Optical Materials 75 (2018) 102e108

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Optical Materials
journal homepage: www.elsevier.com/locate/optmat

Effect of cerium ion modifications on the photoelectrochemical

properties of TiO2-based dye-sensitized solar cells
Guangyu Xing a, b, Zige Zhang a, b, Shibo Qi c, Guangye Zhou a, b, Kaiyue Zhang a, b,
Zijian Cui a, b, Yaqing Feng a, b, Zhongqiang Shan a, b, Shuxian Meng a, b, *
a
Department of Applied Chemistry, School of Chemical Engineering and Technology, Tianjin University, Yaguan Road 135#, Tianjin, 300350, PR China
b
Collaborative Innovation Center of Chemical Science and Engineering, Weijin Road 92#, Tianjin, 300072, PR China
c
School of Environmental and Chemical Engineering, Tianjin Polytechnic University, Tianjin, 300387, PR China

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

Article history: Several different quantities of Ce/TiO2 materials were synthesized in the same condition by a wet
Received 28 August 2017 method. Dye-sensitized solar cells (DSSCs) were fabricated by using porous Ce/TiO2 film electrodes
Received in revised form derived from P25 nanoparticles. Various techniques such as X-ray diffraction, Scanning electron micro-
2 October 2017
scope and Brunauer-Emmett-Teller are used to characterize the products. The short-circuit current
Accepted 3 October 2017
density and photo-electric conversion efficiency reach optimum values: 13.87 mA cm
2 and 7.00%
respectively when the amount of Ce(NO3)3$6H2O is 0.050 g/1 g P25, which may be attributed to better
transportation of electrons and more adsorption of dyes and sunlight.
Keywords:
Cerium
© 2017 Elsevier B.V. All rights reserved.
TiO2
Photoelectrodes
DSSCs

1. Introduction
Compared with conventional solar cells, dye-sensitized solar
cells (DSSCs) have become an attractive alternative due to their low
cost and high energy conversion efficiency [1,2]. While, it is
necessary to further improve the energy-conversion efficiency in
order to commercialize DSSCs successfully. Currently, research ef-
forts are focusing on the improvement of the sensitized photo-
anodes, dyes [3], electrolytes [4], cathodes, their interfaces and the
fabrication technologies [5]. As a vital part of DSSCs, the photo-
anode plays a key role in the aspect of transferring electrons and
adsorbing dyes. Therefore, the methods of improving conversion
efficiency of solar cells have been attributed to two main factors:
the first one is modifying the structure of photoanode to utilize a
wider range of wavelength of sunlight [6,7], the other one is
improving the amount of adsorbed dyes on the photoanode to in-
crease the short circuit current [8]. So far, the most appropriate
material of fabricating photoanode is nano titanium dioxide(nano-
TiO2), as a result of its large specific surface areas, photochemical
* Corresponding author. Department of Applied Chemistry, School of Chemical
Engineering and Technology, Tianjin University, Yaguan Road 135#, Tianjin, 300350,
PR China.
E-mail address: msxmail@tju.edu.cn (S. Meng).
stability and so forth. However, TiO2 has a defect of large band
gap(3.2 eV), which makes TiO2 merely utilize the ultra violet light
which owns higher energy to excite electrons. Thus, how to modify
the nano titanium to make it use a wider range of wavelength of
sunlight has become a novel research hot issues [9,10].
According to previous literatures [11,12], doping nano-TiO2 with
some other elements, especially the rare-earth elements, can solve
the problem effectively. That is because rare-earth elements can not
only ameliorate the internal structure of semi-conductors but also
provide energy conversion properties to improve the photo-electric
conversion efficiency [11e13].
In 2010, Wu et al. doped rare-earth oxide europium-doped yttria
(Y2O3:Eu3þ), a luminescence medium and P-type dopant, into the
DSSCs to improve photocurrent, photovoltage and conversion ef-
ficiency [14]. Photoanodes of hybrid TiO2/La2O3 prepared by
modification of TiO2 films via doping or coating in the isopropanolic
La3þ solution have been studied by Yu et al. [15]. Doping the TiO2
photoelectrodes with Eu3þ and Sm3þ ions, also brings a consider-
able increase in the cell parameters [16]. Doping with Al will
introduce oxygen vacancies which can act as carriers for electron
conduction, hence the conductivity is increased [17e19]. Moreover,
doping titania electrode with lanthanide ions provides complexa-
tion centers on the TiO2 surface, thus its dye adsorption is enhanced
[20]. Asemi et al. made an attempt to introduce the same amount of

https://doi.org/10.1016/j.optmat.2017.10.006
0925-3467/© 2017 Elsevier B.V. All rights reserved.
 G. Xing et al. / Optical Materials 75 (2018) 102e108
Ce3þ into TiO2 nanorods with different reaction time, demon-
strating doping with Ce3þ can improve the conversion efficiency of
photoanode [21]. Overall, rare earth oxides are found to have
multiple physical and chemical properties, strong adsorption
selectivity and ideal thermal stability, due to their f electron and
multi-electron configuration.
In the past, our research team has investigated the modification
of doping photoanode with two rare-earth elements: La3þ [22] and
Sm3þ [23] and has drawn corresponding conclusions: compared
with unmodified photoanode's, the modified photoanode's con-
version efficiency improves by 20%e30%, which may be attributed
to the photo-electric characteristic of rare-earth elements.
Considering about the properties of Ce3þ and no previous reports
on doping nano-TiO2 with different amounts of Ce3þ, we further
investigated the nano-TiO2 photoanode doped with the optimum
amount of Ce3þ at the peak of conversion efficiency and obtained
some conclusions.
2. Experimental
2.1. Materials
TiO2 nanopowder was purchased from Degussa AG, Germany.
Ce(NO3)3$6H2O was purchased from Aladding, China. Anhydrous
lithium iodide(LiI), iodine(I2), 1,2-dimethyl-3-propylimidazolium
iodide (DMPⅡ), 4-tert-butylpyridine (TBP) and guanidine iso-
thiocyanate(GuSCN) were purchased from HeptaChroma, China.
Acetonitrile, valeronitrile and ethyl cellulose(EC) were purchased
from J&K. Fluorine-doped SnO2 conducting glass(FTO, sheet
resistivity ¼ 15U square
1), cis-diisothiocyanato-bis (2,20 -bipyr-
idyl-4,40 -dicarboxylato)ruthenium(Ⅱ) bis(tetrabutylammonium)
(N719) was purchased from Solaronix, Switzerland.
2.2. Synthesis of Ce/TiO2 nano-crystalline particles
Different Ce-TiO2 particles were fabricated by a wet method as
follows: 1 g P25 was dissolved in an amount of 0.1 M nitrite acid
solution under vigorous stirring at 80  C. After 3 h, a light blue
translucent solution was obtained. A certain amount of Ce(N-
O3)3$6H2O (0.030 g, 0.040 g, 0.050 g, 0.075 g, 0.100 g) was added
into the stirred solution for 1 h at 80  C. Then the as-prepared
sample was transferred to an 80 mL Teflon autoclave and kept at
200  C for 12 h. After cooling down to 25  C, the white precipitate
was centrifuged, washed with absolute ethanol and distilled water
for 3 times respectively, and dried at 60  C. Then the powder was
calcined at 500  C for 4 h(5  C min
1). The obtained samples were
then denoted as Ce/TiO2.
2.3. Fabrication of TiO2 photoanode and DSSCs assembly
FTO-coated glasses were cleaned by sonication in water with
detergent, deionized water and ethanol. Next, the TiO2 thick films
were prepared on fluorine-doped tin oxide (FTO) conductive
glasses via a knife-coated method. The Ce-doped or original TiO2
films were calcined at 500  C for 15 min for removing organics.
Prior to dye adsorption, the as-prepared sample was placed in
120 mL of 40 mM TiCl4 solution which was prepared with mixture
of TiCl4 and ice, in a beaker covered with para film at 70  C for
45 min. The resultant films were calcined at 500  C for 30 min at a
heating rate of 5  C min
1. After cooling down to 110  C, the P25 and
Ce-TiO2 films were sensitized in a dye solution of N719 for 22 h.
Then the films were rinsed with absolute ethanol to eliminate
excess unadsorbed dyes and dried in air. Then the photoelectrode
was assembled with Pt counter-electrode and an electrolyte to form
a sandwich-type cell. The electrolyte was composed of 0.6 M DMPII,
103
0.03 M I2, 0.5 M 4-TBP and 0.1 M GuSCN in a mixed solvent of
acetonitrile and valeronitrile by 85:15 vol ratio.
2.4. Characterizations
Morphologies of the samples were observed by a Scanning
Electron Microscope (SEM, S-4800, Japan Hitachi Ltd). X-Ray
Diffraction (XRD) analysis of crystal phases and crystal sizes was
conducted by an X-ray diffractometer(D/MAX-2500, Japan, Rigaku)
with Cu Ka radiation in the condition of a 40 kV working voltage,
40 mA working ampere and a 2q range from 10 to 80 . Nitrogen
adsorption-desorption isotherms of Ce/TiO2 materials were
measured on a domestic N2 adsorption apparatus at
196  C. Prior
to analysis, the samples were degassed at 150  C for 2 h on a vac-
uum line. The Brunauer-Emmet-Teller (BET) method was utilized to
calculate the specific surface area. Photo-
currentephotovoltage(JeV) was measured by a source measuring
unit (model 2400, Keithley) under simulated AM 1.5 one-sun
condition(solar AAA simulator, oriel China, calibrated by a stan-
dard crystalline silicon solar cell). The electrochemical impedance
measurement (EIS) of the photoanodes was obtained by an elec-
trochemical workstation (CHI-660D, Shanghai Brilliance Co., Ltd).
The amount of dye adsorbed was measured by UVevis spectros-
copy. In order to measure the surface concentration of the dye in
the TiO2 electrode, the dye was desorbed into a 0.1 M NaOH solu-
tion in ethanol and water (60:60, v/v) and absorption spectra of the
desorbed-dye solution was measured via a UVevis
spectrophotometer.
3. Results and discussion
X-ray diffraction (XRD) patterns of P25 and the TiO2 doped with
different amounts of Ce show that the anatase structure of TiO2
prevails in the case of the mixed oxides. All peaks of the prepared
samples can be the anatase and rutile phases, indicating that the
anatase and rutile crystal structures are still retained after being
doped. According to the XRD profiles, the anatase crystal structures
and the particle sizes were not easily influenced by Ce with the
different amounts. Ce/TiO2 particles have smaller power than pure
P25 based on characteristic diffraction peaks of the rutile phase,
which is ascribed to the fact that ionic radii of Ce4þ and Ce3þ are
0.093 nm and 0.103 nm, respectively. Meanwhile, ionic radii of Ce4þ
and Ce3þ are larger than 0.068 nm which is ionic radius of Ti4þ.
Therefore, it is difficult to allow doped cerium ions enter into the
TiO2 lattice. Doped cerium ions only exist as the so-called second
phase on the surface of TiO2, which inhibits the crystallite growth of
rutile phase. So the phase transformation of TiO2 is suppressed [24].
No crystalline Ce2O3 and Ti-Ce phase can be observed from XRD
patterns as a result of the tiny amount of dopant. In addition, there
are no obvious shifts in the peak, which indicates that there is no
distortion in the TiO2 and illustrates that Ce ion did not enter into
the bulk lattice of TiO2 [25]. From the full width at half-maximum of
the strongest anatase diffraction, the crystallite sizes are calculated
to be 27 nm for both original and Ce-doped TiO2 samples, which are
consistent with the SEM analysis. In Fig. 2, P25 sample was
compared with that of 0.030 g-Ce/TiO2, 0.040 g-Ce/TiO2, 0.050 g-
Ce/TiO2, 0.075 g-Ce/TiO2 and 0.100 g-Ce/TiO2 mesoporous film in
the same SEM micrographs. Regardless of the substituent, the film
is composed of nanoparticles whose diameters are about 30 nm.
Meanwhile, in the surface of nanoparticles, there are mesopores
ranging from 20 to 30 nm in diameter. This structure is particularly
suitable to guarantee more dye to be loaded and transport electrons
through the pores [26]. These mesopores can even make a contri-
bution to providing more surface and leading to more dye
adsorption, which is also an important reason for the improvement
104 G. Xing et al. / Optical Materials 75 (2018) 102e108

speed of electrons must be faster than the reaction speed with

molecules in the solution [29]. From Table 2, Jsc improves with the
amount of Ce3þ increasing until the quantity of Ce(NO3)3$6H2O is
0.075 g, and then Jsc decreases with the amount of Ce3þ increasing.
Based on Li's previous work [30], the increase of Jsc values in the low
concentration of rare-earth ions mainly comes from the conversion
luminescence of Ce3þ, which is beneficial for harvesting more
incident light. Whereas, when more Ce3þ are introduced into TiO2,
some crystal defects may be produced, especially in high concen-
tration of Ce3þ. Although appropriate amount of defects may lead to
some new physical properties, photoinduced electrons and holes
can also be captured by defects, which has an adverse impact on
photocurrent. In case of this problem, it is important to control the
homogeneity of Ce3þ to prevent local high concentration. Because
even in local area, high concentration will cause the formation of a
large amount of defects, which will seriously hinder the electron
transfer, increase recombination and weaken the performance of
Fig. 1. X-ray diffractogram of samples.
DSSCs as well. For solving this problem, the method of milling was
used to further break up TiO2 and distribute Ce3þ into crystal lattice
of TiO2 uniformly [31], which is beneficial to make sure the ho-
of Jsc values. On the other hand, electrons need to be transferred to
mogeneity of Ce3þ. In addition, for researching defects produced in
the bottom electrode through the mesoporous semiconductor
the TiO2 lattice, we can also introduce the method of photon sub-
network, so these mesopores may become the sites for the com-
system [32], a kind of harmonic approximation, to clarify this
bination of electrons and holes. From Table 1, the surface area
problem. This method can simplify the model of crystals' vacancies
values of Ce/TiO2 increase with the development of the amount of
and defects, which will help us reduce difficulties in process of the
Ce(NO3)3$6H2O, which is attributed to the presence of cerium oxide
research and find the principles easily. Under this condition, the
distributed on the TiO2 matrix and is beneficial to effectively
concentration of defects is assumed to be low and the interaction
enhance surface area of TiO2 as reported in previous studies [27].
between them is ignored. The presence in the small crystals with
Under simulated solar illumination (100 mW cm
2), current
finite number of point defects can cause large rearrangement of
density and voltage (J-V) characteristics for DSSCs were measured
photo spectrum. Meanwhile, photo spectrum will affect the equi-
and the performance parameters were summarized in Table 2.
librium defect concentration. The characters of defects and va-
Practically, this is obtained by measuring the photocurrent e
cancies can be observed very clearly because they are all
photovoltage characteristics of the cells and the photoelectric
independent from each other. After calculating the ideal amount of
conversion efficiency h is given by: h, where Jsc is the integral
photocurrent density (current obtained at short circuit conditions
divided by the area of the cell), FF is the fill factor and the Pin is the Table 1
luminous power of the incident light per unit area [28]. The short- Characteristic of powders.
circuit photocurrent ranges from 12.37 mA cm
2 to 13.87 mA cm
2,
Samples Crystallite size/nm Surface area/m2g
1 Ce/%
with values of Voc and FF being about 770 mV and 0.65, respectively.
P25 22.798 53 0.00
Meanwhile, A photovoltaic conversion efficiency of 7.00% was ob-
0.030 g-Ce/TiO2 28.604 77 0.11
tained, which was higher than that of the original TiO2 thin film. 0.040 g-Ce/TiO2 27.160 77 0.18
The increased Jsc values are ascribed to competitive reactions 0.050 g-Ce/TiO2 27.164 83 0.31
including: (1) the injection speed must be faster than the relaxation 0.075 g-Ce/TiO2 27.164 80 0.39
speed in the excited state of the sensitizer dye; (2) the transport 0.100 g-Ce/TiO2 27.171 86 0.51

Fig. 2. SEM micrographs of the powder.

 G. Xing et al. / Optical Materials 75 (2018) 102e108
Table 2
Photo-voltaic parameters from J-V curves and the amounts of dye adsorption based on different photoelectrode films.
Electrodes Voc/mV Jsc/mA cm
2
P25 770 12.60
0.030 g-Ce/TiO2 770 13.20
0.040 g-Ce/TiO2 770 13.21
0.050 g-Ce/TiO2 770 13.87
0.075 g-Ce/TiO2 770 12.70
0.100 g-Ce/TiO2 780 12.37
defects, the optimum quantity of Ce may be obtained, which can
further optimize the method of doping.
This conclusion explains why Jsc improves firstly and then de-
creases with the increase of Ce(NO3)3$6H2O amount in the DSSCs.
Specially, accompanied by doping with Ce, some defects will be
produced simultaneously.
On the other hand, we conclude that the increased Jsc values are
caused by the increased amount of dye. Analysis of the dye loaded
values, collected in Table 2, shows that each of Ce/TiO2 electrodes
has higher dye loading than that of pure P25 electrode. In this case,
it can be assumed that the electron transportation process has such
significant influence on the cell performance, which is attributed to
the development of the dye loading value which can promote the
photocurrent generation process. The Jsc values firstly increase as
the enhancement of the energy level of TiO2 doped by Ce3þ,
resulting in the improvement of the charge transport at the inter-
face of TiO2/dye. Overall, for performance of DSSCs, it is very crucial
to find the optimum concentration of Ce3þ and keep the homoge-
neity of Ce3þ.
The fill factor is another important parameter to determine the
performance of DSSCs. It depends on the series internal resistance
of the cells and presents approximately 66% (in Table 2). This range
of the FF values is ideal when compared with literature data [33].
Overall photo-electrical energy conversion efficiency (h) is the
most important parameter to characterize DSSCs. The h values for
cells are collected in Table 2. The efficiencies of 0.030 g-Ce/TiO2,
0.040 g-Ce/TiO2, 0.050 g-Ce/TiO2, 0.075 g-Ce/TiO2, 0.100 g-Ce/TiO2
cells are more eminent than that of pure P25 cell. The highest ef-
ficiency is observed for 0.050 g-Ce/TiO2 cell and the value is 7.00%,
which is higher than that of P25 cell (h ¼ 6.37%) by about 10.0%. This
obvious improvement is a consequence of forming an energy bar-
rier (proved by the impedance measurements described above),
which prevents the photoinjected electron back-transfer. Addi-
tionally, the participation of the Ce 4f orbitals in the TiO2 electron
structure formation increases the excited electron lifetime and
curtails the recombination effect [34]. Meanwhile, except for
doping, fabricating ideal size dispersion and various morphology
shape can also reduce recombination and improve the ability of
scattering, which is another crucial factor for improvement of
conversion efficiency of DSSCs [35] (see Fig. 3).
For further testing the stability of parameters with time, we
chose the sample: 0.050 g-Ce/TiO2 which corresponded with the
highest efficiency (7.00%) to detect its main parameters: Voc, Jsc, FF
and h again as time went on, at 0 h, 3 h, 6 h, 12 h and 24 h. In order
to more intuitive comparison, we decided to regard the value of
sample which just finished sensitizing (0 h) as standard one. The
values of remaining samples would be compared with the standard
one to obtain relative values. As is shown in Fig. 4 and Table 3, we
can notice that after 24 h, FF and Voc almost kept stable, maintaining
about 96.5% and 95% respectively, compared with those of the
standard one. However, Jsc has a dramatic decline with time, which
may be caused by the loss of dyes, as well as the conversion effi-
ciency (h). As a kind of organic material, dyes tend to decompose
into others without package. Thus, it is very difficult for the simple
105
FF/% h/% Amount of dye/Mol cm
2  10
7
65.64 6.37 1.164
65.96 6.70 1.288
65.53 6.66 1.412
65.59 7.00 1.908
66.03 6.46 1.536
67.87 6.55 1.486
DSSCs to maintain the ideal condition for a long time. But fortu-
nately, after complete package, the loss of dyes won't be obvious
anymore, which is very beneficial for DSSCs to keep high
performance.
According to Beer's law:
A ¼ KCL
In this equation, A is the absorbance at a specific absorption
wavelength of 515 nm; K is a constant: 1.41  10
4
dm3mol
1cm
1(at 515 nm); L is the width of cuvette, so C can be
calculated.
By measuring a series of standard solutions, the adsorption
quantity of N719 can be obtained. The adsorption amount of dye is
listed in Table 1.
The internal resistance of the DSSCs was studied via electro-
chemical impedance spectroscopy (EIS) in the frequency range of
0.1 Hze100 Hz. Fig. 6 shows the EIS results at forward bias of the
open-circuit voltage under light irradiation and the results are
represented as Nyquist plots. The internal resistances of the DSSCs
consist of one ohmic resistence (R0) and three arcs attributed to
electron S transfer at the electrochemical interface. The ohmic
resistance (R0) of the first semicircular arc on the left remains
nearly constant at the high-frequency range (>100 kHz), which is
primarily related to the sheet resistance of FTO [36]. For DSSCs, the
EIS has been used to describe a device structure with an appro-
priate model for the study of the electrochemical and photoelec-
tron chemical processes, especially for revealing the charge transfer
resistance at the interface of conducting layer/TiO2, Pt/electrolyte,
dye-coated TiO2/electrolyte and diffusion of the I3
/I
redox elec-
trolyte [37e39]. In the Nyquist plots (Fig. 6a), a well defined
semicircle attributed to electron transfer at the TiO2/dye/electrolyte
interface in the low-frequency region (100e1 Hz) dominates the
impedance of the DSSC, and is recognized as the characteristic
shape of recombination through the semiconductor [40]. In Fig. 5a,
the second semicircle which stands for resistance of TiO2/dye/
electrolyte decreases due to the electron transfer from I3
to the
HOMO level of dye and from the LUMO level of the dye to the
conductive band of TiO2 becoming faster. Table 2 presents that the
fitting results of the parameters of the cells with Ce/TiO2 or P25 as
photoanode are at about 0.77 V in the light. The resistance ele-
ments: Rs, R1 and R2 are summarized in Table 3. The Bode diagrams
are shown in Fig. 6(b), and the electron lifetimes can be obtained
via the conversion of the first peak value in these diagrams [41]. The
first peak represents frequency impedance at the interface of Pt/
electrolyte. The second peak stands for frequency impedance
existing at inner of TiO2, the interface of TiO2/dye/electrolyte and
the spread of I
in the electrolyte. Especially, due to the range of
frequency, the impedances of inner electrolyte have been covered
in the second arc, so only two arcs can be seen in the EIS plot.
According to the work by Liu et al. [36], without the consideration
of resistance of the inner electrolyte, the second frequency
impedance reflects two aspects: the electron transport resistance at
the inner of TiO2 photoanode which inverses correlation
106 G. Xing et al. / Optical Materials 75 (2018) 102e108

Fig. 3. (a) J-V curves of Ce doped photoelectrodes with different Ce(NO3)3$6H2O amounts; (b) the curves of efficiency changing with the amount of Ce(NO3)3$6H2O. ((a) is simple
figure).

Fig. 4. The relative remaining value of parameters with time.

Fig. 5. The UVevis of a DSSCs photoanode equipped with different samples.

Table 3
The values of resistances of RS, R1, R2 and frequency at the first peak in Bode plots of that of P25 cell, which denotes that the electron transport resis-
each DSSC sample.
tance cannot remarkably have an effect on the photoelectric
Samples Rs (U) R1 (U) R 2 ( U) tn (ms) properties of DSSC and the electrons must be recombined by redox
P25 18.57 4.56 23.84 23.37 electrolyte at the TiO2/dye/electrolyte interface. Electron lifetime
0.030 g-Ce/TiO2 0.030 g-Ce/TiO2 16.31 5.18 25.19 23.37 (tn) in the TiO2-based films can be determined from the maximum
0.040 g-Ce/TiO2 16.48 7.58 25.21 23.37 frequency of the low-frequency peak (fmax) value based on the
0.050 g-Ce/TiO2 17.57 7.44 25.99 28.32
equation: tn ¼ 1/(2pfmax). Bode phase plots show that the fmax
0.075 g-Ce/TiO2 15.64 10.63 26.21 23.37
0.100 g-Ce/TiO2 17.81 7.05 24.16 23.37 values vary with the amount of Ce doped in TiO2. The induced
charge recombination of the Ce-doped TiO2 cells can be attributed
to lower concentration impurities led by the dopant which acts as a
charge trapping site for the electronehole recombination and the
relationship with the photocurrent of DSSC; the electron transfer analysis of the Ce/TiO2 material structure can effectively reduce the
resistance at the dyed TiO2/electrolyte interface which inverses grain boundary of nanoparticle. These two aspects improve elec-
correlation relationship with electron recombination at this inter- tron lifetime and reduce the electron recombination. Moreover, Ce/
face. Obviously, as the analysis of J-V curves (Fig. 1), the photocur- TiO2 existence of mesopores restricts the electron transmission
rent of cell based on Ce/TiO2 as photoanode is much higher than path to a greater extent [42].
 G. Xing et al. / Optical Materials 75 (2018) 102e108
Fig. 6. Nyquist (a) and Bode (b) plots of DSSCs based on different Ce/TiO2 films.
4. Conclusions
In conclusion, we have successfully synthesized different
quantity Ce-doped TiO2 by hydrothermal method and their
photovoltaic properties in DSSC were investigated. As expected, an
overall 7.00% energy-conversion efficiency was obtained for DSSCs
on 0.050 g-Ce/TiO2, which was an improvement of 10.0% relative to
that of the original DSSC. A systematic investigation on the effect of
doping with Ce will provide valuable insight for the designing of
high-performance DSSCs. We are sure that if the most appropriate
amount of Ce can be doped into semiconductor materials and the
structure can be reasonably controlled, the efficiency will be further
improved. In addition, the price of the rare elements is rather
expensive compared with other parts of DSSCs during recent years,
which can be another factor that controls the application of DSSCs
with rare-earth elements [43]. Therefore, it is still very crucial to
search for other economical and efficient materials to improve
performance of DSSCs.
Foundation item
National Key Technologies R&D Program (21476162).
Acknowledgements
This work is supported by the key project of the National Science
Foundation of China for international academic exchanges (No.
21676187 and 21761132007).
References
[1] B. O'regan, M. Gra €tzel, A low-cost, high-efficiency solar cell based on dye-
sensitized colloidal TiO2 films, Nature 353 (1991) 737e740.
[2] M. Gra€tzel, Conversion of sunlight to electric power by nanocrystalline dye-
sensitized solar cells, J. Photochem. Photobiol. A 164 (2004) 3e14, 2004.
[3] D.P. Hagberg, J.-H. Yum, H. Lee, F. De Angelis, T. Marinado, K.M. Karlsson,
R. Humphry-Baker, L. Sun, A. Hagfeldt, M. Gr€ atzel, M.K. Nazeeruddin, Molec-
ular engineering of organic sensitizers for dye-sensitized solar cell
107
applications, J. Am. Chem. Soc. 130 (2008) 6259e6266.
[4] Y. Bai, Y. Cao, J. Zhang, M. Wang, R. Li, P. Wang, S. Zakeeruddin, M. Gr€ atzel,
High-performance dye-sensitized solar cells based on solvent-free electrolytes
produced from eutectic melts, Nat. Mater. 7 (2008) 626e630.
[5] S. Ito, T. Murakami, P. Comte, P. Liska, M. Gr€ atzel, M.K. Nazeeruddin,
M. Gra €tzel, Fabrication of thin film dye sensitized solar cells with solar to
electric power conversion efficiency over 10%, Thin Solid Films 516 (2008)
4613e4619.
[6] R.F. Zhao, L. Huan, P. Gu, R. Guo, M. Chen, G.W. Diao, Yb, Er-doped CeO2
nanotubes as an assistant layer for photoconversion-enhanced dye-sensitized
solar cells, J. Power Sources 331 (2016) 527e534.
[7] Z.S. Wang, M. Yanagida, K. Sayama, H. Sugihara, Electronic-insulating coating
of CaCO3 on TiO2 electrode in dye-sensitized solar cells: improvement of
electron lifetime and efficiency, Chem. Mater. 18 (2006) 2912e2916.
[8] H.S. Jung, J.K. Lee, M. Nastasi, S.W. Lee, J.Y. Kim, J.S. Park, S.K. Hong, H. Shin,
Preparation of nanoporous MgO-Coated TiO2 nanoparticles and their appli-
cation to the electrode of dye-sensitized solar cells, Langmuir 21 (2005)
10332e10335.
[9] P.P. Pal, J. Manam, Structural and photoluminescence studies of Eu3þ doped
zinc oxide nanorods prepared by precipitation method, J. Rare Earths 31
(2013) 37e43.
[10] M.A. Hern andez-Rodríguez, M.H. Imanieh, L.L. Martín, I.R. Martín, Experi-
mental enhancement of the photocurrent in a solar cell using upconversion
process in fluoroindate, Sol. Energy Mater. Sol. Cells 116 (2013) 171e175.
[11] J.Y. Yue, Y.M. Xiao, Y.P. Li, G.Y. Han, Y. Zhang, W.J. Hou, Enhanced photovoltaic
performances of the dye-sensitized solar cell by utilizing rare-earth modified
tin oxide compact layer, Org. Electron. 43 (2017) 121e129.
[12] N.N. Yao, J.Z. Huang, K. Fu, X.L. Deng, M. Ding, M.H. Shao, X.J. Xu, Enhanced
light harvesting of dye-sensitized solar cells with up/down conversion ma-
terials, Electrochim. Acta 154 (2015) 273e277.
[13] G. Lakshminarayana, S.O. Baki, A. Lira, I.V. Kityk, M.A. Mahdi, Structural,
thermal, and optical absorption studies of Er3þ, Tm3þ, and Pr3þ -doped bor-
otellurite glasses, J. Non-Cryst. Solids 459 (2017) 150e159.
[14] J.H. Wu, G.X. Xie, J.M. Lin, L. Zhang, M.L. Huang, Y.F. Huang, Enhancing pho-
toelectrical performance of dye-sensitized solar cell by doping with
europium-doped yttria rare-earth oxide, J. Power Sour. 195 (2010)
6937e6940.
[15] H. Yu, B. Xue, P. Liu, J. Qiu, W. Wen, S. Zhang, H. Zhao, High-performance
nanoporous TiO2/La2O3 hybrid photoanode for dye-sensitized solar cells, ACS
Appl. Mater. Interfaces 4 (2012) 1289e1294.
[16] H. Hafez, M. Saif, M.S.A. Abdel-Mottaleb, Down-converting lanthanide doped
TiO2 photoelectrodes for efficiency enhancement of dye-sensitized solar cells,
J. Power Sour. 196 (2011) 5792e5796.
[17] Y.J. Choi, Z. Seeley, A. Bandyopadhyay, S. Bose, S.A. Akbar, Aluminum-doped
TiO2 nano-powders for gas sensors, Sens. Actuators B Chem. 124 (2007)
111e117.
[18] K. Hatta, M. Higuchi, J. Takahashi, K. Kodaira, Floating zone growth and
characterization of aluminum-doped rutile single crystals, J. Cryst. Growth
108 G. Xing et al. / Optical Materials 75 (2018) 102e108
163 (1996) 279e284.
[19] I. Sayago, J. Gutierrez, L. Are s, J.I. Robla, M.C. Horrillo, J. Getino, J. Rino,
J.A. Agapito, The influence of the tin-oxide deposition technique on the
sensitivity to CO, Sens. Actuators B Chem. 25 (1995) 507e511.
[20] M. Saif, M.S.A. Abdel-Mottaleb, Titanium dioxide nanomaterial doped with
trivalent lanthanide ions of Tb, Eu and Sm: prepara tion, characterization and
potential applications, Inorg. Chim. Acta 360 (2007) 2863e2874.
[21] M. Asemi, M. Ghanaatshoar, Hydrothermal growth of one-dimensional Ce-
doped TiO2 nanostructures for solid-state DSSCs comprising Mg-doped
CuCrO2, J. Mater. Sci. 52 (2017) 489e503.
[22] Z.G. Zhang, G.X. Li, Z.J. Cui, K.Y. Zhang, Y.Q. Feng, S.X. Meng, Influence of
difference quantity La-doped TiO2 photoanodes on the performance of dye-
sensitized solar cells: a strategy for choosing appropriate doping quantity,
J. Solid State Chem. 237 (2016) 242e247.
[23] Z.G. Zhang, Z.J. Cui, K.Y. Zhang, Y.Q. Feng, S.X. Meng, Samarium ions doped
titania photoelectrodes for efficiency influence of dye-sensitized solar cells,
J. Electrochem. Soc. 163 (2016) 644e649.
[24] Y.H. Xu, H. Chen, Z. Zeng, B. Lei, Investigation on mechanism of photocatalytic
activity enhancement of nanometer cerium-doped titania, Appl. Surf. Sci. 252
(2006) 8565e8570.
[25] J. Zhang, Z. Zhao, X. Wang, T. Yu, J. Guan, Z. Yu, Z. Li, Z. Zou, Increasing the
oxygen vacancy density on the TiO2 surface by Ce-doping for dye-sensitized
solar cells, J. Phys. Chem. C 114 (2010) 18396e18400.
[26] A.K. Chandiran, F. Sauvage, L. Etgar, M. Gra €tzel, Ga3þ and Y3þ cationic sub-
stitution in mesoporous TiO2 photoanodes for photovoltaic applications,
J. Phys. Chem. C 115 (2011) 9232e9240.
[27] C.P. Sibu, S.R. Kumar, P. Mukundan, K.G. Warrier, Structural modifications and
associated properties of lanthanum oxide doped sol-gel nanosized titanium
oxide, Chem. Mater. 14 (2002) 2876e2881.
[28] S. Biswas, M.F. Hossain, T. Takahashi, Fabrication of Gra €tzel solar cell with
TiO2/CdS bilayered photoelectrode, Thin Solid Films 517 (2008) 1284e1288.
[29] J. Liu, H. Yang, W. Tan, X. Zhou, Y. Lin, Photovoltaic performance improvement
of dye-sensitized solar cells based on tantalum-doped TiO2 thin films, Elec-
trochim. Acta 56 (2010) 396e400.
[30] Q. Li, J. Lin, J. Wu, Z. Lan, Y. Wang, F. Peng, M. Huang, Enhancing photovoltaic
performance of dye-sensitized solar cell by rare-earth doped oxide of Lu2O3:
(Tm3þ, Yb3þ), Electrochim. Acta 56 (2010) 4980e4984.
[31] M. Atwater, T. Luckenbaugh, B. Hornbuckle, K. Darling, Advancing commercial
feasibility of intraparticle expansion for solid state metal foams by the surface
oxidation and room temperature ball milling of copper, J. Alloys Compd. 724
(2017) 258e266.
[32] A.E. Glauberman, V.A. Fedorin, Influence of the phonon subsystem on the
probability of formation of proper point defects in nonmetallic crystals, Theor.
Math. Phys. 17 (1973) 1018e1029.
[33] M. Zalas, M. Klein, The influence of titania electrode modification with
lanthanide ions containing thin layer on the performance of dye-sensitized
solar cells, Int. J. Photoenergy 6346 (2012) 1e8.
[34] H. Yang, K. Zhang, R. Shi, A. Tang, Sol-gel synthesis and photocatalytic activity
of CeO2/TiO2 nanocomposites, J. Am. Ceram. Soc. 90 (2007) 1370e1374.
[35] E. Gondek, Y. Djaoued, J. Robichaud, P. Karasin  ski, I.V. Kityk, A. Danel,
K.J. Plucinski, Influence of TiO2 nanoparticles on the photovoltaic efficiency of
the ITO/PEDOT: PSS/fluorine copolymers/polythiophene: TiO2/Al architecture,
J. Mater. Sci. Mater. Electron. 23 (2012) 2057e2064.
[36] Y. Liu, S. Wang, Z. Shan, X. Li, J. Tian, Y. Mei, H. Ma, K. Zhu, Anatase TiO2 hollow
spheres with small dimension fabricated via a simple preparation method for
dye-sensitized solar cells with an ionic liquid electrolyte, Electrochim. Acta 60
(2012) 422e427.
[37] J. Bisquert, Chemical capacitance of nanostructured semiconductors: its origin
and significance for nanocomposite solar cells, Phys. Chem. Chem. Phys. 5
(2003) 5360e5364.
[38] L. Han, N. Koide, Y. Chiba, T. Mitate, Modeling of an equivalent circuit for dye-
sensitized solar cells, Appl. Phys. Lett. 84 (2004) 2433e2435.
[39] X. Lv, X. Mou, J. Wu, D. Zhang, L. Zhang, F. Huang, F. Xu, S. Huang, Improved-
performance dye-sensitized solar cells using Nb-Doped TiO2 electrodes: effi-
cient electron injection and transfer, Adv. Funct. Mater. 20 (2010) 509e515.
[40] Y. Duan, N. Fu, Q. Zhang, Y. Fang, X. Zhou, Y. Lin, Influence of Sn source on the
performance of dye-sensitized solar cells based on Sn-doped TiO2 photo-
anodes: a strategy for choosing an appropriate doping source, Electrochim.
Acta 107 (2013) 473e480.
[41] J. Bisquert, Chemical capacitance of nanostructured semiconductors: its origin
and significance for nanocomposite solar cells, Phys. Chem. Chem. Phys. 5
(2003) 5360e5364.
[42] X. Peng, Y. Feng, S. Meng, B. Zhang, Preparation of hierarchical TiO2 films with
uniformly or gradually changed pore size for use as photoelectrodes in dye-
sensitized solar cells, Electrochim. Acta 115 (2014) 255e262.
[43] M.A. Müller, D. Schweizer, V. Seiler, Wealth effects of rare earth prices and
China's rare earth elements policy, J. Bus. Ethics 138 (2016) 627e648.