core (Mn:ZnS) and shell recorded with a fluorescence spectrophotometer F-4500.
(ZnS) lattice constants and the effective elimination of the surface
defects [20]. In this paper, we introduced the nucleation-doping 3. Results and discussion
strategy to synthesize Mn:ZnS/ZnS (core/shell) quantum dots in
aqueous solution in air. By the growth of an additional ZnS shell 3.1. XRD analysis
on Mn:ZnS d-dots, the emission intensity of Mn2+ in Mn:ZnS/ZnS
core/shell d-dots were enhanced due to the elimination of the sur- The XRD patterns of Mn:ZnS d-dots were shown in Fig. 1. These
face defects. In addition, Mn:ZnS/ZnS (core/shell) d-dots were not diffraction features appearing at 28.5°, 47.5°, and 56.3° corre-
at all air sensitive, while Mn:ZnS d-dots were strongly air sensitive. sponded to the (1 1 1), (2 2 0), and (3 1 1) planes of cubic zinc blende
structure, which was very consistent with the values in the stan-
2. Experimental section dard card (JCPDS No. 77-2100). No characteristic peaks of impurity
phases are observed in the XRD pattern, indicating the high purity
2.1. Chemicals of the final products. In addition, the broadening of the diffraction
peaks of all the Mn:ZnS d-dots were obvious, which was character-
All chemicals used were of analytical grade. Zn (CH3COO)2
istic of nanocrystal. The averaged crystallite sizes D was deter-
2H2O, Mn(CH3COO)2
2H2O, Na2S
9H2O, and thioglycolic acid mined according to the Scherrer equation D = kk/bcos h [27],
(TGA) were obtained from Shanghai Chemical Reagents Company where k was a constant (shape factor, about 0.9), k was the X-ray
and used as received. High-purity water with a resistivity of wavelength (0.15418 nm), b was the full width at half maximum
18.2 MX/cm was used for preparation of all aqueous solutions. (FWHM) of the diffraction line, and h was the diffraction angle.
Based on the FWHM of (1 1 1) zinc blende reflection, the averaged
crystallite sizes of Mn:ZnS d-dots doped with different Mn2+ con-
2.2. Synthesis
centration (0%, 1% and 3%) were estimated to be 3.96, 4.08 and
4.11 nm, respectively.
2.2.1. Synthesis of Mn:ZnS d-dots
TGAZn and TGAMn stock solutions were prepared by adding Zn
3.2. TEM analysis
(CH3COO)2
2H2O and Mn (CH3COO)2
2H2O into 100 ml of TGA
(0.12 M) aqueous solution, respectively. Then the different volume
Fig. 2 showed the TEM results of the as-prepared 1% Mn doped
of TGAMn stock solution was quickly added into the Na2S solution
ZnS/ZnS core/shell quantum dots (ZMS-25). A typical TEM image in
under vigorously stirring, the reaction mixture was stirred at
low magnification was shown in Fig. 2a. It could be seen that the
80 °C for 20 min to form small-sized MnS core. Next, the TGAZn
resultant quantum dots were uniform spherical-shaped particles
stock solution was quickly injected into the above reaction mixture
with a very narrow size distribution. High-resolution transmission
under vigorously stirring, and then the reaction mixture was heated
electron microscopy (HRTEM) image was shown in Fig. 2b. It dem-
at 80 °C for 12 h. The final molar ratio of Mn/Zn was varied from 0 to
onstrated the high crystallinity of the as-prepared quantum dots,
3%. The molar ratio between S-precursor and Zn and Mn precursors
and the distances (0.3174 nm) between the adjacent lattice fringes
was equal to 1.5. The Mn:ZnS d-dots solid powders were obtained
were the interplanar distances of ZnS (1 1 1) plane, agreeing well
by adding excess ethanol to the solutions and then dried in vacuum.
with the (1 1 1) d spacing of the literature value, 0.312 nm (JCPDS
No. 77-2100). However, the core and the shell of the quantum dots
2.2.2. Synthesis of Mn:ZnS/ZnS (core/shell) d-dots
TGAZn and TGAMn stock solutions were prepared by adding Zn
(CH3COO)2
2H2O and Mn (CH3COO)2
2H2O into 100 ml of TGA
(0.12 M) aqueous solution, respectively. Then the TGAMn stock
solution was quickly added into the Na2S solution under vigorously
stirring, the reaction mixture was stirred at 80 °C for 20 min to
form small-sized MnS core. In order to obtained Mn:ZnS/ZnS
core/shell d-dots with different ZnS shell thickness, the TGA-zinc
aqueous solution was injected into the MnS core solution at two-
step. At the first step, 100%, 75%, 50%, and 25% of TGAZn stock solu-
tion was injected into the MnS core solution under vigorously stir-
ring respectively, and heated at 80 °C for 10 h. At the second step,
residual TGAZn stock solution was injected and heated at 80 °C for
another 2 h. The Mn/Zn molar ratios in the four samples were fixed
at 1%. The molar ratio between S-precursor and Zn&Mn precursors
was equal to 1.5. The Mn:ZnS/ZnS core/shell quantum dots were
obtained by adding excess ethanol to the solutions and then dried
in vacuum, and the four different samples with different ZnS shell
thickness were marked as ZMS-0, ZMS-25, ZMS-50 and ZMS-75.

2.3. Characterization

The X-ray diffraction (XRD) patterns of the synthesized samples Fig. 1. X-ray diffraction patterns of Mn:ZnS d-dots with different Mn/Zn molar
were obtained by a D/max-cA diffractometer using Cu Ka radiation ratio.

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Fig. 2. The high-resolution TEM (HRTEM) images of as-prepared d-dots (ZMS-25).

had similar electron densities and lattice parameters, and the im-
age contrast could not be used to distinguish the shell and core.
3.3. Control of the size of the MnS core
In the nucleation-doping strategy, small-sized MnS core was the
first key issue for Mn:ZnS d-dots [8]. Fig. 3 showed the UV–Vis
absorption spectra of MnS nanocrystals with different S/Mn molar
ratio. It was found that the absorption edge gradually shifted from
260 nm to 275 nm with the increase of reaction times when S/Mn
molar ratio was 50 (shown in Fig. 3a), indicating that MnS nano-
crystals continuously growed. When S/Mn molar ratio was higher
than 100, the absorption edge of the MnS nanocrystals were steady
around 265 nm (shown in Fig. 3 b, c). In addition, it was found that
the large excess of S-precursor should be more suitable for the for-
mation of smaller MnS nanocrystals (shown in Fig. 3d). According
to Brus equation [28], the size of MnS nanocrystal was estimated to
1.2 nm when the S/Mn molar ratio was 150.

Fig. 3. Time evolution of the UV–Vis spectra of MnS core with different Mn/S molar ratio. (a) Mn:S = 1:50, (b) Mn:S = 1:50, (c) Mn:S = 1:50 (d) UV–Vis spectra of MnS with
different Mn/S molar ratio heated at 20 min.

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3.4. Photoluminescence (PL) spectra of Mn:ZnS d-dots
Fig. 4 showed the photoluminescence excitation (PLE) spectra of
Mn:ZnS d-dots doped with different Mn2+ doping concentration. It
was found that the PLE spectra of all the doped samples showed
only one emission band at about 340 nm. In addition, PLE intensity
of Mn:ZnS d-dots significantly increased with the increase of Mn2+
concentration, and showed a maximum when Mn2+ doping content
was 1%. If Mn2+ concentration continued to increase, namely more
than 1%, the PLE intensity would decrease. Fig. 5 showed the room
temperature photoluminescence (PL) spectra of Mn:ZnS d-dots
doped with different Mn2+ concentration under 340 nm excitation.
It was found that the PL spectra of undoped samples showed only
one emission band at about 460 nm, which could be assigned to

Fig. 4. The photoluminescence excitation (PLE) spectra of Mn:ZnS d-dots doped Fig. 5. Photoluminescence (PL) spectra of Mn:ZnS d-dots with different Mn/Zn
with different Mn2+ doping concentration. molar ratio.

Fig. 6. The photoluminescence excitation (PLE) spectra of Mn:ZnS d-dots and Mn:ZnS/ZnS core/shell d-dots with different Mn doping concentration (a) 1.33%; (b) 2%; (c) 4%;
(d) the photoluminescence excitation (PLE) spectra of Mn:ZnS d-dots with different ZnS shell thickness.

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the radiative recombination involving defect states in the ZnS
quantum dots [29]. For all the doped samples, two different emis-
sion bands dominated the PL spectra. The first emission band at
about 460 nm also existed in the PL spectrum of the undoped
ZnS quantum dots, this emission band should indeed originate
from the host ZnS but not from Mn2+ ions. The second emission
band was centered at about 585 nm, which was due to 4T1 ? 6A1
transition within the 3d shell of Mn2+ [17]. When Mn2+ ions were
incorporated into the ZnS lattice and substituted for host cation
sites, the mixing between the s and p electrons of the host ZnS
and the d electrons of Mn2+ occurred and made the forbidden tran-
sition of 4T1 ? 6A1 partially allowed, resulting in the characteristic
emission of Mn2+ [17]. Sooklal et al. [30] found that Mn2+ incorpo-
rated into the ZnS lattice led to the Mn2+-based orange emission
while ZnS with surface-bound Mn2+ yielded the ultraviolet emis-
sion. Thus, it could be concluded that the Mn2+ ions were indeed
incorporated into the host ZnS quantum dots by using the nucle-
ation-doping strategy, and when Mn2+ concentration reached a
certain level, the concentration quenching was appeared. In addi-
tion, many researchers found that concentration quenching for
the photoluminescence intensity of Mn2+-doepd ZnS nanocrystals.
Sooklal et al. [30] found an optimal Mn2+ concentration of 2%.
Khosravi et al. [31] observed a maximum luminescence at a doping
concentration of 0.12 wt%. Leeb et al. [32] reported an optimal
Mn2+ concentration of 1%. In our work, concentration quenching
was also observed in our samples (shown in Fig. 5). It was found
that the Mn2+ 4T1 ? 6A1 emission intensity of Mn:ZnS d-dots sig-
nificantly increased with the increase of Mn2+ concentration, and
showed a maximum when Mn2+ doping content was 1%. If Mn2+
concentration continued to increase, namely more than 1%, the
Mn2+ 4T1 ? 6A1 emission intensity would decrease.
Fig. 7. Photoluminescence (PL) spectra of Mn:ZnS d-dots and Mn:ZnS/ZnS core/shell d-dots with different Mn doping concentration (a) 1.33%; (b) 2%; (c) 4% and (d) PL spectra
of Mn:ZnS/ZnS core/shell d-dots with different shell thickness.
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5
3.5. Photoluminescence (PL) spectra of Mn:ZnS/ZnS (core/shell) d-dots
3.5.1. Effect of ZnS shell thickness
Although the Mn/Zn molar ratios in the four samples were fixed
at 1%, the actual Mn doping concentration in the Mn:ZnS d-dots
core varied when the amount of TGA-zinc solution changed at
the first step during the preparation of Mn:ZnS/ZnS (core/shell)
d-dots with different ZnS shell thickness. The actual Mn doping
concentrations were 1%, 1.33%, 2%, and 4% in the Mn:ZnS d-dots
cores of the four different samples (ZMS-0, ZMS-25, ZMS-50, and
ZMS-75), respectively. Fig. 6 showed the photoluminescence exci-
tation (PLE) spectra of Mn:ZnS d-dots with different ZnS shell
thickness. It was found that all of the Mn:ZnS/ZnS (core/shell) d-
dots with different ZnS shell thickness exhibited significantly in-
creased PLE intensity with respect to that of Mn:ZnS d-dots with
the corresponding Mn doping concentrations (shown in Fig. 6a–
c), and ZMS-25 exhibited the most significantly increased PLE
intensity with respect to that of ZMS-0 (shown in Fig. 6d). Fig. 7
shows the room temperature photoluminescence (PL) spectra of
Mn:ZnS d-dots with different ZnS shell thickness under 340 nm
excitation. All of the Mn:ZnS/ZnS (core/shell) d-dots with different
ZnS shell thickness exhibited significantly increased photolumi-
nescence intensity with respect to that of Mn:ZnS d-dots with
the corresponding Mn doping concentrations (shown in Fig. 7a–
c). It was assumed that there were a large amount of surface de-
fects which served as nonradiative recombination paths for the
excitation energy in bare Mn:ZnS d-dots, which would quench
the emission of Mn2+ to some extent [33]. By the growth of an
additional ZnS shell on Mn:ZnS d-dots, the emission intensity of
Mn2+ in Mn:ZnS/ZnS core/shell d-dots were enhanced due to
the elimination of the surface defects [34]. Especially, ZMS-25
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Fig. 8. Photoluminescence (PL) spectra of as-prepared d-dots exposure in air at different time: (a) ZMS-0 and (b) ZMS-25.
exhibited the most significantly increased photoluminescence
intensity (integrated area) by 45% with respect to that of ZMS-0
(shown in Fig. 7d).
3.5.2. Stability of Mn:ZnS/ZnS (core/shell) d-dots in air
Peng et al. [6–7] reported that doped quantum dots (d-dots)
(e.g., Mn:ZnSe d-dots) were much less sensitive to thermal and
environmental variations. In this work, the stability of the prepared
Mn:ZnS/ZnS (core/shell) d-dots solid powders were investigated in
air. Fig. 8 showed the PL spectra of the as-prepared d-dots by expo-
sure to air at different time. It was found that the PL gradually re-
duced in air (shown in Fig. 8a), which indicated that Mn:ZnS d-dots
were strongly air sensitive. However, Mn:ZnS/ZnS (core/shell) d-
dots solid powders synthesized four months ago still retained their
bright PL (shown in Fig. 8 b) and not at all air sensitive.
4. Conclusion
The water-soluble Mn2+-doped ZnS quantum dots (Mn:ZnS d-
dots) were prepared through nucleation-doping strategy in aque-
ous solution in air. It was found that the Mn2+ 4T1 ? 6A1 emission
intensity of Mn:ZnS d-dots significantly increased with the in-
crease of Mn2+ concentration, and showed a maximum when
Mn2+ doping content was 1.0%. If Mn2+ concentration continued
to increase, namely more than 1.0%, the Mn2+ 4T1 ? 6A1 emission
intensity would decrease. By the growth of an additional ZnS shell
on Mn:ZnS d-dots, the emission intensity of Mn2+ in Mn:ZnS/ZnS
core/shell d-dots were enhanced due to the elimination of the sur-
face defects. Mn:ZnS/ZnS (core/shell) d-dots were not at all air sen-
sitive, while Mn:ZnS d-dots were strongly air sensitive.
Acknowledgements
This work was supported by the Provincial Excellent Ph.D. the-
sis Research Program of Hunan (No.2004-141).
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