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Applied Surface Science xxx (2015) xxxxxx

Contents lists available at ScienceDirect

Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Mesoporous anatase TiO2 microspheres with interconnected

nanoparticles delivering enhanced dye-loading and charge transport
for efcient dye-sensitized solar cells
Liang Chu a , Zhengfei Qin b , Qiaoxia Zhang b , Wei Chen a ,
Jian Yang b , Jianping Yang a, , Xingao Li b,
a
School of Science, Nanjing University of Posts and Telecommunications (NUPT), Nanjing 210046, PR China
b
Key Laboratory for Organic Electronics & Information Displays (KLOEID) & Institute of Advanced Materials (IAM), Jiangsu National Synergistic Innovation
Center for Advanced Materials (SICAM), School of Materials Science and Engineering (SMSE), Nanjing University of Posts and Telecommunications (NUPT),
Nanjing 210046, PR China

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

Article history: Mesoporous anatase TiO2 microspheres with interconnected nanostructures meet both large surface
Received 14 September 2015 area and connected-structure for electron transfer as ideal nano/micromaterials for application in solar
Received in revised form 18 October 2015 cells, energy storage, catalysis, water splitting and gas sensing. In this work, mesoporous anatase TiO2
Accepted 3 November 2015
microspheres consisting of interconnected nanoparticles were synthesized by template-free, one-step
Available online xxx
fast solvothermal process, where urea was used as capping agent to control phase and promote oriented
growth. The morphology was assembled by nucleation-growth-assembly-mechanism. The mesoporous
Keywords:
anatase TiO2 microspheres with interconnected nanoparticles were further utilized as efcient photoelec-
Mesoporous anatase TiO2 microspheres
Interconnected nanoparticles
trodes of dye-sensitized solar cells (DSSCs), which were benecial to capacity of dye loading and charge
Photoelectrodes transfer. The power conversion efciency (PCE) based on the optimized thickness of TiO2 photoelectrodes
Dye-sensitized solar cells was up to 7.13% under standard AM 1.5 G illumination (100 mW/cm2 ).
2015 Elsevier B.V. All rights reserved.

1. Introduction Dye-sensitized solar cells (DSSCs) have captured great atten-

Mesoporosity provides the ideal large specic surface area but
many applications as well as desire long-range electronic trans-
port channel [1]. Mesoporous semiconductor microspheres with
connected nanostructures meet both criteria [2]. TiO2 single crys-
tal, due to the high chemical and optical stability, low toxicity,
and appropriate band structure [3], has been widely applied, such
as energy storage and conversion [4,5], photocatalysis [6], elec-
trochromic [7] and sensor [8]. The mesoporous TiO2 microspheres
with interconnected nanostructures have connected nanostruc-
ture, high specic surface area and tunable pore size, being an ideal
nano/micromaterials in realizing enhanced optoelectronic nanode-
vice performance [911]. Nowadays, there are many methods to
design mesoporous TiO2 microspheres, such as template method
[12], two-step process of controlled hydrolysis and subsequent
hydrothermal reaction [13]. However, those processes were too
complicated.
Corresponding authors.
E-mail addresses: yangjp@njupt.edu.cn (J. Yang), iamxali@njupt.edu.cn (X. Li).
tion during the past two decades as a potential, cost-effective
alternative to silicon solar cells with the advantages of high ef-
ciency, low cost, environment friendly, simple fabrication process
[14,15]. Traditionally, standard DSSC device is the combination of
photoelectrode, dye molecules, electrolyte and counter electrode
[16,17]. There, the photoelectrodes profoundly affect the perfor-
mance of DSSCs, which serve as scaffolds for dye molecules and the
transport media for photo-generated electrons [18,19]. For efcient
DSSCs, the photoelectrodes must simultaneously meet the follow-
ing requirements: (1) large specic surface area for loading dye
abundantly, (2) outstanding light scattering for enhancement of
light harvesting, (3) long-range electronic transport channel, (4)
suitable pore sizes and porosities for sufcient electrolyte diffu-
sion, etc. [13,20]. However, the above requirements are mostly not
incompatible with each other in the one nanomaterial.
Mesoporous TiO2 microspheres, as one of the desired nano-
materials to meet the above requirements, have been deemed
to successful photoelectrodes for DSSCs [13,21,22]. To the best
of our knowledge, here it was the simplest method to fabricate
mesoporous anatase TiO2 microspheres with interconnected
nanoparticles by a template-free and fast one-step solution

http://dx.doi.org/10.1016/j.apsusc.2015.11.034
0169-4332/ 2015 Elsevier B.V. All rights reserved.

Please cite this article in press as: L. Chu, et al., Mesoporous anatase TiO2 microspheres with interconnected nanopar-
ticles delivering enhanced dye-loading and charge transport for efcient dye-sensitized solar cells, Appl. Surf. Sci. (2015),
http://dx.doi.org/10.1016/j.apsusc.2015.11.034
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Fig. 1. Schematic of DSSCs based on the mesoporous anatase TiO2 microspheres
with interconnected nanoparticles. The interconnected nanoparticles enhance dye-
loading capacity and charge transport.
process, which were further developed as excellent photoelec-
trodes for DSSCs. The morphology of the specimen was tailored
by controlling the processing parameters, in which the urea
played a key part in controlling phase and promoting oriented
growth. The microspheres were formed through the aggregation of
radiating-stay interconnected nanoparticles. The interconnected
nanoparticles are provided with high specic surface area for
loading dye molecules and structural coherence for long-range
electronic connectivity [23], as shown in Fig. 1; meanwhile the
microsphere structure has superior light scattering capacity
[24]. DSSCs based on the as-prepared mesoporous anatase TiO2
microspheres with interconnected nanoparticles and commercial
ruthenium dye (N719) exhibit a power conversion efciency (PCE)
of 7.13% under standard AM 1.5 G illumination (100 mW/cm2 ).
2. Experimental
2.1. Reagents and materials
Fluorine-doped tin oxide (FTO, 7 /2 ) glasses were
pursued from Nippin Sheet Glass Co., Ltd. Hydrochloric acid
(HCl, 3638 wt%), urea ((NH2 )2 CO, 99.0%), titanium tetra-
chloride (TiCl4 , 99.0%), ethanol (99.7%) and acetone (99.5%)
were purchased from Sinopharm Chemical Reagent Co. Ltd.
Cisbis(isothiocyanato)bis(2,2 -bipyridyl-4,4 -dicarboxylato)
ruthenium(II) bis-tetrabutylammonium (N719) was purchased
from Solaronix. Guanidinium thiocyanate (GuSCN, 99.0%) was from
Amresco. Titanium isopropoxide (C12 H28 O4 Ti, 95%), lithium iodide
(LiI, 99.999%), iodine (I2 , 99.99%), 1-methyl-3-propylimidazolium
iodide (PMII, 98%), 4-tert-butylpyridine (4-TBP, 96%) and tert-
butyl alcohol (99.5%) were obtained from Aladdin. Acetonitrile
(99.8%) and valeronitrile (99%) were from Alfa Aesar. All solvents
and chemicals were reagent grade and were used without any
additional purication.
2.2. Synthesis of mesoporous anatase TiO2 microspheres
Typically, 5 mL of HCl was poured into 25 mL of deionized water
under stirring for 5 min, then the urea with different amounts
(0, 2.3, 4.6 and 9.2 g) was dispersed in the above solution under
stirring for another 10 min, and 1.2 mL of C12 H28 O4 Ti was added
drop-by-drop under vigorous stirring until the solution being
transparent. The above solution was poured into a Teon-lined
stainless steel autoclave with a capacity of 50 mL and loaded into
an oven. The reaction temperature was set at 120 C for different
times (1, 2 and 3 h) and then naturally cooled to room temperature.
After the hydrothermal treatment, the white powder was har-
vested, and washed thoroughly with deionized water and ethanol
for several times via centrifugation. Finally, the TiO2 powder was
dried at 80 C overnight. The morphology of TiO2 products by 3 h
reaction with 9.2 g urea was mesoporous microspheres. In order
Please cite this article in press as: L. Chu, et al., Mesoporous anatase TiO2 microspheres with interconnected nanopar-
ticles delivering enhanced dye-loading and charge transport for efcient dye-sensitized solar cells, Appl. Surf. Sci. (2015),
http://dx.doi.org/10.1016/j.apsusc.2015.11.034
to enhance crystallinity, the mesoporous TiO2 microspheres were
heated at 500 C for 2 h at a mufe furnace under air owing.
2.3. Preparation of TiO2 photoelectrodes
1 g of mesoporous TiO2 microspheres powder was mixed with
0.2 mL of acetic acid, 0.5 g of ethyl cellulose, some terpineol and
ethanol under vigorous agitation, then the mixture was transferred
into a mortar to mill for 20 min, and nally dispersed with ultra-
sonic for about 10 min to form viscous white TiO2 paste. The FTO
glasses were cut into pieces with 2.0 cm 1.2 cm, and washed with
detergent under running water, and sonicated in deionized water,
acetone and ethanol for 20 min, respectively. After dried under
owing argon gas, the well-cleaned FTO glasses were soaked into
0.04 M TiCl4 solution at 70 C for 30 min for a compact TiO2 layer,
and then rinsed with deionized water and ethanol. The TiO2 pastes
were printed onto the TiCl4 -treated FTO glasses by doctor-blading
method. Then the printed TiO2 layers were annealed at 125 C for
15 min, at 325 C for 5 min, at 375 C for 5 min, at 450 C for 15 min,
and then at 500 C for 15 min in a mufe furnace under air owing.
The annealed TiO2 layers were immersed into 40 mM TiCl4 solu-
tion at 70 C for 30 min again, and after being rinsed with deionized
water and ethanol, the lms were sintered at 500 C for 30 min in
mufe furnace. After cooling to about 80 C, the TiO2 photoanodes
were immersed into 0.5 mM N719 dye in solution of acetonitrile
and tert-butanol (volume ratio = 1:1), and kept for 16 h at room
temperature. Afterwards, the sensitized TiO2 photoelectrodes were
washed thoroughly with acetonitrile in order to remove the phys-
ically adsorbed dye molecules.
2.4. Fabrication of DSSCs
The counter electrodes of Pt lms on FTO glasses were prepared
by magnetron sputtering with Pt (99.99% purity) target in an Ar
ambient atmosphere at 100 W. To fabricate a DSSC, the Pt counter
electrode was buckled on the sensitized-TiO2 photoelectrode, being
sealed by 50 m plastic sheet, where the internal space was lled
with a liquid electrolyte. The electrolyte was composed of 0.6 M
PMII, 0.05 M LiI, 0.03 M I2 , 0.1 M GuSCN and 0.5 M 4-TBP in solution
of acetonitrile and valeronitrile (volume ratio = 85:15). The active
area of the solar cell was controlled to be 0.15 cm2 without a mask.
2.5. Measurement and characterization
X-ray diffractometer (XRD, D8 ADVANCE, Bruker) with
CuK ( = 0.15405 nm) radiation, eld-emission scanning elec-
tron microscopy (SEM, S-4800, Hitachi), and transmission electron
microscopy (TEM, FEI Tecnai G2 20 UTwin) were carried out to
investigate structure and phase purity of the as-prepared TiO2
samples. The BrunauerEmmettTeller (BET, V-Sorb 2800P) was
taken to measure the surface area and pore size distribution
of the samples. The TEM sample was prepared by drop cast-
ing ethanolic dispersion of tiny TiO2 powder onto a carbon
coated Cu grid. The current densityvoltage (IV) and elec-
trochemical impedance spectroscopy (EIS) measurements were
performed by an Autolab electrochemic workstation (mode-
lAUT84315, The Netherlands). UVvis absorption spectrometry
(UV-2550, Shimadzu) was employed to test the absorption spectra.
The illumination intensity was AM 1.5 G (100 mW/cm2 , calibrated
with a Si photodiode) using a solar simulator (Newport, USA).
The electrochemical impedance spectroscopy (EIS) measurements
were scanned in dark condition at a bias of 0.70 V with an ampli-
tude of 10 mV in a frequency range from 100 kHz to 0.1 Hz. For
testing the adsorbed dye amounts of the TiO2 photoeletrodes,
the sensitized-TiO2 lms desorbed the dye into 0.1 M NaOH solu-
tion. The measured absorption spectra were used to calculate the
amount of the adsorbed dye amount, expressed in terms of moles
of dye anchored per projected unit area of the photoelectrodes.
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Fig. 2. (a) XRD power patterns of the hydrothermal products synthesized with different urea mounts (i: 0, ii: 2.3 g, iii: 4.6 g, iv: 9.2 g), (b) XRD power patterns of iv sample
with and without calcination treatment.

Fig. 3. SEM images of the hydrothermal products synthesized with different amounts of urea: (a, b) without urea, (c, d) 2.3 g, (e, f) 4.6 g, (g, h) 9.2 g.

Please cite this article in press as: L. Chu, et al., Mesoporous anatase TiO2 microspheres with interconnected nanopar-
ticles delivering enhanced dye-loading and charge transport for efcient dye-sensitized solar cells, Appl. Surf. Sci. (2015),
http://dx.doi.org/10.1016/j.apsusc.2015.11.034
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Fig. 4. SEM images of the as-obtained TiO2 products for different reaction times with 9.2 g urea: (a) 1 h, (b) 2 h. (c) The schematic illustration of the growth process of
mesoporous anatase TiO2 microspheres with interconnected nanoparticles.

Fig. 5. (a) TEM image of the mesoporous anatase TiO2 microspheres with interconnected nanoparticles, (b, c) the enlarged one, (d) the corresponding high resolution TEM
image. The inset of (d) is the SAED pattern.

3. Results and discussion amounts of urea (i: 0, ii: 2.3 g, ii: 4.6 g, iv: 9.2 g). As the amounts of
urea increased to 4.6 g, the phase of the products changed from
3.1. Material characteristics rutile to anatase. In samples i and ii, the broadened diffrac-
tion peaks were indicated as (1 1 0), (1 0 1), (2 1 1), (0 0 2) and (1 1 2)
Fig. 2a gives the XRD powder patterns for the obtained TiO2 planes of rutile TiO2 (PCPDFWIN, 88-1174). It was suggested that
powder samples by hydrothermal reaction for 3 h with different when there was few urea, the rutile TiO2 were formed by direct

Please cite this article in press as: L. Chu, et al., Mesoporous anatase TiO2 microspheres with interconnected nanopar-
ticles delivering enhanced dye-loading and charge transport for efcient dye-sensitized solar cells, Appl. Surf. Sci. (2015),
http://dx.doi.org/10.1016/j.apsusc.2015.11.034
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hydrolysis of titanium isopropoxide in water and the crystallinity
was very poor. On the contrary, when the urea was enough, there
are obvious several broadened diffraction peaks, which correspond
to (1 0 1), (0 0 4), (2 0 0), (1 0 5), (2 1 1), (2 0 4), (1 1 0), (2 2 0) and
(2 0 5) planes of anatase TiO2 (PCPDFWIN, 84-1286). Interestingly,
the urea must take part in the reaction of forming anatase TiO2 , and
the obvious peaks indicate the good crystallinity and pure anatase
phase. After calcination treatment as shown in Fig. 2b, the peaks of
anatase TiO2 (sample iv) become more obvious and sharper, which
suggested that the heating enhanced the crystalline of the obtained
TiO2 product.
The morphology of TiO2 products by hydrothermal reaction for
3 h with different amounts of urea was characterized by FE-SEM
technology as shown in Fig. 3. When there was no urea, the obtained
rutile TiO2 nanoparticles were random shape, as indicated in Fig. 3a
and its enlarged image of Fig. 3b. As the amount of urea was added
to 2.1 g, there were little aggregations of the random-shape rutile
TiO2 nanoparticles as shown in Fig. 3c and d. Adding the amount of
urea to 4.6 g, the product was aggregation without regular shape in
Fig. 3e and its enlarged image of Fig. 3f, and the phase was changed
to anatase by the effect of urea. When the amount was 9.2 g, it was
interesting that as-prepared product revealed microspheres with
uniform morphology. These microspheres had hierarchical struc-
ture and their diameter was 200400 nm, as indicated in Fig. 3g
and h. It was concluded that the urea played as a capping agent to
control phase and promote oriented growth.
The as-obtained TiO2 products for different reaction times with
9.2 g urea were also investigated by SEM technology to investigate
the time-dependent morphological evolution, as shown in Fig. 4a
and b. As explained earlier in the sample prepared for 1 h, there
were TiO2 nanoparticles, nanorods composed of nanoparticles
and numerous starsh-like TiO2 nanospindle aggregates com-
posed of nanoparticles, as indicated in Fig. 4a. When the reaction
was prolonged to 2 h as shown in Fig. 4b, numerous starsh-like
TiO2 nanospindle aggregates and mesoporous TiO2 microspheres
with interconnected nanoparticles were observed. Upon further
increasing the reaction time to 3 h, the as-obtained sample almost
exclusively contained mesoporous TiO2 microspheres as shown
in Fig. 3g and h. According to the above analysis, the formation
mechanism of mesoporous TiO2 microspheres with interconnected
nanoparticles could be concluded by nucleation-growth-assembly-
mechanism, as illustrated in Fig. 4c. At the initial stage, the particles
were formed in the solvothermal process. Then, with the increas-
ing of reaction time, particles aggregated each other into nanorods
and starsh-like TiO2 nanospindle aggregates. Finally, the meso-
porous TiO2 microspheres with interconnected nanoparticles were
obtained by nucleation-growth-assembly-mechanism.
In order to study the detailed morphology and further evi-
dence of TiO2 microspheres, the TEM technology was taken to
observe the sample prepared for 3 h with 9.2 g urea. A TEM image
of Fig. 5a showed the unied microspheres and the enlarged image
of Fig. 5b indicted the microspheres with mesoporous structure.
Fig. 5c clearly showed that the TiO2 mesoporous microspheres
consisted of interconnected nanoparticles with zigzag shape. The
high resolution TEM image in Fig. 5d indicted the fringe spacing
of 0.352 nm, which matches well with the inter-planar spacing of
(1 0 1) planes of the anatase TiO2 (PCPDFWIN, 84-1286), tallying
with the XRD pattern. The inset in Fig. 5(d) revealed a selected area
electron diffraction (SAED) pattern of the anatase mesoporous TiO2
microspheres, in which a set of diffraction rings can be indexed to
the (1 0 1), (1 0 3) and (2 0 0) planes of anatase TiO2 (PCPDFWIN,
84-1286).
Fig. 6 exhibited the nitrogen adsorption isotherm and the cor-
responding pore-size distribution curve (the inset) of the anatase
mesoporous TiO2 microspheres. Observably, the isotherm was of
type IV based on BrunauerDemingDeming Teller classication
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ticles delivering enhanced dye-loading and charge transport for efcient dye-sensitized solar cells, Appl. Surf. Sci. (2015),
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5
Fig. 6. Nitrogen adsorption isotherm of the mesoporous anatase TiO2 microspheres.
The inset is the corresponding pore size distribution curve.
with hysteresis at relative high pressures, which conrmed the
existence of pores in the sample. A narrow pore size distribu-
tion (220 nm) was observed in the pore-size distribution curve
(the inset of Fig. 6). In addition, the BET surface area of the sam-
ple was measured as 46.97 m2 /g, which was close to that of P25,
measured as 49.35 m2 /g, as indicated in Fig. 1S. More importantly,
the anatase mesoporous TiO2 microspheres possess pores and
connected-structures, which are conducive to electron transfer.
In the chemical reaction of forming TiO2 anatase mesoporous
TiO2 microspheres, titanium isopropoxide and urea were used as
titanium source and capping agent, respectively. The chemical reac-
tion can be described as follows [25,26]:
2(NH2 )2 CO + 5H2 O 4NH4 + + OH + HCO3 + CO3 2 (1)
4+
Ti + 4OH Ti(OH)4 TiO2 + H2 O (2)
In aqueous solution, the urea will be decomposed under
hydrothermal condition. Then, OH negative ion of the gener-
ated products (reaction (1)) will react with Ti4+ cation to form
Ti(OH)4 and further to generate TiO2 (reaction (2)). With reaction
proceeding, mall nanoparticles aggregated and formed nanorods.
Then, more primary particles adhered onto the surface of nanorods.
To lower the total energy of the system, smaller particles con-
nected each other to regrow nanorods during Ostwald ripening
[27]. The nanorods were further aggregated to starsh-like TiO2
nanospindles, which were nally transformed into mesoporous
microspheres with prolonging the reaction time.
3.2. Photovoltaic performance
The as-obtained mesoporous anatase TiO2 microspheres were
developed as efcient photoelectrodes for DSSCs. The thickness
of TiO2 photoelectrodes were 5, 13, 14.5, 18 m, respectively, as
revealed in Fig. 2S of the cross-section SEM images. Fig. 7a shows
the IV (current density versus voltage) curves of DSSCs fabri-
cated with different thickness photoelectrodes under standard AM
1.5 G illumination (100 mW/cm2 ). The derived photovoltaic param-
eters such as short-circuit current density (JSC ), open-circuit voltage
(VOC ) and ll factor (FF) with the relative PCE are listed in Table 1.
The DSSCs based on TiO2 photoelectrodes with 14.5 m depict the
superior PCE of 7.13% over another. Much thicker TiO2 photoelec-
trodes can loaded more amount of dye molecules to capture light,
but meanwhile the generated charges should transfer longer. To
quantitatively estimate the dye-loaded amounts, the sensitized-
TiO2 lms were immersed into NaOH solution to desorb the dye
molecule. And the concentration of desorbed N719 dye in aqueous
NaOH was calculated from UVvis absorbance measurements by
using LambertBeers Law [28,29]. According to Fig. 7b, the calcu-
lated data of dye-absorbed amounts were summarized in Table 1,
which increased from 79.2 to 171.0 nmol/cm2 with thickness of
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Fig. 7. (a) IV curves of the DSSCs with TiO2 photoelectrodes with different thicknesses (i: 5 m, ii: 13 m, iii: 14.5 m, iv: 18 m). (b) UVvis spectra of solutions containing
N719 desorbed from sensitized TiO2 photoelectrodes with different thicknesses. (c) EIS measurements were conducted in the dark under 0.7 V bias. (d) An equivalent circuit
ts Nyquist plots.

Table 1
Photovoltaic parameters and dye-loaded amounts of DSSCs based on TiO2 photoelectrodes with different thicknesses.

Photoelectrode thickness JSC (mA/cm2 ) VOC (V) FF PCE Dye amount (nmol/cm2 )

I: 5 m 10.94 0.798 0.649 6.24% 79.2

II: 13 m 12.18 0.776 0.666 6.93% 131.6
III: 14.5 m 12.63 0.775 0.662 7.13% 150.0
IV: 18 m 11.67 0.734 0.609 5.74% 171.0

TiO2 photoelectrodes from 5 to 18 m. Electrochemical impedance
spectroscopic (EIS) measurements were conducted to evaluate that
thicker TiO2 photoelectrodes result in higher charge recombina-
tion, as the Nyquist plots in Fig. 7c and the corresponding simplied
equivalent circuit in Fig. 7d [30,31]. Rs is the series resistance
related to the transport resistance of the FTO substrates, and Rpt is
the charge transfer resistance at the counter electrode/electrolyte
interface corresponding to the small semicircle, which are both
nearly the same. Rct is the charge-transfer resistance reveal-
ing the charge-transfer resistance between TiO2 /dye/electrolyte
interfaces, which corresponds to the big semicircle. The larger
radius of the big semicircle in Nyquist plots indicated a slow
charge recombination at the TiO2 /dye/electrolyte interfaces, and
the values of Rct were simulated as 206.5, 89.58, 73.13 and
59.37  by using the Zview software. It was indicated that the
thick TiO2 photoelectrodes resulted in high charge recombination.
Therefore, a suitable thickness 14.5 m of the obtained TiO2 pho-
toelectrodes has brought the optimal performance of DSSCs. The
best-performing DSSCs exhibited 7.13% PCE, in contrast to 6.08%
PCE for DSSCs based on P25 photoelectrodes with the same thick-
ness, as indicated in Fig. 3S. Consequently, the as-obtained anatase
mesoporous TiO2 microspheres with interconnected nanoparticles
are excellent materials as photoelectrodes for DSSCs.
4. Conclusions
Mesoporous anatase TiO2 microspheres consisting of inter-
connected nanoparticles have been successfully synthesized
by a template-free, one-step fast solvothermal process. The
morphology of mesoporous microspheres was assembled by
nucleation-growth-assembly-mechanism, where the urea played
as capping agent to control phase and promote oriented growth.
The mesoporous anatase TiO2 microspheres with interconnected
nanoparticles have the advantages of large surface area and
connected-structure for electron transfer, which were further uti-
lized as efcient photoelectrodes of DSSCs with outstanding PCE
7.13%. We anticipate that the mesoporous anatase TiO2 micro-
spheres consisting of interconnected nanoparticles with large
surface area and connected-structure for electron transfer is of
great signicance in nanodevice applications, such as energy stor-
age, photocatalysis, fuel cells, and photoelectrochemical water
splitting.
Acknowledgments
We acknowledge the nancial support from the National Basic
Research Program of China (2012CB933301, 2014CB648300), the
Ministry of Education of China (IRT1148), the National Synergis-
tic Innovation Center for Advanced Materials (SICAM), the Natural
Science Foundation of Jiangsu Province of China (BM2012010), the
Project Funded by the Priority Academic Program Development
of Jiangsu Higher Education Institutions (YX03001), the National
Natural Science Foundation of China (51172110, 51372119), the
Natural Science Foundation of Scientic and Technological Depart-
ment of Jiangsu Province (KZ0070715050), the Seed Project Funded
by Introducing Talent of NJUPT (XK0070915022), and Science
and Technology Innovation Training Program (STITP) of NJUPT
(XYB2015303).

Please cite this article in press as: L. Chu, et al., Mesoporous anatase TiO2 microspheres with interconnected nanopar-
ticles delivering enhanced dye-loading and charge transport for efcient dye-sensitized solar cells, Appl. Surf. Sci. (2015),
http://dx.doi.org/10.1016/j.apsusc.2015.11.034
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Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2015.11.
034.
References
[1] S. Chattopadhyay, J. Saha, G. De, J. Mater. Chem. A 2 (2014) 1902919035.
[2] E.J.W. Crossland, N. Noel, V. Sivaram, T. Leijtens, J.A.A. Webber, H.J. Snaith,
Nature 495 (2013) 215220.
[3] X.B. Chen, S.S. Mao, Chem. Rev. 107 (2007) 28912959.
[4] X.D. Li, W. Li, M.C. Li, P. Cui, D.H. Chen, T. Gengenbach, L.H. Chu, H.Y. Liu, G.S.
Song, J. Mater. Chem. A 3 (2015) 27622769.
[5] L. Chu, Z.F. Qin, J.P. Yang, X.A. Li, Sci. Rep. 5 (2015) 12143.
[6] T. Tachikawa, S. Yamashita, T. Majima, J. Am. Chem. Soc. 133 (2011)
71977204.
[7] P. Periyat, N. Leyland, D.E. McCormack, J. Colreavy, D. Corr, S.C. Pillai, J. Mater.
Chem. 20 (2010) 36503655.
[8] S. Mikhaylov, N. Ogurtsov, Yu. Noskov, N. Redon, P. Coddeville, J.-L.
Wojkiewicz, A. Pud, RSC Adv. 5 (2015) 2021820226.
[9] J.Y. Liao, B.X. Lei, D.B. Kuang, C.Y. Su, Energy Environ. Sci. 4 (2011) 40794085.
[10] D.P. Wu, F. Zhu, J.M. Li, H. Dong, Q. Li, K. Jiang, D.S. Xu, J. Mater. Chem. 22
(2012) 1166511671.
[11] D.F. Rohlng, A. Zaleska, T. Bein, Chem. Rev. 114 (2014) 94879558.
[12] H.Q. Wang, Z.B. Wu, Y. Liu, J. Phys. Chem. C 113 (2009) 1331713324.
[13] Y. Ding, L. Zhou, L.E. Mo, L. Jiang, L.H. Hu, Z.Q. Li, S.H. Chen, S.Y. Dai, Adv. Funct.
Mater. 25 (2015) 59465953.
Please cite this article in press as: L. Chu, et al., Mesoporous anatase TiO2 microspheres with interconnected nanopar-
ticles delivering enhanced dye-loading and charge transport for efcient dye-sensitized solar cells, Appl. Surf. Sci. (2015),
http://dx.doi.org/10.1016/j.apsusc.2015.11.034
7
[14] B. ORegan, M. Gratzel, Nature 353 (1991) 737740.
[15] A. Hagfeldt, G. Boschloo, L.C. Sun, L. Kloo, H. Pettersson, Chem. Rev. 110 (2010)
65956663.
[16] N. Wang, L. Han, H. He, N.-H. Park, K. Koumoto, Energy Environ. Sci. 4 (2011)
36763679.
[17] B.E. Hardin, H.J. Snaith, M.D. McGehee, Nat. Photonics 6 (2012) 162169.
[18] X.H. Sun, X. Zhou, Y.L. Xu, P.P. Sun, N. Huang, Y.H. Sun, Appl. Surf. Sci. 337
(2015) 188194.
[19] Z. Sun, J.H. Kim, Y. Zhao, D. Attard, S.X. Dou, Chem. Commun. 49 (2013)
966968.
[20] F. Sauvage, D. Chen, P. Comte, F. Huang, L.P. Heiniger, Y.B. Cheng, R.A. Caruso,
M. Graetzel, ACS Nano 4 (2010) 44204425.
[21] M.D. Ye, C. Chen, M.Q. Lv, D.J. Zheng, W.X. Guo, C.J. Lin, Nanoscale 5 (2013)
65776583.
[22] S.S. Mali, C.A. Betty, P.N. Bhosale, P.S. Shinde, M.R. Pramod, S.R. Jadkar, P.S.
Patil, Cryst. Eng. Commun. 14 (2012) 81568161.
[23] C. Chen, J. Wang, Z.M. Ren, G.D. Qian, Z.Y. Wang, Cryst. Eng. Commun. 16
(2014) 16811686.
[24] Z.F. Zhu, C.K. Zhu, H. Liu, Y.F. Wu, G.H. Chen, T. Lv, Appl. Surf. Sci. 308 (2014)
301305.
[25] H.J. Song, T. Chen, Y.L. Sun, X.Q. Zhang, X.H. Ji, Ceram. Int. 40 (2014)
1101511022.
[26] Q.J. Xiang, J.G. Yu, M. Jaroniec, Chem. Commun. 47 (2011) 45324534.
[27] B. Liu, H.C. Zeng, Small 5 (2005) 566571.
[28] Z.S. Wang, H. Kawauchi, T. Kashima, H. Arakawa, Coord. Chem. Rev. 248
(2004) 13811389.
[29] I. Jang, K. Song, J.H. Park, S.G. Oh, Bull. Korean Chem. Soc. 34 (2013)
28832888.
[30] L. Chu, L.Y. Li, J. Su, F.F. Tu, N.S. Liu, Y.H. Gao, Sci. Rep. 4 (2014) 4420.
[31] W.Q. Wu, H.L. Feng, H.S. Rao, Y.F. Xu, D.B. Kuang, C.Y. Su, Nat. Commun. 5
(2014) 3968.