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Contents lists available at ScienceDirect

Applied Surface Science

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

Dye-sensitized solar cells fabricated by the TiO2 nanostructural

materials synthesized by electrospray and hydrothermal
post-treatment
Bing Hu a , Baoshun Liu b,
a
School of Chemistry and Chemical Engineering, Hubei University of Technology, Wuhan City, Hubei Province 430068, PR China
b
State Key Laboratory of Silicate Materials for Architectures, Wuhan University of Technology, Luoshi Road 122, Wuhan City, Hubei Province 430070,
PR China

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

Article history: Recently, a series of new hierarchical porous TiO2 spheres with specic high surface area and pore vol-
Received 20 June 2015 ume were prepared by the method of electrospray and hydrothermal post-treatment in our group. The
Received in revised form 21 August 2015 applications of these materials in photocatalysis have been investigated. In this research, the application
Accepted 25 August 2015
of them in dye-sensitized solar cells (DSSCs) was studied. The porous TiO2 spheres showed a Gaussian
Available online xxx
distribution with average size of ca. 600 nm, which can be used as good materials for light scattering in
DSSCs. The specic surface areas of these materials are high enough for dye adsorption. The DSSCs made
Keywords:
from the electrosprayed materials shows a 7.2% light-to-electricity efciency, and the maximum external
TiO2 mesoporous materials
Dye-sensitized solar cells
quantum efciency (EQE) at 530 nm is over 90%. The UVVis diffusion reectance and EQE measurement
Electrospray proved that the as-prepared TiO2 materials show dual functions of light scattering and dye-adsorption,
Hydrothermal treatment which is an important functional material in DSSCs.
Light-scattering 2015 Elsevier B.V. All rights reserved.

1. Introduction The alternative method is to increase light harvesting ability

As one of the important light-to-electricity convertors, dye
sensitized solar cells (DSSCs) have attracted signicantly atten-
tions since its rst report [1] due to its low cost. Nowadays, the
researches focus on the further increase of the DSSC energy conver-
sion efciency. The physicalchemical factors that affect the DSSC
efciency mainly include light harvesting ability and electron diffu-
sion length. To date, many works devoted to increasing the electron
diffusion length and the energy conversion efciency by construc-
ting different photoanode structures [2,3]. For example, the solar
cells made of nanotube arrays [1,4], nanorod arrays [57], nano-
bres [8], and other interconnected structures [911] present the
long electron diffusion length and the high performance. More-
over, it was reported that one-dimensional nanomaterials have
higher electron transfer speed than conventional porous electrode
[1214]. Recently, it was also seen that the TiO2 nanoparticles with
exposed {0 0 1} facets can increase DSSC efciency due to charge
recombination retarding and electron diffusion increase [15].
Corresponding author.
E-mail address: liubaoshun@126.com (B. Liu).
within the DSSCs, which includes the use of the dyes with high
extinction coefcient, the increase of dye adsorption capacity, and
the increase of light scattering within photoanode. The features of
photoanode materials, including the specic surface area, the pore
structure, and the morphologies, are important for dye-absorbing
and light-scattering. Although TiO2 nanoparticles are necessary to
assemble DSSCs due to their strong dye adsorption capacity [16],
the photoanodes made of them are almost visible-transparent.
Therefore, additional scattering layers are generally needed, and
due to which, a layer of ca. 400 nm TiO2 particles was coated on top
of TiO2 nanoparticle layer to increase the energy conversion ef-
ciency [17]. Other-shape big particles, such as large nanospindles
[18] and microspheres with exposed mirror-like {0 0 1} facets [19],
were also used to scatter light. Besides TiO2 , other materials like
ZnO and SnO2 , were also used to produce light scattering in DSSCs
[2022]. To further improve the light scattering effect, the struc-
ture of photonic structure was also prepared due to the synergic
effects of structural modications caused during the integration
of photonic crystals [2325]. Besides, mesoporous TiO2 spheres
were also used as a kind of light-scattering material in DSSCs. For
example, DSSCs made of mesoporous TiO2 beads presented 7.2%
efciency due to the dual-functions of dye-adsorption and light-
scattering [26]. If the C101 and C102 dyes were used, which have

http://dx.doi.org/10.1016/j.apsusc.2015.08.221
0169-4332/ 2015 Elsevier B.V. All rights reserved.

Please cite this article in press as: B. Hu, B. Liu, Dye-sensitized solar cells fabricated by the TiO2 nanostructural materials synthesized
by electrospray and hydrothermal post-treatment, Appl. Surf. Sci. (2015), http://dx.doi.org/10.1016/j.apsusc.2015.08.221
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higher molar extinction coefcient, much higher energy conver-
sion efciency (over 10%) can be reached [27]. As the mesoporous
TiO2 nanostructural materials can both increase dye adsorption and
light scattering, they has become an important functional material
in DSSCs.
Among many kinds of materials, the nanostructural TiO2 mate-
rials that integrate special morphologies with high specic surface
area, suitable porous size, and high porous volume should be
important, as they can both adsorb dyes and produce light scat-
tering. From this viewpoint, developing new method to prepare
new nanostructural TiO2 materials is important for highly efcient
DSSCs. Recently, we used a new way, which combined electrospray
and post-hydrothermal treatment, to prepare TiO2 mesoporous
spheres that have tunable specic surface area, tunable pore size,
and tunable pore volume [2832]. We showed that the TiO2 meso-
porous spheres presented high photocatalytic activity under UV
light illumination [32]. Here, we studied the application of these
TiO2 spherical materials in DSSCs. The results showed that these
TiO2 spheres present obvious light-scattering function, in addi-
tional to the high dye adsorption. The DSSC with 7.2% energy
conversion efciency and over 90% external quantum efciency
(EQE) can be obtained. Overall, it is shown that the combination of
electrospray and hydrothermal post-treatment is a good method
to prepare TiO2 hierarchical nano-materials for DSSCs photoanode
fabrication.
2. Experimental
2.1. Preparation of mesoporous TiO2 spheres and TiO2
nanoparticles
The mesoporous TiO2 spheres were prepared using the
method of electrospray followed by hydrothermal post-treatment
according to our previous studies [28,29]. Briey, 0.3 g of
polyvinylpyrrolidone (PVP) K30 was dissolved in the mixture of
2.54 ml of ethanol and 3.82 ml of acetic acid under continuous mag-
netron stirring. About 10 min later, 7.0 ml of tetrabutyl titanate
(Ti(oBu)4 ) was added, and the mixed solution was kept stirring
for ca. 1 h to get a uniform PVP@TBT sol. This sol was loaded in
a plastic tube, and pumped slowly to ow through a small metal
nozzle (a 23 G metal needle), with a large aluminum target being
vertically below the needle ca. 2530 cm away. A high electric eld
was applied between the metal needle and the aluminum target.
The sol was atomized as small charge aerosol droplets at the tip of
the nozzle under the function of high electric eld, which was then
collected by the ground contacted aluminum target. The PVP@TBT
sol was supplied at 1.0 ml/h by a springe pump. The electric eld
strength was set at 35 kV so as to keep a stable Taylor cone aerosol
mode. The sprayed TiO2 spheres on the aluminum target were
carefully collected and dried in air overnight in order to let the
Ti precursors completely hydrolyzed. The dried spheres were put
in a Teon-sealed steel autoclave with a mixture of ethanolwater
solution (20 ml:10 ml) containing 1.0 ml ammonia or not inside. The
hydrothermal reaction was performed at 160 C for 24 h. After the
reaction, the product was ltrated, washed, and dried in air at ca.
50 C. Finally, the product was heat-treated at 500 C for half hour
before making paste (this process is necessary as it can eliminate
the cracks of TiO2 coatings).
The TiO2 nanoparticles were synthesized by using the similar
method. Firstly, the precursor materials were prepared by using
electrospray and the PVP amount used was 0.7 g; secondly, the
sprayed materials were mixed with ethanol, water, and acetic
acid to undergo a strong stirring for more than 2 h; thirdly, the
sample was put in an autoclave for hydrothermal reaction at
160 C for 24 h. After hydrothermal reaction, the product was
Please cite this article in press as: B. Hu, B. Liu, Dye-sensitized solar cells fabricated by the TiO2 nanostructural materials synthesized
by electrospray and hydrothermal post-treatment, Appl. Surf. Sci. (2015), http://dx.doi.org/10.1016/j.apsusc.2015.08.221
dispersed ultrasonically for ca. 2 h. Because the as-synthesized
nanoparticles are very small, it was difcult to be separated
from the hydrothermal solution. We added a little ammonia in
hydrothermal solution to change the pH value. After the solution
changes from acid to base, the nanoparticles quickly aggregate
together and participated, which become easily separated.
2.2. DSSC making
To prepare a screen-printable paste, ethyl cellulose and -
terpineol were mixed in ca. 20 ml ethanol solution, which was
stirring to completely dissolve ethyl cellulose in ethanol. 0.25 g TiO2
mesoporous spheres, TiO2 nanoparticles, or P25 were mixed in the
above solution, and was stirring for ca. 10 min, which were still
followed by 10 min ultrasonic dispersion. After the ethanol in the
mixed solution was removed by heating, the viscous TiO2 pastes
were prepared. To prepare the DSSC working photoanodes, the self-
made pastes were used. These pastes were coated on the conductive
FTO glass (15/square, Nippon Sheet Glass, Japan) by screen-painting
method. The FTO glasses were ultrasonically washed by the diluted
HCl acid, ammonia, acetone, and ultra-pure water, sequentially.
Finally, the washed FTO glasses were subjected to ca. 30 min ozone
treatment. The areas of these TiO2 coatings on FTO glasses were
4 mm 4 mm squares. The coatings were heated at 500 C for ca.
30 min to remove the organic substances. Afterwards, the pho-
toanodes were treated by using TiCl4 water solution at 70 C for
half hour. After washed by water, the TiCl4 treated samples were
annealed at 500 C for another half hour. The annealed TiO2 coatings
were soaked in 0.3 mM N719 dye solution (1:1 acetonitrile and
tertbutanol) at room temperature (25 C) for 24 h for dye loading.
The TiO2 working photoanodes were assembled and hot-sealed
with the sputtered counter Pt electrodes. The electrolyte, 0.6 M
1,2-dimethyl-3-propylimidazolium iodide, 0.1 M LiI, 0.05 M I2 , and
0.5 M 4-tert-butylpyridine in acetonitrile was injected into the cell
quickly by a transfer liquid gun.
2.3. Measurement
Material morphologies were observed by using a eld emission
scanning electron microscope (FE-SEM, type: Hitachi S-4800). X-
ray diffraction (type: RINT-1500) was used to check the crystallinity
and estimate the crystal sizes of the mesoporous TiO2 spheres.
N2 absorption isotherms were measured at 196 C by using a
Micromeritics system. Prior to the measurement, the samples were
rstly degassed at 200 C in a vacuum line for 1 h. The multipoint
BrunauerEmmettTeller (BET) was used to calculate the specic
surface area using the adsorption data of isotherms. The pore size
distributions were derived from the adsorption data of isotherms
based on a BarrettJoynerHalenda (BJH) model. A eld emission
transmittance electron microscope (FE-TEM, type: EM002BF) was
used to see the morphologies and size of the nanoparticles in the
TiO2 spheres. A Shimadzu UVVis photo-spectrometer (UV-2450,
Shimadzu, Japan) was used to check the diffusion spectra of the
TiO2 coatings made of different pastes.
Photovoltaic properties of the sealed solar cells (the active area
is 4 mm 4 mm) were measured by using a Keithley 2400 Source
Meter under illumination of simulated sunlight (1000 W m2 ) pro-
vided by a Peccell Technologies, Inc. solar simulator with an AM1.5G
lter. EQE plotted as a function of excitation wavelength was
recorded on a Keithley 2400 Source Meter under the irradiation
of a 150 W xenon lamp.
3. Results and discussion
Fig. 1(A) shows the FE-SEM image of the TiO2 spheres prepared
without using ammonia during hydrothermal reaction. Fig. 1(B)
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Fig. 1. FE-SEM photos of TiO2 spheres after hydrothermal treatment without using ammonia (A), and using ammonia (B); size distribution of TiO2 spheres (C); TEM photo
of TiO2 as-prepared nanoparticles (D).

shows the FE-SEM image of the TiO2 spheres with using ammo- can induce better crystallization. As we explained in previous
nia during hydrothermal reaction. If ammonia was not used during research [28], the use of ammonia in hydrothermal reaction can
hydrothermal reaction, it can be seen from Fig. 1(A) that the TiO2 make the hydroxyl groups replace the acetic acid groups on TiO2
spheres are composed of uniform TiO2 nanoparticles, with many nanoparticle surface, and the hydroxyl group caped nanoparticles
small pores uniformly distributing on them. If 1.0 ml ammonia was can combined together to form bigger nanoparticles. By using the
used, the spheres showed different structure (Fig. 1(B)) as they Sercherr equation, the average sizes of crystallites in TiO2 spheres
consist of both small and big nanoparticles as compared to the uni- are 8 nm (without using ammonia) and 15 nm (using ammonia).
form nanoparticles in Fig. 1(A), which makes the pore size in this The specic surface areas, the pore sizes, the pore volumes,
material bigger than that of sample without using ammonia. As and the pore distributions of paste-1, paste-2, paste-3, and paste-4
shown in our previous study [23], the big nanoparticle in Fig. 1(B) were measured, and the related data is shown in Table 1. In this
is formed through the small nanoparticle dehydration combina-
tion [23,26]. Fig. 1(C) shows the size distribution of TiO2 spheres,
and the as-prepared TiO2 spheres are poly-dispersed and have a
Gaussian distribution that centers at ca. 600 nm. The FE-TEM image
(Fig. 1(D)) shows that the TiO2 nanoparticles are small and uniform,
with a narrow size distribution from 5 nm to 20 nm. We selected
the above three materials to prepare DSSCs. The TiO2 materials
shown in Fig. 1(A) was used to make micro-sphere paste with small
pore size, named paste-1; The TiO2 materials shown in Fig. 1(B)
was used to make micro-sphere paste with large pore size, named
paste-2; and the TiO2 material shown in Fig. 1(D) was used to make
nanoparticle paste, named paste-3. Moreover, commercial P25 was
also used to prepare paste for comparison, named paste-4.
Fig. 2 shows the XRD patterns of the TiO2 nanoparticles,
the TiO2 spheres prepared with using ammonia, and the TiO2
spheres prepared without using ammonia. It can be seen that
main crystalline phase of our samples are anatase type, with the
crystal facets being labeled directly on the gure. The TiO2 spheres
prepared with using ammonia containing a little brookite phase. Fig. 2. XRD patterns of the TiO2 nanoparticles, the TiO2 spheres after hydrothermal
It can be seen that adding ammonia in hydrothermal reactions treatment without and with using ammonia.

Please cite this article in press as: B. Hu, B. Liu, Dye-sensitized solar cells fabricated by the TiO2 nanostructural materials synthesized
by electrospray and hydrothermal post-treatment, Appl. Surf. Sci. (2015), http://dx.doi.org/10.1016/j.apsusc.2015.08.221
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Table 1 Table 2
The specic surface area, the pore volume, and the pore size of paste-1, 2, 3 and 4. Properties of DSSCs prepared by using paste-1 and paste-3.

Sample SBET (m2 g1 )a Vp (ml g1 )b DP (nm)c Sample d (m)a JSC (mA/cm2 )b Voc (V)c FFd  (%)e

Paste-1 90 0.27 10 Paste-3(1) 7 11.6 0.73 0.67 5.62

Paste-2 70 0.43 45 Paste-3(2) 12 12.8 0.71 0.68 6.14
Paste-3 85 0.42 35 Paste-1(1) 17 11.31 0.68 0.69 5.34
Paste-4 54 0.18 Paste-1(2) 23 12.4 0.68 0.70 5.93
a
Paste-3/paste-1(1) 5 + 10 15.2 0.70 0.66 7.2
Specic surface area.
b
Paste-3/paste-1(2) 12 + 9 13.97 0.66 0.70 6.52
Pore volume.
c
Paste-3/paste-1(3) 17 + 15 11.24 0.63 0.74 5.24
Average pore size conclusions.
a
Coating thickness.
b
Short-circuit photocurrent.
measurement, the pastes were rstly coated on aluminum foils, c
Open-circuit voltage (V).
and then were annealed at 500 C for half hour. After annealing, d
Fill factor of DSSCs.
e
the coatings were peeled off from aluminum foils and used in BET Power conversion.
measurement. The paste-1 has the highest specic surface area and
lowest pore size. The specic surface area of paste-2 decreases as and suitable pore size. Our experiments also veried this point as
compared to that of paste-1, and its pore size increases obviously. the TiO2 nanoparticle layer almost becomes black after dye absorb-
It can be seen that we can successfully adjust the specic surface ing (see Fig. S2(a)). The paste-1 and paste-2 were used to prepare
area and pore size of TiO2 spheres by adding ammonia or not dur- the light-scattering layers of DSSCs in our work. Besides, the TiO2
ing the hydrothermal reactions. The specic surface area and pore spheres can also adsorb dye molecule as they has high specic sur-
size of paste-3 is between that of paste-1 and paste-3. The pore face area, as shown in Fig. S2(b) and (c), so they have dual-function
volume of paste-1 is the smallest due to the smallest pore size. The of dye-absorbing and light scattering.
pore volume of paste-2 is ca. 0.43 ml g1 ; the pore volume of paste- Fig. S3(a)(c) shows SEM photos of TiO2 paintings by screen-
3 is also very high, which is ca. 0.42 cm3 g1 . For comparison, the coating the paste-1 (small porous TiO2 spheres) and paste-3
related data of paste-4 (P25) was also shown, which has the lowest (nanoparticles) on FTO glass substrates. Fig. S3(a) is the single-
specic surface area and pore volume, and average pore size cannot layer TiO2 sphere coating made of paste-1, with the magnication
be determined. Fig. 3 shows the pore size distributions of paste-1, picture being shown in left-corner. It can be seen that this TiO2
paste-2, paste-3, and paste-4. It can be seen that paste-1 shows a coating consists of perfect TiO2 spheres, which was not destroyed
very narrow pore size distribution (the blue line), which centers at during the paste preparation. These spheres compact together
ca. 10 nm. The paste-2 shows a little wider pore size distribution, tightly and connected well from each other, so this should be
with the maximum value being at ca. 45 nm (the green line). The benecial for the electron transport. As compared to the monodis-
paste-3 also shows a wide pore size distribution around 35 nm (the persed TiO2 spheres, this polydispersed sample allows the small
red line). The paste-4 made of P25 has not a clear pore size distri- spheres to enter the voids among big ones, which can effectively
bution in the range of 0100 nm, so the average pore size cannot increase the compacted density of TiO2 painting. Fig. S3(c) shows
be determined. the double-layered TiO2 coatings by coating the paste-3 and paste-
Fig. 4 shows the diffusion reectance of the TiO2 coatings pre- 1 as the bottom and the top layers, respectively, we can see that the
pared by screen-painting the different pastes on conductive FTO nanoparticle layer combines well with the TiO2 sphere layer.
glass substrates. The coatings made of paste-1 and paste-2 show As shown in Table 2, we rstly studied the effect of thick-
strong reectance in the whole wavelength range from 400 nm to ness of nanoparticle coating on the power efciency of DSSCs. The
800 nm, so they should have the functions to scatter light in DSSCs. power efciency increases from 5.62% to 6.14% as the NP thickness
This strong visible light reection is also supported by the pic- increases from 7 m to 12 m. The increase of thickness has little
tures (Fig. S1 (b) and (c)). The TiO2 coatings made of paste-3 shows effect on the ll factor of the DSSCs, while Voc decreases and JSC
the lowest light reection and is semi-transparent (Fig. S1(a)), increases as the nanoparticle coating thickness increases. It can be
as compared to that made of paste-1, paste-2, and paste-4. The seen that the increase of power efciency when increasing coating
nanoparticle coating has high light transmittance, but it was used as thickness is due to the increase of JSC , as more dye molecule can
the dye-adsorbing layer in present research as it is composed of tiny be adsorbed for thicker coating. For the DSSCs made of single layer
nanoparticles (ca. 8 nm) with high specic surface area (85 m2 g1 )

Fig. 4. UVVis diffused reectance spectra of TiO2 coatings made from paste-1, 2, 3
Fig. 3. Pore size distribution of paste-1, paste-2, paste-3, and paste-4. and 4.

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by electrospray and hydrothermal post-treatment, Appl. Surf. Sci. (2015), http://dx.doi.org/10.1016/j.apsusc.2015.08.221
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Table 3
Properties of DSSCs prepared by using paste-2, paste-3, and paste-4.

Sample d (m) JSC (mA/cm2 ) Voc (V) FF  (%)

Paste-4 18 5.29 0.69 0.75 2.77

Paste-2 17 6.65 0.72 0.73 3.53
Paste-2 26 11.04 0.70 0.68 5.27
Paste-3/paste-2(1) 13 + 8 13.85 0.69 0.67 6.39
Paste-3/paste-2(2) 16 + 20 10.96 0.64 0.65 4.52

shown in Fig. S3(a), because these TiO2 spheres are much looser
as indicated by Fig. 1(B). Fig. S4(B) shows that the sphere top-
layer was well combined with the nanoparticle bottom-layer. All
of the coatings were well connected with FTO glass substrates and
crack-free, including the coatings made P25 paste (paste-4).
The performances of the DSSCs made from these pastes are
shown in Table 3. The DSSCs made of 18 m paste-4 (p25) coat-
ing shows 2.77% power efciency, and that made of paste-2 layer
shows efciency of 3.53%. Increasing the thickness of paste-2 layer
to 26 m can increase the power efciency to 5.27% as JSC increases,
which is accompanied by the decrease of Voc , so the increase of
dye adsorption with the thickness increase is the main factor that
affects the DSSCs performance in this case. The DSSCs that coupled
the nanoparticle bottom layer (13 m) and the layer of large porous
spheres (8 m) show 6.39% power efciency. Further increase of
nanoparticle layer thickness and the large pore sphere layer thick-
ness leaded to obvious decrease of power efciency. Fig. 6(A) shows
the JV dependences of DSSCs (see the explanation in Table 3). It can

Fig. 5. JV measurements of DSSCs prepared by using the photoanodes of paste-

1, paste-3, and double paste-3/paste-1 (A); external quantum efciency of DSSCs
prepared by using paste-3 and paste-1 (B) (please see detail in Table 2).

coating of paste-1 (TiO2 spheres with small size pores), the increase
of coating thickness from 17 m to 23 m can increase the JSC , but
the Voc and FF were almost unchanged, resulting in the increase of
power efciency. We also fabricated other three DSSCs with double
layers coated by using paste-3 and paste-1 with different thickness,
and the best power efciency is 7.2%. In this cell, the thickness
of paste-3 coating and paste-1 coatings were 5 m and 10 m,
respectively. Further increasing the thicknesses of coatings made
of paste-3 and pastes leaded to the decrease of power efciency,
which may be due to that the photoanode thickness is beyond
the length of electron transport. Fig. 5(A) shows the JV curves of
DSSCs prepared by using paste-3 and paste-1 (see the explanation
in Table 1). The DSSCs show typical and good JV dependences (high
ll factor), indicating that the DSSCs with good structures have
been made. Fig. 5(B) shows the external quantum efciency (EQE)
of DSSCs made from paste-3 and paste-1. As compared to the DSSCs
made of the TiO2 nanoparticles, it can be seen that the TiO2 sphere
material can obviously increase the light-scattering effect from 600
to 700 nm. Coating additional TiO2 sphere layer on the nanoparticle
layer can effectively increases the EQE of DSSCs, and the maximum
value at 530 nm can reaches 90%. If the glass reection was taken
into account, it can be known that the photon-to-electricity of the
double-layer DSSCs should be near 100%.
Fig. S4 shows the SEM photos of coatings prepare by using
paste-2, the double-layered coatings prepared by using paste-
3 (nanoparticles) and paste 2 (large porous TiO2 spheres), and Fig. 6. JV measurements of DSSCs prepared by using the single-layer photoanodes
of paste-2, double-layer photoanode of paste-3/paste-2, and single-layer photoan-
the coating prepared by using paste-4 (P25). The paste-2 coat-
ode of paste-4 (A) (see detail in Table 3); external quantum efciency of DSSCs
ing is composed of well-compacted TiO2 spheres. However, these prepared by using paste-4, paste-2, double-layer paste-3/paste-4 (B) (please see
spheres were slightly destroyed as compared to the TiO2 spheres detail in Table 3).

Please cite this article in press as: B. Hu, B. Liu, Dye-sensitized solar cells fabricated by the TiO2 nanostructural materials synthesized
by electrospray and hydrothermal post-treatment, Appl. Surf. Sci. (2015), http://dx.doi.org/10.1016/j.apsusc.2015.08.221
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be known that these DSSCs also show good JV characteristics, sim-
ilar to that in Fig. 5(A). Fig. 6(B) shows EQE spectra of DSSCs made of
large porous TiO2 spheres, nanoparticle/large-porous spheres, and
P25 (see detail in Table 3). Similarly, the layer of large pore spheres
on nanoparticle bottom layer can effectively increase the light scat-
tering in the region from 600 nm to 700 nm, which can effectively
increase the photon-to-electricity conversion.
4. Conclusions
The application of nanostructural TiO2 hierarchical spheres pre-
pared by electrospray plus hydrothermal post-treatment in DSSCs
was studied in this research. The TiO2 spheres were poly-dispersed
and had a Gaussian distribution cantered at 600 nm, which is suit-
able for light-scattering in DSSCs. At the same time, the pastes
made of these spheres also have high specic surface area, small
pore size, and high pore volumes, so the as-prepared TiO2 spheres
materials also has high ability to adsorb dyes. It was shown that
this kind of TiO2 materials has dual-functions of light-scattering
and dye adsorption. The DSSC prepared by using the TiO2 spheres
as top-scattering layer shows 7.2% power efciency, and the EQE at
the wavelength of dye maximum adsorption is beyond 90%. There-
fore, the TiO2 spherical materials prepared by electrospray and
hydrothermal treatment are also important functional materials
for DSSC applications.
Acknowledgment
B. Liu acknowledges the Fundamental Research Funds for the
Central Universities (Wuhan University of Technology) (2012-IV-
008).
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.2015.08.
221.
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