Research Article

www.acsami.org

Warm White Light Emitting Diodes with Gelatin-Coated AgInS2/ZnS

Core/Shell Quantum Dots
Xiaojiao Kang, Yanchun Yang,, Lan Wang,, Song Wei,, and Daocheng Pan*,

State Key Laboratory of Rare Earth Resource Utilization Changchun Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun 130022, Peoples Republic of China

University of the Chinese Academy of Sciences, Beijing 100049, Peoples Republic of China
*
S Supporting Information

ABSTRACT: Cadmium-free and water-soluble AgInS2/ZnS core/shell quantum

dots (QDs) with a cost of 2.5 $/g are synthesized in an electric pressure cooker.
The QD powders with dierent Ag/In ratios exhibit bright yellow, orange, and
orange-red luminescence under UV light. Their absolute photoluminescence
quantum yields (PLQYs) can reach as high as 50.5, 57, and 52%, respectively.
Because gelatin is used as the capping agent, the concentrated QDs/gelatin
solution can be directly utilized as phosphor for the fabrication of white light-
emitting diodes (LEDs) by a simple drop-drying process without the need of
resin package. Warm-white LEDs are obtained by combining orange-emitting
QDs with blue InGaN chip. As-fabricated warm-white LED exhibits a luminous
ecacy of 39.85 lm/W, a correlated color temperature (CCT) of 2634 K and a
color rendering index (CRI) of 71 at a drive current of 20 mA. Furthermore, the
electroluminescence (EL) stability of LED device and thermal stability of as-
prepared QDs are evaluated.
KEYWORDS: AgInS2, gelatin, quantum dots, lighting, white LEDs

1. INTRODUCTION phosphors, the light scattering loss is unavoidable, whereas

White light emitting diodes (LEDs) have gained more and
more attention due to their unique properties including
compactness, high energy eciency, environmental friend-
liness, and long operational lifetime compared with conven-
tional incandescent and uorescent lamps.14 Warm-white
LEDs with low correlated color temperature (CCT) are favored
for solid-state lighting applications in room lighting.5,6
Currently, commercial white LED system consists of a 460
nm InGaN blue LED chip and Y3Al5O12:Ce3+ (YAG:Ce) yellow
phosphor, which produces a relatively cold white light.7 To
resolve this problem, many researchers developed a series of
red-emitting phosphors to combine with YAG:Ce.8,9 Another
way may generate warm white light by applying a UV LED chip
to excite blends of tricolor (blue, green, and red) phosphors.
However, the luminous eciency is low in this system due to
the strong reabsorption of the blue light by the red and green
phosphors.10 In addition, emission color may change after long
illumination periods due to the dierent degradation rates of
the phosphors. Hence, direct warm-white LEDs based on
single-component emitter are more expected because of better
color reproducibility and simpler fabrication process.
The converters of phosphor-converted (pc)-white LEDs can
be classied into four categories: inorganic phosphors, organic
phosphors, inorganicorganic phosphors, and semiconductor
QDs.1114 Thereinto, highly luminescent QDs have been
regarded as promising color converters owing to their many
superior advantages. In the case of microsized inorganic
QDs possess no-scattering property because of their small sizes
(<10 nm).15 Besides, emission colors of QDs can be readily
tuned by adjusting composition and/or size of QDs.1618
Usually, QDs with a broad emission band can cover a wide
spectral region, which facilitate achieving high-performance
white LED devices.19 Therefore, a great deal eort has been
made to fabricate QD-based white LEDs.2024 Hong et al.
fabricated white LEDs with color rendering index (CRI) of 91
by combining blue InGaN chip with green-emitting and red-
emitting CdSe-ZnSe QDs.25 However, the high toxicity of the
cadmium elements will impede their practical lighting
applications.21,25,26 It is necessary to develop environment-
friendly alternatives such as ternary IIIIVI QDs to achieve
white LEDs. Recently, low-toxic IIIIVI QDs such as AgInS2
and CuInS2 QDs have been extensively synthesized by an
organic phase approach at high temperature.2738 These highly
luminescent and hydrophobic AgInS2 and CuInS2 QDs have
been successfully utilized in white LEDs as wavelength
converters.2735,38 However, the production cost of hydro-
phobic AgInS2 and CuInS2 QDs is much higher than that of the
most commonly used YAG:Ce phosphor, which hinders their
widespread application in white LEDs. Although the aqueous
phase approach is particularly suitable for large-scale and low-
Received: September 8, 2015
Accepted: December 2, 2015
Published: December 2, 2015

2015 American Chemical Society 27713 DOI: 10.1021/acsami.5b10870

ACS Appl. Mater. Interfaces 2015, 7, 2771327719
ACS Applied Materials & Interfaces
cost synthesis of AgInS2 and CuInS2 QDs, the PLQYs of water-
soluble AgInS2 and CuInS2 QDs are signicantly lower than
those of hydrophobic QDs. Hence, there will be of great
signicance for the aqueous synthesis of highly luminescent and
low-cost AgInS2 and CuInS2 QDs. Recently, we have
successfully prepared water-soluble CuInS2, AgInS2, CuInSe2,
and AgInSe2 QDs on a multigram scale in a 5.0 L of
commercial electric pressure cooker.3941 These water-soluble
QDs have high PLQYs in the range of 2040% with a
production cost less than $3/g, which make it possible to
fabricate white LEDs by using water-soluble IIIIVI QDs.41
In this work, highly luminescent AgInS2/ZnS core/shell QDs
were synthesized in the aqueous solution of gelatin and
thioglycolic acid (TGA) and were used for white LEDs
(Scheme 1). A 1.0 L of electric pressure cooker was used as the
Scheme 1. Fabrication Strategy of Gelatin-Coated AgInS2/
ZnS Core/Shell QDs and the Corresponding QD-based LED
Device
Figure 1. (A) Excitation and (B) PL spectra of (a) QD-1, (b) QD-2, and (c) QD-3. (C) Photographs of corresponding QD powders under
illumination of UV (365 nm) light.
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reaction vessel to synthesize gelatin-coated QDs with a cost of
about $2.5/g. It is worth noting that introduction of gelatin
during the growth of ZnS shell is to prevent aggregation of
QDs in dried states. The powders of resulting QDs have
PLQYs of 50.557%, and they present composition-dependent
PL properties. All AgInS2/ZnS core/shell QDs are tested as
wavelength converters for the fabrication of LEDs. The warm-
white light can be directly realized by combing orange-emitting
QDs with a blue LED chip. The white LED was relatively stable
against the increase of drive current.
2. EXPERIMENTAL SECTION
2.1. Materials. Silver nitrate (A.R.), indium hydroxide (In(OH)3,
99.99%), TGA (A.R.), ammonium sulde solution ((NH4)2S, 4048
wt % in H2O) and gelatin (pharmaceutical grade, 240 g Bloom)
were purchased from Aladdin. Ammonia solution (NH3H2O, A.R.)
were supplied by Beijing Chemical works. All the initial chemicals in
this work were used without further purication.
2.2. Synthesis of AgInS2 Core and AgInS2/ZnS Core/Shell
QDs. AIS core was synthesized according to our previous report, with
some minor modications.40 In a typical synthesis of AIS core with a
Ag/In ratio of 1/8, 4 g of gelatin was added to 700 mL of H2O and
was dissolved at 40 C under agitation. Indium (In) stock solution was
prepared by dissolving 0.2653 g of In(OH)3 in 1.04 mL of TGA, 0.96
mL of NH3H2O and 8 mL of H2O. Subsequently, 0.0679 g of AgNO3
and In stock solution were added into gelatin solution and were
poured into a 1 L electric pressure cooker. Afterward, 0.8 mL of
(NH4)2S was swiftly injected into the above mixture solution under
strong magnetic stirring. Subsequently, the cooker was heated up and
kept up the pressure for 1.0 h. AgInS2 QDs with starting Ag/In ratios
of 1/4 and 1/3 were prepared in the same way as above except for
using dierent amounts of AgNO3 and In(OH)3. After 1.0 h, the
reaction temperature was lowered to 80 C, and 100 mL of the
aqueous solution containing 0.4089 g of ZnCl2, 0.2284 g of thiourea,
and 4 g of gelatin were added into the above cooker. The reaction
would be lasted for another 1.0 h under the pressure to deposite ZnS
shell around the AgInS2 cores. Finally, the core/shell QDs solution
DOI: 10.1021/acsami.5b10870
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ACS Applied Materials & Interfaces
was cooled naturally. The AgInS2/ZnS core/shell QDs with starting
Ag/In ratios of 1/8, 1/4, and 1/3 were denoted as QD-1, QD-2, and
QD-3, respectively. As-synthesized QDs were precipitated with an
excess of ethanol and puried repeatedly with ethanol by
centrifugation.
2.3. Fabrication of LED Devices. The puried QDs were
redispersed into a certain volume of deionized water to form a viscous
solution. The unpackaged blue-emitting InGaN LED chips ( = 460
nm) were used to fabricate the QD-based LED devices. The QDs
solution was directly dropped into the groove of chip. This chip was
placed in an oven and dried at 80 C for 0.5 h. The LED devices using
QD-1, QD-2, and QD-3 were denoted as LED-1, LED-2, and LED-3,
respectively.
2.4. Characterizations. The X-ray diraction (XRD) measure-
ments were performed on a D8 Focus diractometer (Bruker) with Cu
K radiation ( = 0.15405 nm). Transmission electron microscopy
(TEM) was performed using FEI Tecnai G2 S-Twin with a eld
emission gun operating at 200 kV. Thermogravimetric and dierential
scanning calorimetry (TG-DSC) data were recorded with a Netzsch
Thermoanalyzer STA 409 with a heating rate of 10 C/min in N2
environment. UVvis absorption spectra were measured by Metash
5200 spectrophotometer. The PL measurements were performed with
a Hitachi F-7000 spectrophotometer equipped with a 150 W xenon
lamp as the excitation source. Absolute photoluminescence quantum
yields (PLQYs) were measured by the absolute PL quantum yield
measurement system (C9920-02, Hamamatsu Photonics K. K., Japan).
The luminescence decay curves were obtained from a Lecroy Wave
Runner 6100 digital oscilloscope (1 GHz) using a tunable laser (pulse
width = 4 ns, gate = 50 ns) as the excitation source (Continuum
Sunlite OPO). The Commission Internationale de lEclairage (CIE)
chromaticity color coordinates, color rendering index (CRI), and
correlated color temperature (CCT) were measured by Starspec
SSP6612. The temperature dependent PL spectra were monitored by a
Maya 2000 Pro CCD-based ber optic spectrometer (Ocean Optics,
Inc.) in air, and the temperature was programmed to increase from 20
to 150 C. The thickness of gelatin lm was measured by a step
proler (AMBIOS, XP-100). The Fourier transform infrared (FTIR)
spectra were recorded on a Nicolet 6700 spectrophotometer (USA) in
the range of 4000400 cm1.
3. RESULTS AND DISCUSSION
The eco-friendly gelatin-coated AgInS2/ZnS core/shell QDs
were synthesized via a facile aqueous method. Figure 1a,b show
the normalized excitation and emission spectra of three types of
QD powders. The excitation spectra contain three bands with
the peaks at 280 nm, 370 and 460 nm, which cover the UV,
near-UV, and blue regions (from 230 to 520 nm). The
emission color of QDs could be tuned by varying the starting
Ag/In ratios. Three visible emissions, namely, yellow, orange,
and orange-red, were observed in the digital photo, as shown in
Figure 1c. Compared with PL emission spectra of QD solutions
with the same Ag/In ratio, the emission peak positions of QD
powders shift to longer wavelength.40 The QDs in liquid and
solid state have dierent optical properties including PL peak
position, PLQYs and lifetime. The distances between the QDs
became shorten after drying. It enhances the energy transfer
from smaller QDs in the ensemble to larger ones, leading to the
red shift of the PL band.42 The measured absolute PLQYs of
QD powders at 460 nm excitation were 50.5, 57, and 52%,
respectively. High-quality luminescence in the solid state is
attributed to the uniform distribution of QDs in gelatin matrix.
Due to the broad PL emission and the high absorption in UV
and blue region, QDs could be used as wavelength converters,
which are combined with a blue InGaN LED chip.
Structure characterizations were carried out by means of
XRD and TEM measurements. Figure S1A shows the XRD
patterns of AgInS2 core (Ag/In = 1/4) and QD-2. Both core
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and core/shell QDs adopt the tetragonal chalcopyrite crystal
structure.40,43 A right-shift of the corresponding diraction
peaks is observed upon modication with ZnS, which is an
indication of the formation core/shell structure. The XRD
patterns of QD-1 and QD-3 are also displayed in Figure S1B.
Figure S2 shows TEM image of QD-2. The AgInS2/ZnS core/
shell QDs are well dispersed in a gelatin matrix. The QDs have
an average size of about 3.0 nm. The clear lattice fringes are
observed in HR-TEM image. The space between two adjacent
fringes was measured to be 0.32 nm, which is accordance with
the d-value of the (112) plane of the tetragonal AgInS2.
Concentrated gelatin/QD solutions are poured into the
molds with dierent shapes at elevated temperature (50 C)
and formed jelly at room temperature. As displayed in Figure
S3, QD-based jelly exhibited bright luminescence under UV
light irradiation (365 nm). Figure 2 shows the luminescence
Figure 2. Fluorescence decay curves of (a) QD-1, (b) QD-2, and (c)
QD-3.
decay curves of gelatin-coated QD powders under the
excitation of 460 nm. The calculated average PL decay lifetimes
for QD-1, QD-2, and QD-3 are 432.41, 364.69, and 271.84 ns,
respectively. The measurement of as-prepared QD lumines-
cence kinetics shows biexponential decay, with a fast
component and a slow component. The shorter and the longer
lifetime can be assigned to surface trap states and donor
acceptor transition, respectively. As-prepared QDs exhibit a
long PL lifetime of several hundreds of nanoseconds. Dierent
from binary CdSe/ZnS core/shell QDs, they usually exhibit a
single-exponential decay with a short PL lifetime of tens of
nanoseconds, which can be assigned to the bandband
emission.44,45
To evaluate the device performance for the synthesized QDs,
we fabricated white LEDs by combing blue chips (460 nm)
with yellow-, orange- and orange-red-emitting QDs. The
chromaticity coordinates of three LEDs with CCTs of 4006,
2634, 2249 K under an operating current of 20 mA, (0.3801,
0.3764), (0.4197, 0.3323), and (0.4177, 0.2928), are marked in
CIE 1931 color spaces, respectively (see Figure 3a). Generally,
QDs were embedded in the encapsulant (e.g., epoxy or silicone
resin) in literature.2731,46 In this case, it may lead to the
exudation and aggregation of QDs due to the lack of chemical
bonding between QDs and resin. Additionally, the introduction
of a thick resin layer will reduce LED eciency and increase the
production cost. Gelatin is a natural nontoxic, biocompatible
biopolymer which is produced by partial hydrolysis of
collagens.47 Gelatin can form a three-dimensional network
with zones of intermolecular microcrystalline junctions and the
dehydration of this system may produce transparent lms.48 In
our system, inexpensive gelatin is chosen not only as the
capping agent to synthesize QDs but also as the encapsulant to
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Figure 3. (a) CIE chromaticity diagram and (b) photograph of three as-fabricated LEDs; photographs of (c) lighted LED-1, (d) LED-2, and (e)
LED-3; EL spectra of (f) the three LEDs under 20-mA drive current and (g) LED-2 under various drive currents.

fabricate LEDs. Hence, QD/gelatin dispersion could be directly Table 1. EL Parameters of As-Fabricated LEDs
dropped onto the LED chip to form a homogeneous QD/
chromaticity
gelatin hybrid lm after drying. Photographs of as-fabricated coordinate
LEDs and three lighted ones are shown in Figure 3be. Figure CCT current ecacy
S4a,b show TG curves of QD-2 and pure gelatin. The TG result sample (K) CRI x y (mA) (lm/W)
demonstrates that the powder contains 13 wt % QDs. A large LED-1 4006 68.6 0.3801 0.3764 20 46.24
amount of gelatin surrounds QDs to prevent serious LED-2 2634 70.9 0.4197 0.3323 20 39.85
agglomeration. Using the gelatin-coated QDs with dierent 2608 73.1 0.4220 0.3325 40 30.67
emission colors, the CCT decreases from 4006 to 2249 K. 2630 73.3 0.4180 0.3289 60 19.85
Cold-white, warm-white, and red lights are successfully created 2650 72.0 0.4156 0.3266 80 14.51
with QD-1, QD-2, and QD-3, respectively. Because of uniform 2664 71.1 0.4135 0.3241 100 11.35
dispersion of QDs on top of LEDs, our devices show uniform 2674 70.7 0.4110 0.3227 120 9.26
color distribution, which are more advantageous than LEDs LED-3 2249 66.6 0.4177 0.2928 20 15.41
using bulk phosphor/resin as wavelength converter. The EL
spectra of the devices were measured and are displayed in water-soluble AgInS2/ZnS QDs using as color converter are
Figure 3f. The sharp emission band at 460 nm is ascribed to a more advantageous for comparison.
blue InGaN chip. The three broad emission bands centered at Small color uctuation under varied excitation powers is
571, 595, and 613 nm correspond to QD-1, QD-2, and QD-3, crucial for the long-term service of LEDs. Normalized EL
respectively. The emission spectra are quite broad. As a result, spectra of LED-2 as a function of drive current from 20 to 120
LED-2 can emit bright warm-white light, with a CRI of 71 at 20 mA remained essentially the same, as shown in Figure 3g. The
mA. Table 1 shows EL properties such as CCT, CRI and CIE color coordinates changed from (0.4197, 0.3323) to
luminous ecacy for the three LEDs. We also summarized the (0.4110, 0.3227), as shown in Figure 4a. The blue-shifted color
properties of white LEDs based on IIIIIV QDs in previous coordinates of the warm-white LED is ascribed to thermal
quenching eect of the QDs at high drive current.33 The slight
literature, as listed in Table S1. Park et al. reported that the
variation of the chromaticity coordinate, merely 0.0087 for
CuInS2/ZnS QDs-based white LED showed a high luminous CIE-x and 0.0096 for CIE-y, respectively, reconrms the
ecacy of 81.1 lm/W, a CRI of 72, and CCT of 5497 K.31 negligible color uctuation. In addition, Figure 4b shows the
However, the CCT value was higher than those (27003500 variations of CRI/CCT of LED-2 as a function of current from
K) of warm white. At the similar CCT, our gelatin/QDs-based 20 to 120 mA. With increasing current CCTs increase from
LED device exhibited similar or better EL properties including 2634 to 2674 K. CRI was kept between 70.7 and 73.3. A slight
luminous ecacy and CRI compared to other reported white change in LED parameters under dierent drive currents
LEDs.34,35 Thereinto, only our QDs were prepared in aqueous demonstrated a good EL stability of the LED device. In
phase, which is more cost-eective and greener. Hence, our addition, EL spectra and CIE color coordinates of LEDs can be
27716 DOI: 10.1021/acsami.5b10870
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Figure 4. (a) Variations of CIE color coordinates and (b) CRI/CCT
of LED-2 as a function of current from 20 to 120 mA.
also tuned by varying the amount of QD-2 solution. With
increasing the content of QDs, orange emission increased, as
shown in Figure 5. Meanwhile, the color shifted from blue to
purple, white, warm-white, and yellow, respectively.
Figure 5. (a) EL spectra and (b) CIE color coordinates of LEDs with
dierent amounts of QD-2.
As LED packaging materials, they are preferably easily
processable and optically transmissive with respect to the
wavelength of light produced by the LED chip and phosphors.
In addition, it could provide protection as moisture, gas, and
lipid barriers to prolong service life of LED. With the operation
time of LED device increasing, the junction temperature
increases. Therefore, it is very necessary to study the
transmittance and lifetime of gelatin during the high temper-
ature. To prepare the gelatin lm, gelatin solution (4 wt %) was
dropped onto the surface of the glass (2 2 cm). The gelatin
lms were formed after water evaporation at room temperature
(RT). The thickness of gelatin lm was determined to be
around 10 m. Figure S5 shows optical transmittance spectra of
gelatin lm after heating treatment. With the increase of heating
temperature, the transmittances of gelatin lms decrease
slightly. The gelatin lm after heating at 100 C for 10 h
shows average transmittance as high as 94.22% in the visible
region. The photographs (Figure S5b inset) further manifest
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that the gelatin lm is transparent with high transmittance.
Furthermore, Figure S6 displays FTIR spectra of gelatin lm
before and after heating at 100 C for 10 h. There is no obvious
change in these two spectra. The characteristic bands from OH
(3440 cm1), COOH (1645 cm1), and NH2 (1532 cm1)
groups can be observed. TG-DSC curves revealing thermal
degradation behavior of gelatin are illustrated in Figure S4. The
exothermal peak at 350 C is attributed to the degradation of
gelatin. These results indicate that the gelatin as the
encapsulant possesses good transmittance and stability during
LED device operation.
For LED applications, the thermal quenching of QD
luminescence is also critically important. Figure S7 shows the
thermal stability of gelatin-coated QDs. Upon heating to 150
C in air, the emission intensities of QDs were gradually
reduced. There is a 78, 66, and 57% loss of intensity after
heating up to 150 C, respectively. The thermal quenching of
PL could be involved with the thermal emptying of radiative
intragap levels, accompanied by a higher probability of
thermally activated nonradiative recombination of photoexcited
carriers.4951 Figure S7bd depicts 3D temperature-dependent
PL spectra of QD-1, QD-2 and QD-3. A slight red shift (10
nm) of PL peak was observed with increasing temperature from
20 to 150 C. These results reveal that the thermal stability of
as-prepared QDs is acceptable. In our ongoing experiments, we
will further improve the thermal stability and quantum yield of
AgInS2/ZnS core/shell QDs by increasing the thickness of ZnS
shell.
Finally, we compared as-prepared AgInS2/ZnS QDs with
conventional LED phosphors (YAG:Ce) as color converters.
Our QDs possess the following advantages: low temperature
synthesis, no-scattering property, and direct fabrication of
warm-white LED (low CCT). High-temperature solid-state
reaction is commonly used to prepare YAG:Ce phosphors. The
synthetic process is energy-consuming. Whereas, the reaction
temperature of our AgInS2/ZnS QDs is 120 C, which is
much lower than that of synthesizing YAG:Ce phosphors. In
YAG:Ce-based white LEDs, the light scattering loss is inevitable
due to the microsized and agglomeration of phosphors. This
phenomenon leads to the reduction of blue-to-yellow
conversion eciency and consequently limits device luminous
ecacy. These are no such problems in our QDs-based system
since the AgInS2/ZnS QDs with a diameter of 3 nm can be well
dispersed in the gelatin matrix. In addition, the YAG:Ce-based
white LEDs emit a cold white light which are not suitable for
room lighting. Warm-white LEDs with low CCT can be directly
obtained by combing our orange-emitting QDs with a blue
LED chip. The above analysis indicates that gelatin-coated
AgInS2/ZnS QDs are good candidates for white LEDs.
4. CONCLUSION
In summary, we have successfully synthesized highly
luminescent gelatin-coated AgInS2/ZnS core/shell QDs using
the electric pressure cooker as the reaction vessel. The gelatin-
coated QDs in solid state displayed high PLQYs of 50.557%
and composition-tunable emission colors from yellow, orange
to orange-red. All core/shell QDs are tested and used as
wavelength converters for the fabrication of LEDs. Cold-white,
warm-white, and red lights are realized by combining blue chip
with single-component QDs. In addition, the fabricated white
LED shows good EL stability with varied drive current. These
results indicate that as-prepared core/shell QDs are promising
luminescent materials for blue LED-pumped white LEDs.
DOI: 10.1021/acsami.5b10870
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ACS Applied Materials & Interfaces
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsami.5b10870.
XRD patterns of AgInS2 core (Ag/In = 1/4) and QD-2;
XRD patterns of QD-1, QD-2 and QD-3; TEM and HR-
TEM images of QD-2; photograph of QDs-based jelly
with dierent shapes under illumination of UV light; TG
curve of QD-2 and TG-DSC curves of pure gelatin;
optical transmittance spectra of gelatin lm with a
thickness of 10 m after heating at dierent temperatures
for 1 h and heating at 100 C for dierent time; digital
photograph of gelatin lm before and after heating
treatment; FTIR spectra of gelatin lm before and after
heating at 100 C for 10 h; the temperature-dependent
emission intensity and 3D PL spectra of QDs; CCT,
CRI, and luminous ecacy of white LEDs based on I
IIIIV QDs in previous literatures and our report.
(PDF)
AUTHOR INFORMATION
Corresponding Author
*Tel.: +86-431-85262941. E-mail: pan@ciac.ac.cn.
Notes
The authors declare no competing nancial interest.
ACKNOWLEDGMENTS
This work was supported by the National Natural Science
Foundation of China (grant no. 51402285; 5117229;
51202241; 91333108).
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ACS Appl. Mater. Interfaces 2015, 7, 2771327719