Article

pubs.acs.org/JPCC

Controlled Synthesis of Ag2S Quantum Dots and Experimental

Determination of the Exciton Bohr Radius
Yejun Zhang,† Yongsheng Liu,‡ Chunyan Li,† Xueyuan Chen,‡ and Qiangbin Wang*,†
†
Suzhou Key Laboratory of Nanobiomedical Characterization, Division of Nanobiomedicine and i-Lab, Suzhou Institute of
Nano-Tech and Nano-Bionics, Chinese Academy of Sciences, Suzhou 215123 China
‡
Key Laboratory of Optoelectronic Materials Chemistry and Physics, Fujian Institute of Research on the Structure of Matter, Chinese
Academy of Sciences, Fuzhou 350002, China

ABSTRACT: Ag2S quantum dots (QDs) have attracted increasing attention due to
their appealing optical properties in the near-infrared regime. However, a full
understanding of the quantum confinement effect of Ag2S QDs has not been achieved
so far. Herein, for the first time, the size-dependent excited state optical properties of
Ag2S QDs are systematically investigated by photoluminescence (PL), PL excitation
(PLE), and time-resolved PL spectroscopy. Experimentally, we determine the exciton
Bohr radius of Ag2S QDs as 2.2 nm, which is highly consistent with theoretical results.

■ INTRODUCTION
Ag2S quantum dots (QDs) have been attracting intense interest
in recent years due to their appealing near-infrared (NIR)
photoluminescence (PL) in the second window (NIR-II,
1000−1400 nm), which promises in vivo fluorescence imaging
with higher penetration depth and higher signal-to-noise ratio
in comparison with the optical probes in NIR-I window (650−
950 nm).1−4 Much progress has been achieved in in vitro and
in vivo imaging by using Ag2S QDs.5−10 For example, highly
selective targeting and imaging of different cell lines in vitro
were accomplished by using Ag2S QDs conjugated with specific
ligands.5 Highly sensitive in vivo imaging of xenograft tumor on
a mouse model was realized by injecting Ag2S QDs via the tail
vein because of the enhanced permeability and retention (EPR)
effect of tumor vasculature.6 Furthermore, negligible toxicity
promises the potential clinical applications of Ag2S QDs.7−10 In
addition to their biomedical applications, Ag2S QDs present
enormous potential for applications in solar cell and electronic
transport.11−13
So far, most attention has been paid on the applications of
the Ag2S QDs. As a typical direct band gap semiconductor
nanocrystalline, the quantum confinement effect of Ag2S QDs
has been overlooked. In quantum confinement effect study,
there is an important parameter to understand the confinement
mechanism that is exciton Bohr radius, which describes the
smallest possible radius of an electron orbiting the nucleus in an
atom. To the best of our knowledge, there is no experimental
evidence of the exciton Bohr radius of Ag2S been reported in
previous reports. Pang et al. reported the tunable emission of
Ag2S QDs from 690 to 1227 nm by increasing the size of
Ag2S.14 However, there were only two typical sized Ag2S QDs
of 1.5 and 4.6 nm presented with emissions located at 813 and
1227 nm, respectively. Later, they reported the successful
synthesis of Ag2S QDs with emission from 510 to 1221 nm, in
which no systematical investigation of the size-dependent
emission was included either.10 More recently, Yu et al.
presented water-dispersible Ag2S QDs with emission tunable
from 1050 to 1294 nm as the size of the Ag2S QDs increasing
from 1.6 to 6.8 nm.15 Whereas, quantitative understanding of
the quantum confinement effect of Ag2S QDs was not satisfied
due to the poor size distribution and broad PL spectra of the
products. It still remains challenging in controlled synthesis of
high quality Ag2S QDs with tunable emission and narrow size
distribution and thus the fundamental understanding of the
confinement effect of Ag2S QDs.
Great efforts have been put on the controlled synthesis of
monodisperse semiconductor nanocrystals.16−24 For example,
Peng and co-workers recently demonstrated a simple and
general dispersion−decomposition approach to the synthesis of
metal sulfide nanocrystals, in which high-quality Ag2S, Cu2S,
PbS, Ni3S4, CdS, and ZnS nanocrystals were successfully
synthesized by direct heating of inorganic metal salts and
alkylthiol as the raw materials.21 In these methods, thermal
decomposition of single-source precursor method has been
considered as an effective way to produce the size- and shape-
controlled nanocrystals. Herein, a series of high quality Ag2S
QDs with different sizes from 2.4 to 7 nm were successfully
synthesized by using our previously reported single-source
Received: February 5, 2014
Revised: February 12, 2014
Published: February 19, 2014

© 2014 American Chemical Society 4918 dx.doi.org/10.1021/jp501266d | J. Phys. Chem. C 2014, 118, 4918−4923
The Journal of Physical Chemistry C Article

Table 1. Experimental Details and Products Characteristics

sample reaction temperature (°C) reaction time (min) size (nm) size dispersity (%) PL λmax (nm) fluorescence lifetime (ns) atomic ratio of Ag to S
A 130 1 2.4 22.1 975 57 1.30:1
B 140 2 2.8 19.6 1052 58 1.34:1
C 160 3 3.1 10.9 1091 84 1.45:1
D 180 2 3.7 6.5 1130 103 1.58:1
E 200 30 4.4 4.8 1175 132 1.69:1
F 210 60 5.4 3.9 1175 157 1.79:1
G 230 60 7.0 3.6 1175 181 1.86:1

Figure 1. Typical TEM images and size distribution (A−G) of as-prepared Ag2S QDs. A, 2.4 nm; B, 2.8 nm; C, 3.1 nm; D, 3.7 nm; E, 4.4 nm; F, 5.4
nm; G, 7 nm.

precursor method.25−27 The size-dependent optical properties,

including the absorption and PL spectra, PL excitation (PLE)
spectra, and PL lifetime, etc., were systematically studied.
Finally, the exciton Bohr radius of Ag2S QDs is experimentally
determined to be 2.2 nm, which is highly consistent with the
theoretical result.
4919
■ EXPERIMENTAL SECTION
Chemicals. 1-Dodecanethiol (DT, 98%, Aladdin), AgNO3,
(C2H5)2NCS2Na·3H2O (Na(DDTC)), ethanol (AR), and
chloroform (AR), (Sinopharm Chemical Reagent Company)
were used. All chemicals were used as received without further
purification.
dx.doi.org/10.1021/jp501266d | J. Phys. Chem. C 2014, 118, 4918−4923
The Journal of Physical Chemistry C
Preparation of Ag(DDTC). The preparation of single-
source precursor of Ag(DDTC) was referred to our previous
report.26 In a typical reaction, 0.05 mol of AgNO3 and
Na(DDTC) were first dissolved in 100 mL of distilled water,
respectively. Then, the two solutions were mixed with stirring
in a 500 mL beaker. After constant stirring at ambient condition
for 3 h, the resulting yellow precipitate was filtered, washed
with distilled water, and dried in air at 60 °C.
Synthesis of Ag2S QDs. Seven different-sized DT-capped
Ag2S QDs (2.4, 2.8, 3.1, 3.7, 4.4, 5.4, and 7 nm) were obtained
by thermal-decomposing Ag(DDTC). Thermal decomposition
of single-source precursor method has been considered as an
effective way to produce the size- and shape-controlled
nanocrystals.26 In a typical reaction, 0.1 mmol of Ag(DDTC)
was added into 10 g of DT in a three-necked flask (100 mL) at
room temperature. Then, oxygen was removed from the slurry
with vigorous magnetic stirring under vacuum for 5 min. The
reaction temperature was then raised to 130 °C with a rate of
10 °C/min and retained at this temperature for 1 min to allow
the growth of Ag2S QDs under N2 atmosphere. Ending the
reaction, 2.4 nm-sized DT-coated Ag2S QDs were obtained,
which were freely dispersed in chloroform solution. Different
sized Ag2S QDs were successfully prepared by tuning the
reaction conditions, and further characterization was carried out
with the final products (Table 1).
Characterization. The size and morphology of Ag2S QDs
and their high-resolution transmission electron microscopy
(TEM) (HR-TEM) images were examined by a Tecnai G2 F20
S-Twin TEM (FEI, USA) operated at 200 kV equipped with an
energy dispersive X-ray spectroscopy (EDS). TEM samples
were prepared by a drop-casting technique by putting 1 drop of
the chloroform solution onto a carbon-coated Cu grid, and the
solvent was evaporated at room temperature in the air. Powder
X-ray diffraction (XRD) patterns of the dried powders were
recorded on a Bruker D8 Advance powder X-ray diffractometer
at a scanning rate of 4° min−1, using Cu−Kα radiation (λ =
1.5406 Å) in the range of 20−60°. The UV−vis−NIR
absorption spectra were obtained on a Lambda 75 UV−vis−
NIR spectrometer (Perkin-Elmer, USA). The NIR fluorescence
spectra were executed on Applied NanoFluorescence Spec-
trometer (USA) at room temperature, applying an excitation
laser source of 785 nm. The PLE and fluorescence lifetimes
were measured on a spectrometer equipped with both
continuous (450 W) xenon and pulsed flash lamps (FLS920,
Edinburgh Instrument). NIR-II fluorescence imaging was
performed with a 640 × 512 pixel two-dimensional InGaAs/
SWIR camera (Photonic Science, U.K.). The atomic ratio of Ag
to S was measured by atomic absorption spectrum
(SpectrAA240FS-GTA120).
■
RESULTS AND DISCUSSION
Figure 1 shows TEM images of the as-prepared Ag2S QDs. In
general, the particles have isotropic shapes with relatively
narrow size distributions. The average sizes and size
distributions are listed in Table 1 by counting 150 Ag2S
QDs. It was found that the reaction temperature plays an
important role in determining the final product sizes and size
distributions. For example, the smaller-sized Ag2S QDs, such as
2.4 and 2.8 nm, prepared at lower reaction temperatures of 130
and 140 °C possess a wider size distribution in comparison with
the larger-sized Ag2S QDs, which were synthesized at higher
reaction temperature. This was attributed to coexistence of the
nucleation and growth processes during the reaction. It has
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been reported that Ag2S nucleation occurs at 120 °C triggered
by the dissociation of the Ag(DDTC).26 Thus, the growth
temperature of 130 or 140 °C is close to the nucleation
temperature, resulting in the wider size distribution of the
products. Elevating the growth temperature to 160 °C and
above, the effective separation of nucleation and growth
processes lead to the successful synthesis of monodisperse
Ag2S QDs, resulting from the different temperature depend-
ence of nucleation and growth kinetics, which has been
successfully illustrated in the previous study.28 The insets in
Figure 1 show HR-TEM images of Ag2S QDs with well-
developed lattice fringes, indicating good crystallinity of all
samples. The atomic ratio of Ag to S of seven different sizes was
shown in Table 1. The high sulfur content can be explained by
the face that DT as the capping agent is anchored on the
nanoparticles surfaces, which contributes the excess S. It is
notable that the ratio of Ag to S decreases as the size of Ag2S
QDs decreases, which was attributed to the larger specific
surface area of smaller QDs that associates more DT capped on
the surface.
Figure 2 presents the crystal structures of the resultant Ag2S
QDs. As nanocrystal size decreases, the XRD pattern peaks
Figure 2. XRD patterns of different-sized Ag2S QDs.
become broader. For the Ag2S with size smaller than 3.7 nm, a
broad peak is observed, which could be described to the major
crystal faces of Ag2S QDs. With the size larger than 3.7 nm,
characteristic diffraction peaks appeared, which can be assigned
to the monoclinic Ag2S (JCPDS No. 14-0072: a = 4.229 Å, b =
6.931 Å, and c = 7.862 Å). No impurities were detected in our
XRD measurement of the products.
The optical properties of the obtained Ag2S QDs such as
absorption and PL spectra are shown in Figure 3. It is observed
that the absorption spectra of Ag2S QDs are featureless with no
first discrete absorption feature evidence (Figure 3A), which is
different from the II−VI QDs that usually exhibit an evident
discrete absorption feature. We attribute this featureless
absorption spectrum to the special electronic property of
Ag2S QDs.29,30 Figure 3C presents the size-dependent PL of
Ag2S QDs, in which the fluorescence of Ag2S QDs is tunable
from 975 to 1175 nm by increasing the size from 2.4 to 4.4 nm.
The much narrower full width at half-maximum (fwhm) of the
prepared Ag2S QDs compared with the previous documenta-
tions14,15 endows the potential in vivo multiplex imaging with
higher spectral resolution. By keeping Ag2S QDs constant,
absorbance intensity at 808 nm, and a reference NIR dye (Dye-
26) with its absorbance at 808 nm, 10 times of that of Ag2S
QDs (Figure 3B), various PL intensities were observed when
dx.doi.org/10.1021/jp501266d | J. Phys. Chem. C 2014, 118, 4918−4923
The Journal of Physical Chemistry C Article

Figure 3. Optical properties of the as-prepared Ag2S QDs. (A) UV−vis-NIR absorption spectra; (B) daylight images; (C) PL emission spectra under
an excitation of 785 nm; (D) NIR-II fluorescence images.

Figure 4. PLE spectra (A) and time-resolved PL spectra (B−H) of the as-prepared Ag2S QDs.

illuminating by an 808 nm laser diode at a power density of 5.8
mW cm−2 (Figure 3D). As depicted in Figure 3D, the PL
brightness of Ag2S QDs was significantly brighter than that of
Dye-26 even with a much lower (1/10) concentration,
demonstrating the high PL brightness nature of Ag2S QDs.
Meanwhile, the PL brightness showed a decreasing tendency
with the increase of the QD sizes from 2.4 to 4.4 nm, which was
consistent with the reported results.31,32 Namely, the overlap
between electron and hole wave functions in an electron−hole
pair becomes smaller on increasing particle size, leading to a
4921
reduced radiative rate, and as a result, decreased brightness.33
Regarding the enhanced PL brightness of 5.4 and 7 nm sized
Ag2S QDs in comparison with that of 4.4 nm sized Ag2S QDs,
which may be attributed to the better crystallization of the
larger sized QDs. It is notable that it is difficult to quantify the
quantum yield (QY) of the Ag2S QDs with emission from 975
to 1175 nm since the QY of the InGaAs detector of the NIR
fluorescence spectrometer is not available. Nevertheless, Figure
3D illustrates the much higher brightness of Ag2S QDs than
that of the Dye-26.
dx.doi.org/10.1021/jp501266d | J. Phys. Chem. C 2014, 118, 4918−4923
The Journal of Physical Chemistry C
Interestingly, as shown in Figure 3C, we found that the PL
emission peaks red-shift from 975 to 1175 nm with the size of
Ag2S QDs increasing from 2.4 to 4.4 nm and keep constant at
1175 nm with further increase of the size from 4.4 to 7 nm. The
continuous red-shift of the PL emission of Ag2S QDs can be
attributed to the quantum confinement effect, which narrows
down the band gap energy as the Ag2S size increases. In
contrast, the PL emission peak remains constant at 1175 nm
with the continuous increase of the Ag2S size from 4.4 to 7 nm,
which could be explained as being out of the strong quantum
confinement regime and being in the weak quantum confine-
ment regime. Therefore, we experimentally speculate the Bohr
radius of Ag2S as 2.2 nm. In order to confirm this observation,
the exciton radius was calculated according to Griffiths
equation:34
4πεℏ2 ⎛ 1 1 ⎞
a0 = 2
⎜ + ⎟ support from the Special Project of National Major Scientific
e ⎝ me* mh* ⎠
where a0 is Bohr radius, ε is the bulk optical dielectric constant,
ℏ is the reduced Planck constant, e is the charge on the
electron, and me* and mh* are the effective masses of the
electron and hole, respectively. In the case of Ag2S, ε is 8.36,35
m*e equals 0.286m0, and m*h equals 1.096m0, respectively.36
Therefore, the exciton diameter of Ag2S is calculated to be 4.4
nm, which is highly consistent with our experimental
observation.
Furthermore, PLE and time-resolved PL spectra of the
obtained Ag2S QDs were measured as presented in Figure 4.
Figure 4A shows the normalized PLE spectra of the Ag2S QDs.
With size increasing from 2.4 to 4.4 nm, the excitation spectra
red-shifted. However, the PLE spectra remained unchanged as
the size of Ag2S QDs surpassed its Bohr radius up to 5.4 and 7
nm. This size dependence PLE feature is consistent with
CdSe37 and InAs/GaAs38 QDs. The lifetimes of the as-prepared
Ag2S QDs were also measured, and the decay constants were
presented in Figure 4B−H. The decay time of Ag2S band gap
emission increased from 57 to 181 ns as the size of Ag2S QDs
increasing from 2.4 to 7 nm. The strong size dependence of
lifetime component was attributed to the quasifree electron−
hole pair recombination emission process. The probability of
recombination decreased with the increased size due to the
relative large surface scattering rate.39 It is also probably related
to the surface defects of particles that have the smaller size with
more defects.40
■ CONCLUSIONS
The quantum confinement effect of Ag2S QDs was systemati-
cally studied and the exciton Bohr radius of Ag2S QDs was
experimentally determined as 2.2 nm. In order to quantitatively
understand the quantum confinement effect of Ag2S QDs, a
series of uniform Ag2S QDs sizing from 2.4 to 7 nm with
narrow size distribution were successfully synthesized by using
a facile single-source precursor method in which the size was
precisely controlled by modifying the reaction conditions. The
obtained Ag2S QDs exhibit well-defined PL spectra with
emission from 975 to 1175 nm and high PL brightness. The PL
and PLE results illustrate that the size-dependent optical
properties of Ag2S QDs were restricted in the range of 2.4 to
4.4 nm, that is the strong quantum confinement regime, and no
size-dependent optical property was observed when the size of
Ag2S QDs was larger than 4.4 nm. Experimentally, we
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determine the exciton Bohr radius of Ag2S QDs as 2.2 nm,
which is highly consistent with theoretical results.
■
AUTHOR INFORMATION
Corresponding Author
*(Q.W.) E-mail: qbwang2008@sinano.ac.cn. Tel/Fax: 86-512-
62872620.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
Q.W. acknowledges the financial support from CAS Bairen Ji
Hua and Strategic Priority Research Program (XDA01030200),
MOST (2011CB965004), NSFC (21073225), and NSF of
Jiangsu Province (BK2012007). X.C. and Y.L. acknowledge the
Equipment Development of China (2012YQ120060) and
Scientific Equipment Development Project of CAS
(YZ201210).
■
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