Article

pubs.acs.org/JPCC

Enhanced Photoelectric Properties in Dye-Sensitized Solar Cells

Using TiO2 Pyramid Arrays
Wei Jiang, Hongzhong Liu,* Lei Yin, Yongsheng Shi, and Bangdao Chen
State Key Laboratory for Manufacturing Systems Engineering, Xi’an Jiaotong University, Xi’an 710049, China
*
S Supporting Information

ABSTRACT: In this study, the improved device performance

obtained by introducing pyramid-structured photoanodes has
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been investigated. The periodical pyramid arrays in the TiO2

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active layer are fabricated by soft imprint lithography. The

pyramid-structured photoanodes are characterized by scanning
electron microscope, UV−vis spectroscopy, and electro-
chemical impedance spectroscopy. The experimental results
demonstrate that pyramid-structured photoanodes can reduce
the transmission light loss over a broad wavelength region and
result in increased light reflection and scattering effect. Hence,
dye-sensitized solar cells with periodical pyramid arrays can increase the light absorption in the active layer and enhance the
photovoltaic performance. The overall efficiency of such structured devices is increased by 20% in comparison with the device
without periodical pyramid arrays and scattering layers. Fabrication of periodical pyramid arrays of mesoporous inorganic oxide
films also can be applied for other various devices with micro-/nanostructures at low cost using readily available pastes and soft
imprint lithography.

1. INTRODUCTION In order to solve the above issues, some kind of bilayer

Nowadays, the growing consumption of fossil fuel and
increasing environmental awareness are driving people to
look for new alternative energy resources. Solar energy is clean
and nonpolluting and can be used without limit. Photovoltaic
technology is regarded as one of the most efficient light
utilization technologies.1,2 New photovoltaic production
technologies with low cost and simple processes are of great
interest to academia and industry.3 For the past few decades, as
one of the next generation solar cells, dye-sensitized solar cells
(DSSCs) have attracted more and more researchers’ attention
owing to its inexpensive and environmental friendly pro-
cesses.4−6 However, the photovoltaic efficiency of current
DSSCs has not reached the theoretical level.7,8 The device
performance strongly depends on the joint effect of different
combinations of photoanode morphologies, sensitizers, electro-
lytes, and counter electrodes.9,10 With regard to the photo-
anode, it is mainly charged with the dye molecules uptake,
incident light capture, and providing electrons and electrolyte
ions pathway. Therefore, the photoanode plays an important
and decisive role in DSSCs operation principle.11 Generally, the
photoanode is composed by mesoporous TiO2 nanoparticle
networks, which have a high surface area and an average particle
size less than 30 nm. But the thin planar nanoparticles film has
high light transparency leading to a negligible light scattering
effect, and the thick planar nanoparticles film has more
complicated nanoparticle grain boundaries resisting the
mobility of photoinduced electrons.12 Hence, the above-
mentioned drawbacks significantly limit the further enhance-
ment of the device efficiency.
photoanodes,13 in which small size TiO2 nanoparticles are used
as underlayer and large size TiO2 nanoparticles14 or other
nanostructures aggregates 15−17 as overlayer, have been
demonstrated to be efficient methods to improve the
performance of DSSCs. Also, some other hierarchical
structured photoanodes including spherical/core−shell aggre-
gates have been introduced to enhance the photoelectric
conversion efficiency of DSSCs.18,19 For instance, the 3D
macroporous TiO2 sphere with controlled macropore sizes are
synthesized by using well-arrayed poly(methyl methacrylate)
with different diameters.20,21 However, in order to further
expedite the electron transport and reduce the costs, the next
generation DSSCs will require a much thinner active layer,
rendering most of the above-mentioned methods ineffective.
Aiming at these problems, light trapping strategies have been
developed to enhance the light absorption of the limited film
thickness of the active layer. In conventional silicon-based solar
cells, light trapping technologies have been generally used to
enhance the photoelectrical properties by pattering silicon
substrate with low reflection and reduced resistivity. These light
trapping structures can substantially reduce reflection loss as
well as significantly increase the effective optical path length by
total internal reflection within the cell. A large augmentation
achieving to 24.4% in silicon cell efficiency by integrated light
trapping structures has been reported.22 Accordingly, some
Received: March 15, 2016
Revised: April 20, 2016
Published: April 21, 2016

© 2016 American Chemical Society 9678 DOI: 10.1021/acs.jpcc.6b02687

J. Phys. Chem. C 2016, 120, 9678−9684
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light-trapping strategies have also been developed in DSSCs to
enhance the light absorption for the limited film thickness of
the active layer. For example, Ki Seok Kim23 et al. reported a
functionalized photoanode with periodically aligned ZnO
hemisphere crystals. Nanopatterned photoanodes obtained
from etched transparent conducting glasses24 and nano-
imprinting TiO2 nanoparticles25,26 film by the patterned master
also have been introduced to enhance the light absorption of
the photoanodes in some public reports.
Therefore, the light trapping structures can both result in
cheaper devices and better performance by strengthening the
light absorption ability and producing larger current. Similarly,
in order to further increase the competitive advantages of
DSSCs, efforts on maximizing the light absorption ability of the
photoanodes are still strongly expected. Pyramid structures
have been extensively used to fabricate optoelectronic devices,
particularly in photovoltaic fields over the decades owing to the
multiple internal light reflection and absorption on the angular
surface.27−31 The pyramid structures can increase the optical
path length by factors as high as 40 and have been
experimentally demonstrated to be one of the most efficient
light trapping structures.31,32 Teck Kong Chong et al.33
confirmed that 91% of the ideal light trapping limit (the
Lambertian limit) could be achieved by a skewed silicon
pyramid grating placed on the front of a thin silicon solar cell.
Accordingly, some efforts should also been tried on integrating
the pyramid structures into the DSSCs photoanodes. And the
pyramid structures are expected to increase the light harvesting
capacity of the active layer for the optimum performance.
In this paper, we report on the fabrication of pyramid-
structured photoanodes prepared by soft imprint lithographic
technique for DSSCs application. The pyramid-structured TiO2
nanoparticle film not only reduces incident light transmission
loss but also increases the cell’s effective optical thickness.
Meanwhile, the enhanced interface area between the scattering
layer and active layer can lead to more incident light being
scattered and absorbed by an enlarged interface area. The
schematic cell based on periodical pyramid arrays is shown in
Figure 1. The photovoltaic performance was investigated by
Figure 1. Schematic diagram of DSSCs for periodical pyramid-
structured photoanodes.
optoelectronic and electrochemical measurements in detail.
The characteristics of the pyramid-structured DSSCs were
compared with those of flat reference DSSCs in the motivation
to explore the effectiveness of pyramid-structured photoanodes
and soft imprint lithographic technologies. In the present
scenario of photoelectric research, this report may be useful for
the researchers to fabricate some efficient patterned structures
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on electrodes via cost-effective methods and to achieve the
improved efficiency.
2. EXPERIMENTAL SECTION
2.1. Fabrication of the Inverted Pyramid Poly-
(dimethylsiloxane) (PDMS) Stamp. The masterplate with
periodically inverted pyramid arrays were fabricated on silicon
substrate by using conventional microfabrication techniques
based on traditional photolithography and wet etching process.
The wet etching process proceeded in a solution containing 30
g of NaOH and 1000 mL of water at 80 °C. The complete
fabrication process flow is described as in the following steps,
which is shown in Figure 2. As the first step of this process, a
Figure 2. Schematic representation of the preparation of inverted
pyramid PDMS stamp.
200 nm thick Cr layer was deposited on a ⟨100⟩ silicon wafer
by magnetic sputtering. After depositing the Cr layer, the
periodical holes were patterned in photoresist on the surface of
Cr layer by photolithography. The following pattern trans-
ferring onto the Cr layer was performed by a Ce(NH4)2(NO3)6
(ammonium ceric nitrate) solution etching process. Sub-
sequently, the wafer was etched in NaOH solution to fabricate
the pyramid structures. The reason for applying NaOH solution
was that it can etch silicon anisotropically, yielding a self-
aligned pyramid structure. The morphologies of the generated
pyramid structure can be tuned by varying the period, exposure,
and etching conditions. Then, the Cr mask was removed by
Ce(NH4)2(NO3)6 solution after the etching process. The
resultant pyramid structures were cleaned with acetone,
isopropyl alcohol, and ethanol in sequence. In order to reduce
the damage to the pyramid mold during the replication process,
the obtained pyramid mold was further treated with
trimethylchlorosilane to lower the surface energy and realize
easy PDMS peel-off in the following steps. During PDMS
replication process, the precursor and cross-linker mixture (a
10:1 ratio, Sylgard 184, Dow Corning) was stirred together and
deposited on the pyramid master. After being degassed under
vacuum for 10 min and cured at 100 °C for 1 h, the solidified
PDMS pyramid stamp was detached from the pyramid silicon
mold.
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2.2. Assembly of DSSCs. The pyramid-structured TiO2
nanoparticle (P25 Degussa) film acting as the active layer was
prepared by soft imprint lithographic technique, and the
inverted pyramid-structured large particle (200 nm TiO2
nanoparticle) film acting as the scattering layer was prepared
by conformal contact deposition. The detailed fabrication
process is described as follows and is shown in Figure 3. First,
Figure 3. Schematic illustration for the fabrication of pyramid-
structured photoanode with conformal contacted scattering layer.
the TiO2 paste was coated on the transparent conductive
substrate, and all the samples with or without patterns have the
same initial content of TiO2 paste. Then, the thin PDMS stamp
was manually placed on the top of the wetted TiO2 paste with
proper pressure and maintained at room temperature for 12 h,
which can allow the solvent to be evaporated off fully and drive
the TiO2 paste to penetrate into the pyramid space in the
PDMS stamp. After the stamp was peeled off, the obtained
pyramid-structured TiO2 film was sintered at 450 °C for half an
hour. The scattering layer was prepared by coating the large
TiO2 particles onto the surface of periodical TiO2 pyramid
arrays. Then, the solidified TiO2 films were heated at 500 °C
for 30 min to remove the organics completely. As for the
photoanode sensitization, the cooled electrode was impreg-
nated with the N719 dye solution (0.3 mM) for 24 h. In terms
of the electrolyte, it comprised 0.6 M 1,2-dimethylimidazolium
iodide(DMPII), 0.1 M LiI, 0.05 M I2, and 0.5 M tert-
butylpyridine. On the part of the counter electrode, Pt
nanoparticles were deposited on the surface of the transparent
conductive substrate by the rf-magnetron sputtering technique.
The photoanode and counter electrode were adhered together
by a 50 μm thick urlyn polymer. And the electrolyte solution
was drawn into the cell under a vacuum through the drilled
hole on the counter electrode. Finally, the punched hole was
sealed with a 25 μm thick urlyn polymer film and a glass cover
by hot pressing. The detailed fabrication process follow our
prievous report.34
2.3. Characterizations and Measurements of DSSCs.
The surface morphologies of the pyramid-structured photo-
anodes were observed by using a SU8000 field emission SEM.
The optical properties of the prepared samples were
characterized by a UV−vis-NIR spectrophotometer (Shimadzu
UV3600, Shimadzu, Japan). The current density−voltage (J−
V) curves were characterized by using a digital source meter
(Keithley 2612) and a 300 W xenon light source (AM 1.5, 100
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mW cm−2). The electrochemical impedance spectra (EIS) of
the cells were measured by employing the CHI-660D in the
frequency range from 0.05 to 105 Hz. The applied bias voltages
were set at the open-circuit voltage of the cells with an ac
amplitude of 10 mV.
3. RESULTS AND DISCUSSION
3.1. Morphologies of Pyramid Patterned Mold and
TiO2 Photoanodes. The morphologies of the pyramid
mastertemplate were investigated by SEM as shown in Figure
4. It can be seen from the figure that the arrayed structures with
Figure 4. (a) SEM images of microhole arrays with 4 μm period on Cr
layer. (b) NaOH-etched inverted pyramid arrays with Cr mask. (c)
Obtained inverted pyramid arrays mold with removed Cr layer.
inverted pyramid-shaped profiles were successfully obtained
with a period of 4 μm and a depth of 1.4 μm approximately in
the resultant template. The top view SEM images of the open
aperture arrays in Cr layer and the resulting pyramid arrays in
silicon substrate are shown in Figure 4, parts a and c, which is
related to the inverted pyramids etched with lithographic Cr
mask layer and the following Cr layer removed in the
experiment, respectively. The Cr layer mask exhibits trans-
lucent, intact, and perforated morphologies in NaOH wet
etching process (shown in Figure 4b), which effectively
protected the underlying silicon from NaOH solution
corrosion. The unprotected silicon surface was etched resulting
in a typical inverted-pyramid structure after NaOH treatment.
Figure 5 shows the SEM images of the patterned TiO2
photoanodes with periodical pyramid arrays (4 μm period)
Figure 5. (a) Overview SEM image of pyramid patterned TiO2
nanoparticles film. (b)Top view image of the pyramid arrays with a
4 μm period. (c) Enlarged image of the single pyramid composed by
TiO2 nanoparticles. (d) Cross sectional overview image of pyramid-
structured photoanode with scattering layer. (e) Enlarged cross
sectional image. (f) Interface between the active layer and scattering
layer.
with and without light scattering layer. Parts a−c of Figure 5
show the SEM graphs of TiO2 pyramid patterns in active layer
after annealing, which was carried out by a pyramid PDMS
stamp with a period of about 4 μm and depth of about 1.4 μm.
As we can see from the figures, the pyramid structures were
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Figure 6. Optical schematic diagrams for (a) planar TiO2 photoanode, (b) pyramid-structured photoanode without scattering layer, and (c)
pyramid-structured photoanode with conformal contacted scattering layer.
successfully transferred from PDMS stamp to the TiO2 active
layer, which verifies that the flexibility and permeability of the
PDMS stamp can effectively make the conformal contact intact
and compact between the stamp and the TiO2 film, thus to
obtain a perfect TiO2 pyramid replication and to reduce the
damage to the TiO2 film. As shown in Figure 5, parts a−c, the
acquired patterned pyramid arrays are well uniform and evenly
distributed with mesoporous TiO2 nanoparticles network.
To characterize the light-scattering and charge-generating
properties with comparative studies, we also prepared a double
layer photoanode using large sized particles as scattering layer.
Parts d−f of Figure 5 show the cross-sectional SEM images of
the bilayer photoanodes based on the pyramid-structured TiO2
active layer/light scattering layer. As can be seen from Figure 5,
parts d and e, the double layer structured photoanode, with an
under-layer composed of 4 μm periodical TiO2 pyramid arrays
and top-layer consisting of large sized TiO2 particles with a 5
μm thickness, can be successfully fabricated. The overlayer
exhibits good adhesion to the nanocrystalline underlayer and
no peeling is observed after annealing. In addition, Figure 5f
shows that the TiO2 nanoparticles can fully fill into the spacing
between the adjacent pyramid grating structures. The
morphologies of the patterned TiO2 pyramid arrays are
unaffected by the coating large sized TiO2 particles, and the
covered large sized TiO2 particles network are tight and
crackless.
3.2. UV−Vis Optical Absorption. The main motivation
for making patterned pyramid structures is to increase the
optical path length within the sensitized TiO2 electrodes by
optical diffraction and light scattering effects. The incident light
that reaches the surface of periodical pyramid arrays is
diffracted and scattered in deflected beams traveling in different
directions. Thus, the residence time of incident photons
traveling in the active layer is prolonged, leading to the
enhanced light absorption. These different optical behaviors
based on patterned pyramid structures could be further
explained by the schematic diagram in Figure 6. As can be
seen from Figure 6a, the large amount of incident light traveling
in the photoanode would pass through the planar TiO2 film due
to the small particle size. This drawback results in a great loss of
incident photons. In Figure 6b, periodical pyramid arrays are
distributed on the surface of the planar TiO2 film, but still some
incident light is missed after passing through the patterned
structures due to the incomplete light diffraction and scattering
effects. However, as large TiO2 particles deposited on the
surface of the arrayed pyramid structures (as shown in Figure
6c), the formed inverted pyramid scattering layer can effectively
scatter a large proportion of the incident light returning into the
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nanocrystalline active layer and strongly trap the incident
photons within the photoanode, which could largely enhance
the light harvesting efficiency and compensate for the loss of
incident photons. These features were further experimentally
confirmed by dye-sensitized films with various structures for
larger area (1 cm × 1 cm) and the corresponding UV−vis
absorption spectra is shown in Figure 7.
Figure 7. UV−vis spectra of absorption from different photoanodes.
As we can see from the Figure 7, the planar and pyramid
patterned photoanodes with and without scattering layer are
presented. The pure planar TiO2 nanopartcle photoanode is
denoted as TP, the pyramid patterned TiO2 nanoparticle film is
denoted as TP-PY, and the TP film and TP-PY film attached
with scattering layer are denoted as TP−SC and TP-PY-SC,
respectively. The absorption peaks spanning from 300 to 400
nm can be owing to the absorption of the TiO2 nanoparticles,
and the absorption band during the wavelength range of 450 to
650 nm can be mainly attributed to the additional dye
absorption. Interestingly, among the various photoanodes, the
PYTP−PYSC photoanode demonstrates the best optical
absorption with an intense and wide absorption band ranging
from 400 to 800 nm. The TiO2 photoanodes without scattering
layer exhibit lower optical absorption than the TiO2 photo-
anodes with scattering layer for visible wavelength, which
indicates that the scattering layer can reduce the light
transmission loss and reflect the incident light inner the film
due to their relatively larger particles. The result also shows that
the optical absorption of the pyramid patterned TiO2
photoanode is greater than that of a planar photoanode in
the range of 400−800 nm. The enhanced light absorption of
the samples with periodical pyramid structures is owing to the
joint effects of the antireflection and scattering functions
acquired by combination of the larger dimensions and grating
diffraction properties of the periodical pyramid arrays. Incident
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light can be reflected inner the pyramid active layer before
reaching the scattering layer, thus, leading to much longer
optical path lengths. Furthermore, for the photoanodes with
scattering layer group and without scattering layer group, the
various photoanodes in the same group have the same amount
of TiO2 nanoparticles and dye loading due to the same initial
TiO2 film deposited by the doctor blading method. Although
the planar photoanodes adsorbed the same amount of dyes, the
pyramid-structured photoanodes were found to absorb more
incident photons than the planar photoanodes. It indicates that
the periodical pyramid arrays play a critical role in the light
absorption of the DSSCs. In order to further investigate the
optical properties of periodical pyramid arrays, we also show
the other two kinds of periodical pyramid photoanodes in the
Supporting Information.
3.3. Effects of Periodical TiO2 Pyramid Arrays on the
Performance of DSSCs. To investigate the influences of the
pyramid patterned structures on the device performance, the
photovoltaic characteristics of prepared samples (three cells for
each kind) were measured under illumination of AM 1.5 100
mW cm2. The corresponding J−V curves for different kinds of
photoanode-based cells are presented in Figure 8. The short-
Figure 8. J−V curves of the DSSCs based on planar and pyramid-
structured DSSCs.
circuit current density of the cell based on 4 μm periodical
pyramid-structured TiO2 film (PYTP) and single planar TiO2
film (TP) are 9.68 mA/cm2 and 8.31 mA/cm2, and the
corresponding efficiencies are 4.81% and 3.96%. In particular,
we noted that the Jsc of pyramid-structured cell is increased
over 16% in comparison with the conventional planar TiO2 cell.
The improved current density indicates that the periodical
pyramid arrays in the TiO2 active layer can increase the optical
path length within the sensitized photoanode by diffraction
effects. In addition, the short-circuit current density of the cell
based on pyramid-structured bilayer structure (PYTP−PYSC)
and planar bilayer structure (TP−SC) are 12.65 mA/cm2 and
11.12 mA/cm2, and the corresponding efficiencies are 6.39%
and 5.64%. The further improved light trapping design exhibits
over 13% enhancement in comparison with the TP−SC cell,
which indicates that the periodical pyramid arrays attached with
conformal contacted scattering layer can further increase the
optical pathlengths and prolong the residence time of photons
in the active layer leading to the improved device performance.
3.4. Incident Photon to Current Conversion Efficiency
(IPCE). The corresponding IPCE curves of the planar and
pyramid-structured photoanodes with and without scattering
layer are shown in Figure 9. Generally, the profile of the IPCE
curve is similar to that of the absorption spectrum, because the
IPCE curves reflect the electron generation rate in external
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Figure 9. IPCE spectra of the DSSCs based on the TP, PYTP, TP−SC
and PYTP−PYSC photoanodes.
circuit at a given incident light wavelength. The variation in Jsc
can be tested and verified by IPCE measurements. As can be
seen from the figure, the pyramid-structured photoanode with
scattering layer (PYTP−PYSC) has the maximum IPCE values,
following the trend showed in the J−V curves. In comparison
with the single-layer photoanodes (TP, PYTP), the double-
layer photoanodes (TP−SC, PYTP−PYSC) present substan-
tially enhanced IPCE values in the whole wavelength range
owing to the addition of the scattering layers. Furthermore, it
also can be seen from the figure that pyramid patterned devices
presented enhanced IPCE values than those of flat device
(PYTP versus TP, PYTP−PYSC versus TP−SC). The
improvement of the pyramid-structured cells primarily arise
from the marginally superior optical performance of the
periodical pyramid arrays augmented by navigating more
number of incident photons into the active layer and yielding
more photoelectrons. Thus, the IPCE spectra demonstrate a
direct evidence for the enhanced effective light absorption of
the periodical TiO2 pyramid arrays.
3.5. EIS. In order to analyze the interfacial carrier transfer
behaviors, which are significantly related to the device
performance, EIS measurements were implemented at dark
with 0.8 V bias by testing the cells based on planar and
pyramid-structured photoanodes with and without scattering
layer, as shown in Figure 10. All the EIS spectra are made up of
two semicircles distributed in high and medium frequency
regimes. The semicircle in the medium frequency region
represents the carrier transfer processes at the TiO2/dye/
electrolyte interface according to the previous report, and the
size of the semicircle at dark condition mainly reflects the
carrier recombination resistance in the photoanode.35,36 As
shown in Figure 10 b, the second semicircle of the cell with the
pyramid-structured electrode (PYTP) is larger than that of the
cell with flat electrodes (TP), reflecting the suppressing carrier
recombination in the pyramid electrode. The suppressing
recombination rate can be ascribed to the increased contact
area at the interface of pyramid-structured TiO2 film/electrolyte
as well as effective electrolyte penetration.
The Bode phase graph exhibited in Figure 10 (c), presents
the characteristic frequency values during the charge transfer
processes. The lifetime of the electrons traveling in the device
can be estimated from the characteristic frequencies of the
impedance semicircle at medium frequencies, according to the
equation τe = 1/(2πf max), where f max is the maximum frequency
of the medium frequency peaks. The f max of the cell with the
pyramid-structured electrode (PYTP) slightly shifts to a much
lower value in comparison with the flat TiO2 electrode (TP).
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Figure 10. (a) Equivalent circuit used to fit the EIS spectra for DSSCs:
Rs is the series resistance; R1 and CPE1 represent the charge transfer
resistance and corresponding constant phase element at the TiO2/
dye/electrolyte interface; Zw is the electrolyte diffusion resistance; RPt
and CPEPt are the charge-transfer resistance and corresponding
constant phase element at the counter electrode. (b) Nyquist plots and
(c) Bode phase plots for solar cells based on TP and PYTP
photoanodes.
The characteristic frequency shifting from a high value to a low
value reveals a much faster carrier transport process. All above
analyses suggest that the photoanodes with integrated pyramid
patterned TiO2 nanoparticles film can effectively enhance the
carrier transfer at the interface of the photoanode/electrolyte
and resist the corresponding interfacial electron recombination.
4. CONCLUSION
In summary, we have successfully fabricated the periodical
pyramid arrays directly in the mesoporous TiO2 nanoparticle
film. The periodical TiO2 pyramid arrays were prepared by the
soft imprint lithography technique. Among the different types
of photoanodes employed, the pyramid-shaped TiO2 photo-
anode exhibits the improved light absorption ability and hence
the enhanced photovoltaic performance. There is a strong
evidence that the periodical pyramid arrays can confine the
incident light within the active layer more effective without
causing any destructive side effects such as aggravating carrier
recombination. The enhanced light absorption properties of
periodical pyramid arrays make pyramid-structured photo-
anodes promising candidates as effective photoanodes for
photovoltaic applications. This work also further provides us
with some new chances for fabricating high-performance
photovoltaic devices based on micro/nanostructures design
and operation of the light-trapping structures.
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■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.jpcc.6b02687.
SEM images of the pyramid molds and the pyramid
patterned photoanodes and the corresponding UV−vis
absorption spectra in 20 and 40 μm periods (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*(H.L.) E-mail: hzliu@mail.xjtu.edu.cn. Fax: 86-29-83399508.
Telephone: 86-29-83399508.
Notes
The authors declare no competing financial interest.
■ ACKNOWLEDGMENTS
This work is supported by the Major Research Plan of National
Natural Science Foundation on Nanomanufacturing (No.
91323303), National Natural Science Foundation of China
(No. 51275400), National Science and Technology Project
(Nos. 2011ZX04014-071, SK201401A53-01, CERS-1-X1), the
Fundamental Research Funds for the Central Universities, and
the China Postdoctoral Science Foundation (Nos.
2015M572549).
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9684 DOI: 10.1021/acs.jpcc.6b02687

J. Phys. Chem. C 2016, 120, 9678−9684