Materials Letters 95 (2013) 139–141

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Materials Letters
journal homepage: www.elsevier.com/locate/matlet

A strategy to achieve superior photocurrent by Cu-doped quantum dot

sensitized solar cells
Zongbo Huang, Xiaoping Zou n, Hongquan Zhou
Research Center for Sensor Technology, Beijing Key Laboratory for Sensor, Ministry-of-Education Key Laboratory for Modern Measurement and Control Technology,
School of Applied Sciences, Beijing information Science and Technology University, Jianxiangqiao Campus, Beijing 100101, PR China

a r t i c l e i n f o abstract

Article history: We employed successive ionic layer adsorption and reaction method to dope PbS by Cu2 þ for
Received 19 November 2012 fabricating quantum dot sensitized solar cells with a photoanode of the TiO2 mesoporous film
Accepted 26 December 2012 deposited by Cu-doped-PbS/CdS, Pt counter electrode and sulfide/polysulfide electrolyte. A power
Available online 3 January 2013
conversion efficiency (  2.01%) coupled with a remarkably superior short circuit current density (up to
Keywords: 21 mA cm  2) was achieved in the resulting Cu-doped-PbS/CdS quantum dot-sensitized solar cell.
Solar energy materials The related mechanism was discussed with Xray diffraction (XRD), scanning electron microscopy (SEM)
Optical materials and properties and transmission electron microscopy (TEM), respectively. The lattice distortion of Cu doped PbS is
Thin films found by XRD. The ability of PbS for capturing incident photons is noticeably enhanced by Cu doped.
Photocurrent
Crown Copyright & 2013 Published by Elsevier B.V. All rights reserved.

1. Introduction
PbS with Eg ¼0.41 eV [1], has attracted enormous interest in
sensitizers because they can extend the absorption band toward
the NIR part of the solar spectrum. Recently, the absorption band
toward the NIR and superior electron transfer efficiency in solar
cells was demonstrated with PbS QD/N719 dye cosensitizers [2].
Currently, the highest short circuit current density (Jsc, nearly
20 mA cm  2) [3] was observed in the PbS/CdS co-sensitized solar
cells based on photoanodes with hierarchical pore distribution.
Unfortunately, conduction band (CB) of PbS is located at lower
energy compared to that of TiO2 [4], and thus the electron
injection from PbS into TiO2 is suppressed. Therefore, optimizing
the structure of photoanode and effective surface treatment
methods are highly significant to further improve the perfor-
mance of PbS quantum dot-sensitized solar cells (QDSCs) [5].
Doping optically active transition metal ions, such as Mn, Mg, has
demonstrated many benefits [6,7]. For example, the doped system
may modify the electronic and photophysical properties of QDs.
In addition, it is also possible to tune the optical and electronic
properties of semiconductor nanocrystals by controlling the type
and concentration of dopant [8]. Very recently, Kamat, et al.
fabricated Mn-doped-CdS/CdSe quantum dot solar cells and
yielded the highest efficiency (5.42%) for the QDSCs with a
remarkable Jsc ( 20.7 mA cm  2) [9].
Here in this work, a combination of Cu-doped-PbS and CdS
QDs has been in situ deposited onto TiO2 mesoporous substrates
n
Corresponding author. Tel.: þ86 10 64884673 818; fax: þ86 10 64879486.
E-mail address: xpzou2005@gmail.com (X. Zou).
by the successive ionic layer adsorption and reaction (SILAR) [10].
The doped system has now succeeded in significantly optimizing
the structure of photoanode and improving the performance of
QDSCs. The Jsc (up to 21 mA cm  2) has been achieved when
utilizing Cu-doped-PbS semiconductor QDs as the sensitizer of
the QDSCs. Despite of low power conversion efficiency (2.01%
under 1sun of simulated irradiation AM1.5G, 100 mW cm  2)
because of the low open circuit voltage (Voc) as well as low fill
factor (FF), the Jsc here is much higher than other QDSCs with the
polysulfide electrolytes and Pt counter electrodes in the literature.
2. Experimental
Fabrication of Cu-doped-PbS/CdS electrode: In this experiment,
the Cu2 þ solution (100%, 20%, 10%, 5%, 2%) were considered as the
concentration for incorporating Cu dopants in the PbS films. In
brief, corresponding concentration of the CuCl2 were mixed with
Pb(NO3)2 (0.1 M) in an ethanol and deionized water (1:1) mixed
solution as cation source, respectively. Na2S (0.1 M) in methanol
was used as anion source. Each cycle of SILAR consisted of
successive immersion of the FTO glass electrode (thickness:
2.2 mm, Pilkington, 14 O/square) precoated with transparent
active TiO2 layers (10 mm-thickness) in the metalion cation and
sulfide anion solutions for 1 min, respectively, followed by rinsing
with corresponding solvent and drying. The co-adsorption of
Cu2 þ and Pb2 þ ions was achieved in the process, which in turn
facilitated incorporation of Cu2 þ in the PbS film. Subsequently,
the TiO2/Cu-doped-PbS films were alternately dipped into
Cd(NO3)2 (0.1 M) aqueous ethanol solution and Na2S (0.1 M)
methanol solutions for 5 min at 30 1C.

0167-577X/$ - see front matter Crown Copyright & 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.matlet.2012.12.095
140 Z. Huang et al. / Materials Letters 95 (2013) 139–141

Fig. 1. SEM images of the cross-section view (a) and top view (b) of the TiO2 mesoporous film deposited by Cu-doped-PbS/CdS. Inset in (b) is the corresponding EDS
spectrum. Low-magnification (c) and high-magnification (d) TEM images of the whole film.

0.025
TiO2 FTO PbS
M-1 9.61 0.41 0.18 0.72
M-5 13.7 0.47 0.26 1.39
0.020 M-10 18.2 0.39 0.23 1.66
Current density (A/cm2)

M-20 20.2 0.34 0.29 2.02

M-50 14.1 0.31 0.39 1.71
0.015

0.010

0.005

0.000
0.0 0.1 0.2 0.3 0.4 0.5
Voltage (V)

Fig. 3. The J  V characteristics of different working electrodes base on Cu doped

amount: 100%, 20%, 10%, 5%, 2%. Corresponding sample of the M-1, M-5, M-10,
Fig. 2. The XRD patterns of PbS/CdS and Cu-doped-PbS/CdS films.
M-20, M-50, respectively.

Preparation of QDSCs: All the working electrodes and Pt-coated
counter electrodes were finally assembled by using 60 mm thick
sealing materials (SX-1170-60, Solaronix SA). A mixed methanol
and deionized water solution (1:1) of Na2S (0.5 M), S (2 M) and
KCl (0.2 M) was used as the liquid electrolyte [11]. Solar cell
performance was evaluated under simulated AM1.5 irradiation
conditions.
3. Results and discussion
Fig. 1(a) shows scanning electron micrograph (SEM) of the
TiO2 film deposited by Cu-doped-PbS/CdS with a thickness of
12 mm. Fig. 1(b) suggests that the morphology of TiO2 electrode
deposited by Cu-doped-PbS/CdS. Furthermore, the corresponding
EDS spectrum of the Cu doped film is shown in inset of Fig. 1(b),
which demonstrated the Cu in the film. The deposition of
Cu-doped-PbS QDs on TiO2 nanoparticles was clearly evidenced
from the transmission electron micrograph (TEM) patterns shown
in Fig. 1(a,b). A clear morphology with a grain size of QDs
nanoparticles ranges from 4 to 6 nm remained on the surface of
TiO2 nanoparticles after the doped precursor solution immersion,
indicating that Cu-doped-PbS QDs are markedly adsorbed on the
surface of TiO2 nanoparticles.
The TiO2 films sensitized with Cu-doped-PbS quantum dots
were also demonstrated with X-ray diffraction patterns. For
comparison The TiO2 films sensitized with Cu-doped-PbS quan-
tum dots were also demonstrated with X-ray diffraction patterns.
For comparison, Fig. 2 shows the XRD pattern of TiO2/PbS and
TiO2/Cu-doped-PbS films at room temperature (RT) and 200 1C,
respectively. The typical X-ray diffraction pattern of SILAR depos-
ited PbS films with diffraction peaks at 2y values of approxi-
mately 31.781, 48.241 and 63.011, which are related with (111),
(220) and (222 ) crystalline planes of cubic phase (galena) of PbS,
respectively. The X-ray diffraction pattern of the Cu doped PbS
phase at room temperature was matched well with that of
 Z. Huang et al. / Materials Letters 95 (2013) 139–141
Fig. 4. (a) IPCE spectra of semiconductor films deposited on TiO2 mesoporous films: PbS/CdS (’), Cu-doped-PbS/CdS (%). (b) J  V characteristics of different working
electrodes: undoped PbS/CdS (’), Cu-doped-PbS/CdS (%). Inset in (a) diffusion reflectance absorbance spectra for corresponding electrodes. The working electrodes areas
were both at 0.09 cm2.
undoped PbS phase at room temperature and 200 1C. However, when
the TiO2/Cu-doped-PbS nanoporous film annealed at 200 1C, (2 2 0)
crystalline planes of cubic phase of PbS happen slightly shifting form
48.241 to 47.271. It is suggests that the Cu doped leads to the lattice
distortion of PbS, which exhibits the formation of Cu in the
as-prepared samples. Although only the most intense peak of the
Cu doped PbS was observed due to the relatively low quantity of Cu
dopant.
The J  V characteristics of different working electrodes base on
Cu doped amount were shown in Fig. 3. Obviously, there was a
great effect of the Cu doped amount on performance of the QDSCs.
When the Cu doped concentration decreased, there was a clearly
different performance from the Jsc, FF and Voc. The highest overall
power conversion efficiency (2.02%) was achieved with the most
optimized Cu doped amount M-20 (5%). The actual Cu concentra-
tion, applied on an Inductively Coupled Plasma Optical Emission
Spectroscopy (ICP-OES), was found to be 0.89% in the PbS film.
Higher Cu doped concentration might damage the performance.
For comparison, two different types of semiconductor photoa-
nodes were prepared: (i) 2 SILAR cycles of undoped PbS and 6 SILAR
cycles of CdS, (ii) 2 SILAR cycles of Cu-doped-PbS and 6 SILAR cycles
of CdS base on the most optimized Cu-doped concentration (5%). The
Incident photon-to-electron conversion efficiency (IPCE) spectra of
the doped and un-doped QDSCs at different incident light wave-
lengths were shown in Fig. 4(a). Compared to the PbS/CdS ones, much
improved overall photocurrent response, specifically in the longer
wavelength, was observed in the Cu-doped-PbS/CdS electrodes, with
a maximum IPCE close to 50%. The normalized absorption spectra of
these electrodes and corresponding photographs of the photoanodes
were shown in the inset of Fig. 4(a). Absorption around 1200 nm was
found in the absorption spectra of Cu-doped-PbS/CdS deposited film,
demonstrating enhanced ability for capturing incident photons.
The J V characteristics of these two QDSCs were presented in
Fig. 4(b). Surprisingly, Cu-doped-PbS/CdS films exhibited significant
increment close to 60% (from 13.7 mA cm  2 to 21.6 mA cm  2) in the
photocurrent, compared to the corresponding undoped films. Simi-
larly, the Voc was found to dramatically increase from 0.36 V to 0.44 V
after doping. Although the FF still remained very low level, the
increase in the Jsc and the Voc with Cu doped system leads to the
enhancement in the overall power conversion efficiency, suggesting a
higher efficiency of 2.01% based on the undoped one (1.05%).
The higher Jsc of the Cu-doped-PbS/CdS films is mainly attrib-
uted to the midgap states created by Cu doping, which traps and
screen electrons from charge recombination with holes in QD
layers. Indeed, the improved photovoltage in the QDSCs with
doped semiconductor films indicates that Cu-doping assists in
electron accumulation within the QD layers, thus shifting the
141
Fermi level to more negative potentials and increasing the CB of
PbS above that of TiO2. The structure of TiO2/Cu-doped-PbS/CdS is
considerably similar to that of TiO2/Mn-doped-CdS/CdSe [9],
suggesting the energy level of Cu dopant is higher than TiO2. This
cascade structure may also improve Jsc because the electronic
transmission path is optimized, which makes faster electronic
transfer and reduced charge recombination between the TiO2/ PbS
semiconductor interface. At the same time, the narrow band gap
of PbS is sustained, which benefits multi-exciton generation.
4. Conclusions
In summary, SILAR method was carried out to dope PbS by
Cu2 þ for fabricating QDSCs. A record setting value of short circuit
current density up to 21 mA cm  2 was observed in the resulting
cells with doped QDs, mainly associated with the improvement in
the electron and hole separation and charge transfer. The results
in this work demonstrate promising potentials in fabricating high
performance QDSCs.
Acknowledgment
This work was supported by Key Project (3131001) of Beijing
Natural Science Foundation, Key Project (91233201) of Natural
Science Foundation of China, Key Project (KZ201211232040) of
Beijing Education Committee Science & Technology Plan, State 863
Plan of MOST of China (2011AA050527), and State Key Laboratory of
ATMSP of Wuhan University of Technology (2012-KF-6).
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