Research Article

[Link]

High-Throughput Screening and Optimization of Binary Quantum

Dots Cosensitized Solar Cell
Ding Yuan,† Lina Xiao,† Jianheng Luo,‡ Yanhong Luo,‡ Qingbo Meng,‡ Bing-Wei Mao,†
and Dongping Zhan*,†
†
State Key Laboratory of Physical Chemistry of Solid Surfaces, Department of Chemistry, College of Chemistry and Chemical
Engineering, Xiamen University, Xiamen 361005, China
‡
Key Laboratory for Renewable Energy, Chinese Academy of Sciences, Beijing Key Laboratory for New Energy Materials and
Devices, Beijing National Laboratory for Condensed Matter Physics, Institute of Physics, Chinese Academy of Sciences, Beijing
100190, People’s Republic of China
*
S Supporting Information

ABSTRACT: Quantum dots (QDs) are considered as the

alternative of dye sensitizers for solar cells. However, interfacial
construction and evaluation of photocatalytic nanomaterials
still remains challenge through the conventional methodology
involving demo devices. We propose here a high-throughput
screening and optimizing method based on combinatorial
chemistry and scanning electrochemical microscopy (SECM).
A homogeneous TiO2 catalyst layer is coated on a FTO
substrate, which is then covered by a dark mask to expose the
photocatalyst array. On each photocatalyst spot, different
successive ionic layer adsorption and reaction (SILAR)
processes are performed by a programmed solution dispenser
to load the binary PbxCd1−xS QDs sensitizers. An optical fiber
is employed as the scanning tip of SECM, and the photocatalytic current is recorded during the imaging experiment, through
which the optimized technical parameters are figured out. To verify the validity of the combinatorial SECM imaging results, the
controlled trials are performed with the corresponding photovoltaic demo devices. The harmonious accordance proved that the
methodology based on combinatorial chemistry and SECM is valuable for the interfacial construction, high-throughput
screening, and optimization of QDSSCs. Furthermore, the PbxCd1−xS/CdS QDs cosensitized solar cell optimized by SECM
achieves a short circuit current density of 24.47 mA/cm2, an open circuit potential of 421 mV, a fill factor of 0.52, and a
photovoltaic conversion efficiency of 5.33%.
KEYWORDS: scanning electrochemical microscopy, quantum dots sensitized solar cell, high-throughput screening, SECM, QDSSC

1. INTRODUCTION QDSSCs.17−19 Sometimes it is not the photoelectrode, but the

Taking the advantages of tunable absorption spectrum from counter electrode that limits the photovoltaic conversion
visible to near IR region, low cost, and easy preparation, QDs efficiency. To obtain the intrinsic properties of photocatalysts,
have been considered as the alternative of dye sensitizers in the it is essential to ensure that the counter electrode has sufficient
TiO2 nanocatalyst-based solar cell system.1−6 Although the power capacity.20,21 Because of the lack of theoretical guidance,
photovoltaic conversion efficiency of QDSSCs was improved huge workload has to be tried to optimize the technical formula
rapidly in the past few years, it is still lower than that of the dye of QDSSCs with the demo photovoltaic devices.
sensitized solar cells.7−13 Interfacial design and construction is Combinatorial chemistry is a subfield of chemistry that aims
crucial to improve the performance of QDSSCs.6 For example, to combine a small number of chemical reagents, in all
the chemical stability of QDs and energy match between the combinations defined by a given reaction scheme, to yield a
QDs sensitizer and TiO2 nanocatalyst should be fully large amount of well-defined products in a form that is easy to
considered during the preparations of QDSSCs.14,15 On the screen for properties of interests.22,23 Traced back to the 1960s,
one hand, the band gap of QDs is tunable in principle by both it is proposed initially as a chemical synthetic method. With the
geometric size and chemical components. However, it is loaded development of microfabrication techniques, the reaction
opportunistically in experiments by either the successive ionic
layer adsorption and reaction (SILAR) processes or the Received: May 21, 2016
chemical bath methods.16 On the other hand, the counter Accepted: June 29, 2016
electrode plays an important role in the performance of

© XXXX American Chemical Society A DOI: 10.1021/acsami.6b06029

ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

systems of combinatorial chemistry are miniaturized and built procedures, including chemical bath deposition of CdS layer and then
on chip.24,25 Positioning systems are therefore integrated into SILAR deposition of ZnS passivation layer, were the same as reported
various analytical instruments to identify what happens in each before.48 The electrolyte used in QDSSCs was prepared by dissolving
reaction unit.26−29 Because of its high-throughput screening 1.0 mol/L Na2S and 1.0 mol/L S in deionized water under the
protection of pure nitrogen atmosphere. A Cu/Cu2S foil was adopted
and optimizing capabilities, combinatorial chemistry is applied as the cathode.18
rapidly into analytical, material, biological, and pharmic Preparations of the SECM Substrate. The sintered FTO glass
science.23,30−32 In material science, it is employed not only to slides with dual layer TiO2 catalyst were prepared as described above.
synthesize new materials, but also to screen the best one with An array of holes was fabricated by penetrating a hot needle (diameter:
expected properties.23,32 500 μm) quickly through a thin but nontransparent black PET film
Scanning electrochemical microscopy (SECM) is a special (thickness: 100 μm) with a micromanipulator. The prepared TiO2
scanning probe technique with the capability to image the local photoelectrode was encapsulated by the hole-array PET mask. Thus,
chemical reactivity of substrates.33,34 In 2005, Dr. Bard only the TiO2 arrays are exposed, and the other parts are isolated from
introduced the methodology of combinatorial chemistry into both light and electrolyte. A program-controlled microdispenser (CHI
1550, CHI Instruments Co.) was employed to perform the micro-
SECM.35−37 They synthesized metal alloy electrocatalyst array SILAR processes: (1) the cations’ precursor solution (0.01 M
on glassy carbon substrate and imaged their catalytic properties Pb(NO3)2 + x M CdCl2) was dropped onto the TiO2 spots; (2)
on the oxygen electroreduction in proton exchange membrane after 30 s of standing, the spots are rinsed by deionized water; (3) the
fuel cells. To study the photovoltaic conversion system, an array equimolar Na2S solution was dropped onto the TiO2 spots; and (4)
of photoelectrocatalyst spots is prepared with a combinatorial after 30 s of standing, the TiO2 spots are rinsed by deionized water.
formula on the substrate (e.g., ITO, FTO, Ti slide, etc.). The Steps 1−4 compose one SILAR circle. Beause the micro-SILAR
photocatalytic current feedback is collected by SECM when the procedures were performed automatically by a programed micro-
substrate is illuminated either by a scanning optic fiber or by a dispenser, the volumes of dispensed microdrops should equal be to
macroscale light source, from which the photocatalytic each other. Thus, the amount of the precursor can be controlled
strictly during the micro-SILAR procedures. To improve the
properties can be judged visually.38−40 By using a redox photovoltaic performance, usually a few SILAR circles are needed to
mediator, the interfacial charge transfer kinetics can also be ensure both the size and the loading amount of the QDs sensitizer.
figured out through the SECM feedback mode.41−46 The Finally, the chemical bath for the loading of CdS QDs and the SILAR
advantage of the optic fiber scanning mode lies in that the processes for the loading of ZnS passivation layer were performed as
capacity of counter electrode is in no need of being considered reported before.48
because it is usually much larger in size than the single spots of Measurements and Characterizations. A CHI 920c work-
photocatalyst. station (CH instrument Co.) was employed to perform the SECM
To improve the signal/noise ratio, we have proposed a light imaging experiments.47 An optical fiber (diameter: 200 μm) connected
mask method to isolate the substrate area other than the with a xenon light source was adopted as the scanning probe to
stimulate the photoelectrocatalytic reaction, and the current flowing
photocatalyst array.47 In this article, we use this method for the through the substrate was collected for SECM imaging. The substrate
high-throughput screening of the binary QDs, PbxCd1−xS, was well leveled by a screw microcalliper. A force sensor and a video
cosensitized solar cell. The technical parameters are optimized monitor were employed to determine the zero-point where the tip
rapidly and also verified by the photovoltaic demo devices. The touched right with the isolate film. The optic fiber was withdrawn to a
PbxCd1−xS QDs are actually a solid-state solution, which has a tip−substrate distance of 100 μm. The scanning rate is 300 μm/s
better stability than PbS QDs and a better energy matching to during imaging. All of these experimental operations are controlled
CdS QDs/TiO2 system. The performance of PbxCd1−xS/CdS carefully to ensure the comparability of the imaging results. In the
QDs cosensitized solar cell was promoted with a short circuit SECM experiments, a platinum (Pt) electrode was employed as both
current density of 24.47 mA/cm2, an open circuit potential of the counter and the reference electrode. The other auxiliary
electrochemical experiments were performed on a model 263A
421 mV, a fill factor of 0.52, and a photovoltaic conversion
potentiostat (Princeton Applied Research Co.). A homemade Solar
efficiency of 5.33%. Cell System with a standard solar simulator (Oriel 91192, intensity: 1.5
AM) was employed in the measurements with demo QDSSC devices.
2. EXPERIMENTAL SECTION Transmission electron microscopy (TEM, JEM-2100, JEOL Co.),
Chemicals and Materials. Sodium sulfide (Na2S), sulfur (S), energy dispersive X-ray spectroscopy (EDS, S-4800, Hitachi Co.), X-
ammonium chloride (NH4Cl), hydrochloric acid (HCl), lead nitrate ray diffraction spectra (XRD, X’pert Pro, Panalytical Co.), and X-ray
(Pb(NO3)2), hydrate cadmium chloride (CdCl2·2H2O), hydrate zinc photoelectron spectroscopy (XPS, Quantum 2000, PHI Quantera Co.)
acetate (Zn(Ac)·2H2O), and hydrate sodium sulfide (Na2S·9H2O) were employed to characterize the morphology and components of the
were of analytical grade and provided by Sinopharm Co., China. FTO quantum dots, which were synthesized and loaded on TiO 2
conductive glass slides (thickness 2.2 mm, 14 Ω/cm2) were purchased nanoparticles by SILAR processes.
from Jing Ge Solar Tech Co., Wuhan. All aqueous solutions were
prepared with deionized water (18.2 MΩ cm, Milli-Q, Millipore Co.). 3. RESULTS AND DISCUSSION
Preparations of the Demo QDSSCs. A dual-layer TiO2 catalyst
was deposited on a FTO glass slide by doctor blading technique: the SILAR is the best empirical approach to control the sizes and
inner layer was 10-μm thick with 15 nm-diameter TiO2 nanoparticles loading amount of QDs sensitizer on TiO2 nanocatalyst. Figure
and the outer layer was 15-μm thick with 300 nm-diameter TiO2 1 shows the HRTEM images of PbS and PbxCd1−xS QDs
nanoparticles (see Figure S1). The raw TiO2 photoelectrode was deposited on the TiO2 photoelectrode. It is observed that the
sintered at 450 °C for 30 min in a muffle furnace. After cooling to QDs formed on the surface of TiO2 nanoparticles are
ambient temperature, it was immersed in an aqueous solution homogeneous with an average size of 5 nm. Although the
containing a specified molar ratio of Pb(NO3)2 over CdCl2 and then
in a Na2S aqueous solution for 30 s, alternately, to finish one SILAR sizes of different QDs are very close to each other, it should be
circle. After each immersion, the TiO2 photoelectrode was washed noted that the lattice constant decreases from 0.342 to 0.322
thoroughly with deionized water. During the SILAR procedure, the nm, which indicates the formation of PbxCd1−xS QDs.49,50
total molar ratio of cations (Pb2+ and Cd2+) over inion (S2−) was 1:1 Because the solubility products (Ksp) of PbS and CdS are 8.0 ×
to form PbxCd1−xS QDs on TiO2 nanoparticles. The subsequent 10−28 and 8.0 × 10−27, respectively,51 Pb2+ and Cd2+ can
B DOI: 10.1021/acsami.6b06029
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

results (see Figure S2) show that the characteristic peaks (2θ:
31°) and the half-peak width of PbS remain the same if CdS
QDs were deposited separately after the deposition of PbS.
However, when Pb2+ and Cd2+ are coprecipitated by S2−, the
XRD peak mentioned above shifts and the half-peak width
becomes wider (see Figure S2). A similar phenomenon was
observed for the characteristic peaks at 2θ of 44°. The
individual peak and the enhanced intensities at 2θ of both 31°
and 44° indicate the crystalline structure should be
homogeneous. The results show that both Cd2+ and Pb2+
occupy the lattice sites of the PbxCd1−xS solid-solution QDs.53
The schematic diagram of the SECM imaging is depicted in
Figure 2b. Because of the light mask, all of the area is isolated
from the electrolyte and illumination light except the
PbxCd1−xS/CdS QDs cosensitized TiO2 nanocatalyst array.
The background caused by the electric double-layer charging
current and the photocatalytic current of FTO itself at the
nonspot area are therefore eliminated. Thus, the signal/ratio is
pretty high as reported by us previously.47 When the optical
fiber is scanning above the spots, the PbxCd1−xS/CdS QDs
cosensitized TiO2 nanocatalyst will be illuminated and give out
the photocurrent feedback. From the SECM images shown in
Figure 1. HRTEM images of PbS QDs (a and b) and TiO2/PbxCd1−xS
QDs (c and d) loaded on the TiO2 nanoparticles with 5 SILAR cycles. Figure 2c, it is observed that, because of the light mask, the
The precursor solution contains 0.01 M Pb(NO3)2 and 0.3 M CdCl2. background of the photocurrent is almost zero, and the signal/
noise ratio is pretty high as reported previously.47 The first spot
coprecipitate in the presence of S2−, and, in principle, the from left giving a photocurrent of 6.5 μA is actually the PbS/
content of Pb2+ should be higher than that of Cd2+ (see Tables CdS QDs cosensitized TiO2 nanocatalyst. When the precursor
S1−S3). Moreover, due to the lattice size of PbS crystal (5.91 solution contains 0.20−0.50 M CdS, the photocurrent can be
Å) being very close to that of CdS crystal (5.82 Å), a solid increased doubly as an average of 12.5 μA. The results show
solution will be formed during the SILAR processes.52 XRD that the binary PbxCd1−xS QDs is a better sensitizer than PbS

Figure 2. (a) Schematic diagram of the TiO2/PbxCd1−xS/CdS/ZnS photoelectrode; (b) schematic diagram of the SECM imaging mode with an
optical fiber as the scanning tip; and (c) SECM images of local photocurrent of the TiO2/PbxCd1−xS/CdS/ZnS catalyst array. Substrate potential, 0.2
V vs Pt electrode; illumination intensity, 50 mW/cm2; tip−substrate distance, 100 μm; and scanning rate, 300 μm/s; the electrolyte is an aqueous
solution with 0.1 M Na2S and 0.1 M S.

C DOI: 10.1021/acsami.6b06029
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

Figure 3. SECM images of the TiO2/PbxCd1−xS/CdS/ZnS nanocatalyst array prepared with different SILAR circles at fixed Cd2+ concentration in
the precursor solutions: (a) 0.2 M Cd2+, (b) 0.3 M Cd2+, (c) 0.4 M Cd2+. Substrate potential, 0.2 V vs Pt electrode; illumination intensity, 50 mW/
cm2; tip−substrate distance, 100 μm; and scanning rate, 300 μm/s; the electrolyte is an aqueous solution with 0.1 M Na2S and 0.1 M S.

Figure 4. SECM images of the TiO2/PbxCd1−xS/CdS/ZnS nanocatalyst array prepared with different Cd2+ concentrations in the precursor solutions
at fixed SILAR circles: (a) 3 cycles; (b) 5 cycles; (c) 7 cycles. Substrate potential, 0.2 V vs Pt electrode; illumination intensity, 50 mW/cm2; tip−
substrate distance, 100 μm; and scanning rate, 300 μm/s; the electrolyte is an aqueous solution with 0.1 M Na2S and 0.1 M S.

QDs, and the SECM imaging mode is proved effective in the concentration of Cd2+ in the precursor solutions. The
screening of the QDs sensitizer for QDSSCs. photocurrents of the spots with 5 SILAR circles are higher
Combinatorial chemistry methodology is employed now to than those with 3 and 7 SILAR circles. Thus, the combinatorial
scheme and optimize the technical processes for the interfacial screening is helpful to optimize the technical parameters: 0.3 M
construction of the QDs sensitized TiO2 nanocatalyst.47 Figures Cd2+ concentration in the precursor solution and 5 SILAR
3 and 4 show the SECM images of the TiO2 nanocatalyst spots circles.
with different precursor solutions and different SILAR circles. To verify the results of the combinatorial screening by SECM
As observed in Figure 3, at a fixed precursor solution, the imaging mode, the controlled trials are performed with the
photocurrent increases first and then decreases with the SILAR corresponding photovoltaic demo devices. The photovoltaic
circles. With 0.3 M Cd2+ in the precursor solution, the conversion efficiencies of the demo devices are shown in Figure
photocurrent is improved obviously with 4−7 SILAR circles. As 5, which is in harmonious accordance with the combinatorial
observed in Figure 4, at the fixed SILAR circles, the SECM imaging results shown in Figure 4. At the fixed
photocurrent increases first and then decreases with the precursor solution, the demo devices with 5 SILAR circles
D DOI: 10.1021/acsami.6b06029
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

Figure 5. Photovoltaic conversion efficiencies of the binary PbxCd1−xS/CdS/ZnS QDSSCs demo devices with different precursor solutions and
different SILAR circles.

Figure 6. J−V curves of (a) TiO2/PbS/CdS/ZnS and (b) TiO2/PbxCd1−xS/CdS/ZnS QDSSCs demo devices with different SILAR cycles. The
counter electrode is a Cu/Cu2S electrode, and the aqueous electrolyte contains 1 M Na2S and 1 M S.

Figure 7. (a) Absorbance spectra of TiO2/PbS, TiO2/CdS, and TiO2/PbxCd1−xS nanocatalysts. The inset shows the estimation of Eg values of the
QDs. (b) Schematic diagram of electron transfer at the boundaries between the QDs cosensitizer, CdS QDs, and TiO2 nanocatalyst.

present the best photovoltaic conversion efficiency. At the fixed Further experiments are performed (Figure 6) to compare
SILAR circles, the photovoltaic conversion efficiency increases the device performance sensitized by PbS/CdS QDs (i.e., 0 M
first and then decreases with the increased Cd2+ concentration Cd2+ in the precursor solution) and PbxCd1−xS/CdS QDs (0.3
in the precursor solution. With 0.3 M Cd2+ precursor solution, M Cd2+ in the precursor solution) with 3, 5, and 7 SILAR
circles. It is observed that the binary PbxCd1−xS QDs can
the demo devices give the best performance. Because it is a
promote the device performance more dramatically than PbS
huge workload for the optimization of multicomponent QDs QDs. The short circuit current density is improved from 14.66
sensitized solar cells with demo devices, the combinatorial mA/cm2 for PbS/CdS QDs to 24.47 mA/cm2 for PbxCd1−xS/
SECM screening provides a facile method with high CdS QDs, and the photovoltaic conversion efficiency is
throughput. improved from 2.66% to 5.33% (see Table S4). Figure 7 may
E DOI: 10.1021/acsami.6b06029
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

be helpful to understand why PbxCd1−xS QDs are better than

PbS QDs. This is actually caused by the energy matching
■ AUTHOR INFORMATION
Corresponding Author
between the cosensitizers, CdS QDs, and TiO2 nanocatalyst.
Comparing with the previous report in which PbxCd1−xS QDs *E-mail: dpzhan@[Link].
is also adopted as the cosencitizer, the energy band of the Notes
binary QDs is much closer to that of CdS QDs because the Cd The authors declare no competing financial interest.

■
content is found much higher than Pb content.51 In our
experiment, the Cd content is found much lower than Pb ACKNOWLEDGMENTS
content (see Table S1). As shown in Figure 7, the property of
The financial support of the National Basic Research Program
our binary PbxCd1−xS QDs is closer to that of the PbS QDs.
of China (2012CB932902) and the National Natural Science
Nevertheless, the performances of QDSSCs cosensitized by
Foundation of China (91323303, 21327002, 21573054 and
PbxCd1−xS QDs are better than those cosensitized by PbS QDs.
21321062) is appreciated.

■
Further discussion should be addressed on the empirical
SILAR processes in the interfacial construction of the
photoelectrodes. The size of the QDs sensitizer as well as the REFERENCES
loading amount will increase with the increasing SILAR circles, (1) Kamat, P. V. Quantum Dot Solar Cells. Semiconductor
which determines their energy band gap and the enhancement Nanocrystals as Light Harvesters. J. Phys. Chem. C 2008, 112,
of photovoltaic conversion. There should be an optimal size 18737−18753.
that matches well with both the CdS QDs and the TiO2 (2) Rühle, S.; Shalom, M.; Zaban, A. Quantum Dot Sensitized Solar
photocatalyst. On the other hand, if the loading amount is too Cells. ChemPhysChem 2010, 11, 2290−2304.
(3) Sambur, J. B.; Novet, T.; Parkinson, B. Multiple Exciton
small, the charge transfer efficiency is limited by the insufficient Collection in a Sensitized Photovoltaic System. Science 2010, 330, 63−
amount of photogenerated charges; if the loading amount is too 66.
high, the mass transfer should be blocked by the loaded QDs. (4) Kamat, P. V. Boosting the Efficiency of Quantum Dot Sensitized
That is why the photocurrent increases first and then decreases Solar Cells Through Modulation of Interfacial Charge Transfer. Acc.
with the increased SILAR circles. The size as well as the loading Chem. Res. 2012, 45, 1906−1915.
amount of the QDs cosensitizer are the key issues to the (5) Albero, J.; Clifford, J. N.; Palomares, E. Quantum Dot Based
performance of QDSSCs. Future study should be emphasized Molecular Solar Cells. Coord. Chem. Rev. 2014, 263, 53−64.
on the theoretical predictions on the size and loading amount, (6) Yang, J.; Choi, M. K.; Kim, D. H.; Hyeon, T. Designed Assembly
and how to realize it in the interfacial construction of the and Integration of Colloidal Nanocrystals for Device Applications. Adv.
photoelectrode. Recently, the QDs cosensitizers are becoming Mater. 2016, 28, 1176−1207.
(7) Lan, X.; Voznyy, O.; Kiani, A.; García de Arquer, F. P.; Abbas, A.
more multicomponent.9 Therefore, the proposed high- S.; Kim, G. H.; Liu, M.; Yang, Z.; Walters, G.; Xu, J. Passivation Using
throughput screening method based on SECM imaging mode Molecular Halides Increases Quantum Dot Solar Cell Performance.
and combinatorial chemistry methodology has a prospective Adv. Mater. 2016, 28, 299−304.
potential in optimizing the technical protocols of QDSSCs. (8) Jiao, S.; Wang, J.; Shen, Q.; Li, Y.; Zhong, X. Surface Engineering
of PbS Quantum Dot Sensitized Solar Cells with a Conversion
4. CONCLUSIONS Efficiency Exceeding 7%. J. Mater. Chem. A 2016, 4, 7214−7221.
(9) Du, J.; Du, Z.; Hu, J. S.; Pan, Z.; Shen, Q.; Sun, J.; Long, D.;
Combining SECM imaging mode with combinatorial chemistry Dong, H.; Sun, L.; Zhong, X. Zn−Cu−In−Se Quantum Dot Solar
methodology, we proposed a high-throughput and high signal/ Cells with a Certified Power Conversion Efficiency of 11.6%. J. Am.
noise ratio screening method for the optimization of the binary Chem. Soc. 2016, 138, 4201−4209.
QDs cosensitized solar cells. Meanwhile, we designed an (10) Ren, Z.; Wang, J.; Pan, Z.; Zhao, K.; Zhang, H.; Li, Y.; Zhao, Y.;
intermediate layer, the PbxCd1−xS QDs, as the cosensitizer Mora Sero, I.; Bisquert, J.; Zhong, X. Amorphous TiO2 Buffer Layer
between the CdS sensitizer and TiO2 nanocatalyst. On the basis Boosts Efficiency of Quantum Dot Sensitized Solar Cells to Over 9%.
of the optimized technical protocols screened by SECM, the Chem. Mater. 2015, 27, 8398−8405.
PbxCd1−xS/CdS QDs cosensitized TiO2 soalr cell achieves a (11) Kim, G. H.; García de Arquer, F. P.; Yoon, Y. J.; Lan, X.; Liu,
short circuit current density of 24.47 mA/cm2, an open circuit M.; Voznyy, O.; Yang, Z.; Fan, F.; Ip, A. H.; Kanjanaboos, P. High-
potential of 421 mV, a fill factor of 0.52, and a photovoltaic Efficiency Colloidal Quantum Dot Photovoltaics via Robust Self-
Assembled Monolayers. Nano Lett. 2015, 15, 7691−7696.
conversion efficiency of 5.33%. We consider that the size and (12) Mathew, S.; Yella, A.; Gao, P.; Humphry-Baker, R.; Curchod, B.
the loading amount of QDs cosensitizer are the key issues in F.; Ashari-Astani, N.; Tavernelli, I.; Rothlisberger, U.; Nazeeruddin, M.
the interfacial construction of the photoelectrode. Because the K.; Grätzel, M. Dye-Sensitized Solar Cells with 13% Efficiency
QDs cosensitizers are becoming more multicomponent, the Achieved Through the Molecular Engineering of Porphyrin Sensi-
proposed combinatorial SECM screening method is a good tizers. Nat. Chem. 2014, 6, 242−247.
choice due to its high throughput, high efficiency, and high (13) Li, Y.; Zhu, J.; Chu, H.; Wei, J.; Liu, F.; Lv, M.; Tang, J.; Zhang,
signal/noise ratio. B.; Yao, J.; Huo, Z.; Hu, L.; Dai, S. BiVO4 Semiconductor Sensitized

■
Solar Cells. Sci. China: Chem. 2015, 58, 1489−1493.
ASSOCIATED CONTENT (14) Mu, L.; Liu, C.; Jia, J.; Zhou, X.; Lin, Y. Dual Post-treatment: a
Strategy Towards High Efficiency Quantum Dot Sensitized Solar
* Supporting Information
S Cells. J. Mater. Chem. A 2013, 1, 8353−8357.
The Supporting Information is available free of charge on the (15) Kim, J.; Choi, H.; Nahm, C.; Kim, C.; Kim, J. I.; Lee, W.; Kang,
ACS Publications website at DOI: 10.1021/acsami.6b06029. S.; Lee, B.; Hwang, T.; Park, H. H. Graded Bandgap Structure for
PbS/CdS/ZnS Quantum-Dot-Sensitized Solar Cells with a PbxCd1−xS
SEM images and XRD spectra of the TiO2 nanocatalyst Interlayer. Appl. Phys. Lett. 2013, 102, 183901−183904.
and photoelectrodes, EDS data of the PbxCd1−xS QDs, (16) Hossain, M. A.; Koh, Z. Y.; Wang, Q. PbS/CdS-Sensitized
and detailed data about the performance of demo devices Mesoscopic SnO2 Solar Cells for Enhanced Infrared Light Harnessing.
(PDF) Phys. Chem. Chem. Phys. 2012, 14, 7367−7374.

F DOI: 10.1021/acsami.6b06029
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX
ACS Applied Materials & Interfaces Research Article

(17) Kim, H. J.; Lee, H. D.; Rao, S. S.; Reddy, A. E.; Kim, S. K.; Microscopy. M-Co (M: Pd, Ag, Au). J. Am. Chem. Soc. 2005, 127,
Thulasi-Varma, C. V. Well-dispersed NiS Nanoparticles Grown on a 357−365.
Functionalized CoS Nanosphere Surface as a High Performance (37) Fernández, J. L.; White, J. M.; Sun, Y.; Tang, W.; Henkelman,
Counter Electrode for Quantum Dot-Sensitized Solar Cells. RSC Adv. G.; Bard, A. J. Characterization and Theory of Electrocatalysts Based
2016, 6, 29003−29019. on Scanning Electrochemical Microscopy Screening Methods.
(18) Xiao, L.; Yuan, D.; Li, P.; Huang, L.; Mao, B. W.; Zhan, D. Langmuir 2006, 22, 10426−10431.
Copper/Cuprous Sulfide Electrode: Preparation and Performance. Sci. (38) Ye, H.; Lee, J.; Jang, J. S.; Bard, A. J. Rapid Screening of BiVO4-
China: Chem. 2015, 58, 1039−1043. Based Photocatalysts by Scanning Electrochemical Microscopy
(19) Wang, L.; Zhang, K.; Cheng, F.; Chen, J. Polypyrrole-Cobalt- (SECM) and Studies of Their Photoelectrochemical Properties. J.
Carbon Nanocomposites as Efficient Counter Electrode Materials for Phys. Chem. C 2010, 114, 13322−13328.
Dye-Sensitized Solar Cells. Sci. China: Chem. 2014, 57, 1559−1563. (39) Park, H. S.; Kweon, K. E.; Ye, H.; Paek, E.; Hwang, G. S.; Bard,
(20) Gopi, C. V.; Venkata-Haritha, M.; Lee, Y.-S.; Kim, H. J. ZnO A. J. Factors in the Metal Doping of BiVO4 for Improved
Nanorods Decorated with Metal Sulfides as Stable and Efficient Photoelectrocatalytic Activity as Studied by Scanning Electrochemical
Counter-Electrode Materials for High-Efficiency Quantum Dot- Microscopy and First-Principles Density-Functional Calculation. J.
Sensitized Solar Cells. J. Mater. Chem. A 2016, 4, 8161−8171. Phys. Chem. C 2011, 115, 17870−17879.
(21) Yu, X. C.; Zhu, J.; Liu, F.; Wei, J. F.; Hu, L. H.; Dai, S. Y. Metal (40) Berglund, S. P.; Lee, H. C.; Nunez, P. D.; Bard, A. J.; Mullins, C.
Chalcogenide Complex-Mediated Fabrication of Cu2S Film as B. Screening of Transition and Post-Transition Metals to Incorporate
Counter Electrode in Quantum Dot Sensitized Solar Cells. Sci. into Copper Oxide and Copper Bismuth Oxide for Photoelec-
China: Chem. 2013, 56, 977−981. trochemical Hydrogen Evolution. Phys. Chem. Chem. Phys. 2013, 15,
(22) Czarnik, A. W. Peer Reviewed: Combinatorial Chemistry. Anal. 4554−4565.
Chem. 1998, 70, 378A−386A. (41) Kylberg, W.; Wain, A. J.; Castro, F. A. Screening of Photoactive
(23) Woodhouse, M.; Parkinson, B. A. Combinatorial Approaches for Dyes on TiO2 Surfaces Using Scanning Electrochemical Microscopy. J.
the Identification and Optimization of Oxide Semiconductors for Phys. Chem. C 2012, 116, 17384−17392.
Efficient Solar Photoelectrolysis. Chem. Soc. Rev. 2009, 38, 197−210. (42) Mengesha Tefashe, U.; Nonomura, K.; Vlachopoulos, N.;
(24) Claus, P.; Hönicke, D.; Zech, T. Miniaturization of Screening Hagfeldt, A.; Wittstock, G. Effect of Cation on Dye Regeneration
Devices for the Combinatorial Development of Heterogeneous Kinetics of N719-Sensitized TiO2 Films in Acetonitrile-Based and
Catalysts. Catal. Today 2001, 67, 319−339. Ionic-Liquid-Based Electrolytes Investigated by Scanning Electro-
(25) Zhang, H.; Wang, J. J.; Fan, J.; Fang, Q. Microfluidic Chip-Based chemical Microscopy. J. Phys. Chem. C 2012, 116, 4316−4323.
Analytical System for Rapid Screening of Photocatalysts. Talanta (43) Zhang, B.; Yuan, H.; Zhang, X.; Huang, D.; Li, S.; Wang, M.;
2013, 116, 946−950. Shen, Y. Investigation of Regeneration Kinetics in Quantum-Dots-
(26) Arai, T.; Konishi, Y.; Iwasaki, Y.; Sugihara, H.; Sayama, K. High- Sensitized Solar Cells with Scanning Electrochemical Microscopy. ACS
Throughput Screening Using Porous Photoelectrode for the Develop- Appl. Mater. Interfaces 2014, 6, 20913−20918.
ment of Visible-Light-Responsive Semiconductors. J. Comb. Chem. (44) Barker, A. L.; Macpherson, J. V.; Slevin, C. J.; Unwin, P. R.
2007, 9, 574−581. Scanning Electrochemical Microscopy (SECM) as a Probe of Transfer
(27) Dogan, C.; Stowe, K.; Maier, W. F. Optical High-Throughput Processes in Two-Phase Systems: Theory and Experimental
Screening for Activity and Electrochemical Stability of Oxygen Applications of SECM-Induced Transfer with Arbitrary Partition
Reducing Electrode Catalysts for Fuel Cell Applications. ACS Comb. Coefficients, Diffusion Coefficients, and Interfacial Kinetics. J. Phys.
Sci. 2015, 17, 164−75. Chem. B 1998, 102, 1586−1598.
(28) Weidenhof, B.; Reiser, M.; Stowe, K.; Maier, W.; Kim, M.; (45) Bandarenka, A. S.; Ventosa, E.; Maljusch, A.; Masa, J.;
Azurdia, J.; Gulari, E.; Seker, E.; Barks, A.; Laine, R. High-Throughput Schuhmann, W. Techniques and Methodologies in Modern Electro-
Screening of Nanoparticle Catalysts Made by Flame Spray Pyrolysis as catalysis: Evaluation of Activity, Selectivity and Stability of Catalytic
Hydrocarbon/NO Oxidation Catalysts. J. Am. Chem. Soc. 2009, 131, Materials. Analyst 2014, 139, 1274−1291.
9207−9219. (46) Shen, Y.; Nonomura, K.; Schlettwein, D.; Zhao, C.; Wittstock,
(29) Xiang, C.; Suram, S. K.; Haber, J. A.; Guevarra, D. W.; G. Photoelectrochemical Kinetics of Eosin Y-Sensitized Zinc Oxide
Soedarmadji, E.; Jin, J.; Gregoire, J. M. High-Throughput Bubble Films Investigated by Scanning Electrochemical Microscopy. Chem. -
Screening Method for Combinatorial Discovery of Electrocatalysts for Eur. J. 2006, 12, 5832−5839.
Water Splitting. ACS Comb. Sci. 2014, 16, 47−52. (47) Yuan, D.; Xiao, L.; Jia, J.; Zhang, J.; Han, L.; Li, P.; Mao, B.-W.;
(30) Zhang, Y.; Chan, H. F.; Leong, K. W. Advanced Materials and Zhan, D. Combinatorial Screening of Photoelectrocatalytic System
Processing for Drug Delivery: the Past and the Future. Adv. Drug with High Signal/Noise Ratio. Anal. Chem. 2014, 86, 11972−11976.
Delivery Rev. 2013, 65, 104−120. (48) Zhou, N.; Chen, G.; Zhang, X.; Cheng, L.; Luo, Y.; Li, D.;
(31) Newman, D. J.; Cragg, G. M. Natural Products as Sources of Meng, Q. Highly Efficient PbS/CdS Co-Sensitized Solar Cells Based
on Photoanodes with Hierarchical Pore Distribution. Electrochem.
New Drugs Over the 30 Years from 1981 to 2010. J. Nat. Prod. 2012,
Commun. 2012, 20, 97−100.
75, 311−335.
(49) Watanabe, S.; Mita, Y. CdS-PbS Heterojunctions. J. Electrochem.
(32) Ling, S. G.; Gao, J.; Xiao, R. J.; Chen, L. Q. High-Throughput
Soc. 1969, 116, 989−993.
Theoretical Design of Lithium Battery Materials. Chin. Phys. B 2016,
(50) Braga, A.; Giménez, S.; Concina, I.; Vomiero, A.; Mora-Seró, I.
25, 97−105.
Panchromatic Sensitized Solar Cells Based on Metal Sulfide Quantum
(33) Wain, A. J. Scanning Electrochemical Microscopy for
Dots Grown Directly on Nanostructured TiO2 Electrodes. J. Phys.
Combinatorial Screening Applications: a Mini-Review. Electrochem.
Chem. Lett. 2011, 2, 454−460.
Commun. 2014, 46, 9−12.
(51) Dean, J. A., Ed. Lange’s Handbook of Chemistry, 13th ed.;
(34) Bertoncello, P. Advances on Scanning Electrochemical
McGraw Hill: New York, 1985.
Microscopy (SECM) for Energy. Energy Environ. Sci. 2010, 3,
(52) Fernee, M.; Watt, A.; Warner, J.; Cooper, S.; Heckenberg, N.;
1620−1633.
Rubinsztein-Dunlop, H. Inorganic Surface Passivation of PbS Nano-
(35) Fernandez, J. L.; Mano, N.; Heller, A.; Bard, A. J. Optimization
crystals Resulting in Strong Photoluminescent Emission. Nano-
of ″Wired″ Enzyme O2-Electroreduction Catalyst Compositions by technology 2003, 14, 991−997.
Scanning Electrochemical Microscopy. Angew. Chem., Int. Ed. 2004, 43, (53) Thangavel, S.; Ganesan, S.; Chandramohan, S.; Sudhagar, P.;
6355−6357. Kang, Y. S.; Hong, C. H. Band Gap Engineering in PbS
(36) Fernández, J. L.; Walsh, D. A.; Bard, A. J. Thermodynamic Nanostructured Thin Films from Near-Infrared Down to Visible
Guidelines for the Design of Bimetallic Catalysts for Oxygen Range by in Situ Cd-Doping. J. Alloys Compd. 2010, 495, 234−237.
Electroreduction and Rapid Screening by Scanning Electrochemical

G DOI: 10.1021/acsami.6b06029
ACS Appl. Mater. Interfaces XXXX, XXX, XXX−XXX