Electrochim Acta 75, 2012
Electrochim Acta 75, 2012
Electrochim Acta 75, 2012
http://dx.doi.org/10.1016/j.electacta.2012.04.087
Abstract
Here we analyze the effect of two relevant aspects related to cell
preparation on quantum dot sensitized solar cells (QDSCs) performance: the
architecture of the TiO2 nanostructured electrode and the growth method of
quantum dots (QD). Particular attention is given to the effect on the
photovoltage, Voc, since this parameter conveys the main current limitation
of QDSCs. We have analyzed electrodes directly sensitized with CdSe QDs
grown by chemical bath deposition (CBD) and successive ionic layer
adsorption and reaction (SILAR). We have carried out a systematic study
comprising structural, optical, photophysical and photoelectrochemical
characterization in order to correlate the material properties of the
photoanodes with the functional performance of the manufactured QDSCs.
The results show that the correspondence between photovoltaic conversion
efficiency and the surface area of TiO2 depends on the QDs deposition
1
both the architecture of the wide bandgap oxide semiconductor TiO2 and
the light absorbing semiconductor deposition strategy on the photovoltaic
performance of QDSCs. We have paid special attention to the effect of both
issues on the device photovoltage, Voc, since this parameter conveys the
main current limitation of QDSCs. Current Voc values for QDSCs lay
significantly below those reported for DSCs [22], while photocurrents, Jsc, as
high as 18.4 mA/cm2[16], and fill factors, FF, higher than 0.62, have been
reported for QDSCs [23], which are close to the values reported for high
efficient DSCs.
One of the key points responsible for the high performance obtained with
DSCs is the nanostructured electrodes. A monolayer of light absorbing
molecular dye can only absorb a small quantity of the incident light.
However, the use of nanostructured electrodes allows a factor 1001000
increase of the effective surface area, and consequently, a similar increase
of the optical density, or even higher if for example a light scattering layer is
employed. When light absorbing materials with different properties are used
(for example semiconductor QDs), the most suitable electrode structure
leading to optimal functionality has to be found for several reasons. The
smallest TiO2 nanoparticles (around 1015 nm), which are desired for high
effective surface area, lead to the formation of 510 nm pores, leading to
serious difficulties for QD loading and penetration of the electrolyte, which
are deleterious for sensitized solar cell performance [19]. In addition, the
much higher molar extinction coefficient of semiconductor QDs compared to
molecular dyes, lead to a relaxation of the requirements related to the
surface area of the mesoporous electrode in QDSCs [24]. In fact, high
performing QDSCs, have been reported with alternative low surface area
morphologies like TiO2 inverse opals [25], SiZnO hierarchical pine-tree
structures [22], or ZnO nanowires [22], [26] and [27]. It is particularly
relevant, the high Voc, up to 0.77 V, values obtained with ZnO nanowires
[22].
Another significant difference between semiconductor QDs and molecular
dyes is the strong dependence of QD properties, and consequently solar cell
performance, on the QD growth method and the attaching mode to the wide
bandgap nanostructured semiconductor [21], [28], [29], [30], [31] and [32].
There are two main approaches for QD sensitization: (i) to use previously
synthesized colloidal QDs [13], [29] and [30] and (ii) to directly grow the QD
on the surface of the wide bandgap semiconductor [12], [19], [20], [23] and
[33]. The direct growth of semiconductor QDs on the surface of the
nanostructured electrode does not allow a fine control of the QDs properties,
but produces a significant higher QD loading, increasing the solar cell
photocurrent. In fact the highest efficiencies reported for QDSCs have been
reported using a direct growth method [1], [5] and [23].
Taking into account these considerations, in the present study we have
analyzed nanostructured electrodes with different architectures directly
sensitized with CdSe QDs grown by chemical bath deposition (CBD) [23] and
3
[34] and successive ionic layer adsorption and reaction (SILAR) [12]. Both
methods are based on low cost solution processes, ideal for up-scaling and
fabrication of cost-effective photovoltaic devices. We have carried out a
systematic study comprising structural, optical, photophysical and
photoelectrochemical characterization in order to correlate the material
properties of the photoanodes with the functional performance of the
manufactured QDSCs. Particular attention is given to the correspondence
between Voc and both the electrode structure and QD growth method.
2. Experimental
2.1. Synthesis of the TiO2 structures
Six different TiO2 morphological structures were tested. Three structures
were based on nanoparticles (P20, P250 and P20450), two on hollow fibers
(F and F + P20) and one on inverse opal structures (O). The three
nanoparticulated structures (P20, P250 and P20450) were obtained from
commercial pastes from Dyesol: DSL-18NR-T (TiO2 particle size 20 nm), WER
2-O (TiO2 particle size 250 nm) and DSL-18NR-AO (TiO2 particle size 20450
nm), respectively. The first paste produces electrodes with high effective
surface area, while the other two are commonly employed as light
scattering layers in DSCs. The hollow fibers (F) were synthesized as
previously described [35] and [36]. A solution of ethyl cellulose solution was
prepared by dissolving 1 g of ethyl cellulose in 12.5 ml ethanol assisted by
ultrasonication. The paste for doctor blading was prepared by milling 0.2 g
hollow fibers and 1 ml of the prepared solution of ethyl cellulose in ethanol
in a mortar for 30 min while 1 ml of terpineol was added dropwise during the
milling process. The F + P20 structure was prepared by mixing 60 wt% of
the P20 paste with 40 wt% of the F paste.
Finally the inverse opals were prepared by infiltration of a three dimensional
photonic colloidal crystal made of polystyrene spheres of 300 nm and 400
nm diameter. Spheres were deposited by spin coating, self-assembling on
the substrate [37]. Next, a 2% methanolic TiCl4 solution was added onto the
self-assembled polystyrene spheres and samples were stored during 30 min
at 80 C. This process was repeated three times. After that, a thermal
treatment (450 C, 1 h, ramp: 1/min) was applied to remove the ordered
polysterene template and to consolidate the TiO2 inverse opal structure.
All the photoanodes (with the only exception of the O material) were doctorbladed on transparent conducting fluorine doped tin oxide (FTO) glass
substrates (sheet resistance 10 /). The resulting photoelectrodes were
sintered at 450 C, to obtain good mechanical and electrical contact at the
interfaces TiO2/TiO2 and TiO2/substrate. Before deposition of the different
TiO2 structures, the FTO substrates were coated by a compact layer of TiO2
deposited by spray pyrolysis (100 nm thick). These electrodes were
calcinated at 450 C for 30 min. For samples O and F, it has been detected a
low mechanical stability and poor adhesion with the substrate.
water [13] and [14]. The Cu2S counter electrodes were prepared by
immersing a brass foil in HCl solution at 70 C for 5 min and subsequently
dipping it into polysulfide solution for 10 min, resulting in a porous Cu2S
electrode. The geometric area of the cells was 0.28 cm2.
2.4. Photoanode and solar cell characterization
Gas adsorption measurements, BET, were performed on a Micromeritics
ASAP 2020 surface area and porosity analyzer with the ASAP 2020 V3.04 E
software. Three measurements were carried out for each specimen in order
to assess the reproducibility of the results. Microstructural examination of
the sensitized photoanodes was carried out by a JSM-7000F JEOL FEG-SEM
system (Tokyo, Japan). Transmission electron microscopy was carried out by
using a high resolution TEM (HRTEM) Field Emission Gun JEM-2100 electron
microscope (JEOL) operated at 200 kV. TEM samples were prepared by
raking off the mesoporous sensitized photoanodes from the FTO coated
glass. The powder specimens were sonicated in absolute ethanol for 5 min,
and a few drops of the resulting suspension were deposited onto a holeycarbon film supported on a copper grid, which was subsequently dried.
The optical absorption spectra of the photoanodes were recorded in the
range of 300800 nm by a Cary 500 UV-VIS Varian spectrometer, no
integrating sphere has been employed in the measurement. Current
potential (JV) curves, impedance spectroscopy (IS) measurement, applied
bias voltage decay (ABVD) [42] were carried out with a FRA equipped
PGSTAT-30 potentiostat from Autolab. JV measurements were carried out
using mask (0.24 cm2). Cells were illuminated using a solar simulator at
AM1.5 G, where the light intensity was adjusted with an NREL calibrated Si
solar cell with a KG-5 filter to one sun intensity (100 mW/cm2). Incident
photon to electron conversion efficiency (IPCE) measurements have been
performed employing a 150 W Xe lamp coupled with a computer-controlled
monochromator. The photocurrent was measured using a nanoammeter
70310 from Oriel Instruments. Impedance spectroscopy measurements were
carried out in dark conditions applying a 20 mV AC signal with the frequency
ranging between 400 kHz and 0.1 Hz at different forward biases. Ultrafast
carrier dynamics have been evaluated by the lens-free heterodyne detection
transient grating (LF-HD-TG) technique. The principles and experimental
setup of the technique have been described before [43], [44], [45] and [46].
In the present study, the laser source was a titanium/sapphire laser (CPA2010, Clark-MXR Inc.) with a wavelength of 775 nm, a repetition rate of 1
kHz, and a pulse width of 150 fs. The light was separated into two parts. Half
of it was used as a probe pulse. The other half of the light was used to pump
an optical parametric amplifier (OPA) (a TOAPS from Quantronix) to
generate light pulses with a wavelength tunable from 290 nm to 3 m; used
as a pump light in the TG measurement. In this study, the pump pulse
wavelength was 520 nm and the probe pulse wavelength was 775 nm. Since
most reliable results are obtained working in transmission configuration,
only P20 and F specimens were tested.
6
11
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Papers
Brief
16
Figure captions
Figure 1. Top view micrographs of the different tested TiO2 structures. (a) F,
(b) P20450, (c) P250, (d) P20, (e) F + P20 and (f) O. The scale bar is 500
nm for all micrographs.
Figure 2. Size distribution extracted from BET measurements for the
different structures tested.
Figure 3. Optical absorbance of the sensitized electrodes and IPCE of the
respective manufactured solar cells.
Figure 4. JV curves of the different solar cells.
Figure 5. Photovoltaic parameters for the different TiO2 morphologies
ranked by surface area (O < F < P250 < P20450 < F + P20 < P20) for both
QDs deposition methods, CBD and SILAR.
Figure 6. Voc values obtained for the different TiO2 structures and for both
QDs deposition methods, CBD and SILAR. O300 and O400 indicate the
inverse opal pore size, 300 and 400 nm, respectively.
Figure 7. Chemical capacitance of P20, P20450 and P250 samples
normalized to TiO2 electrode volume comparing CBD and SILAR.
Figure 8. Rrec for the different TiO2 morphologies comparing CBD vs SILAR.
Figure 9. (a) Scheme of the different charge trapping and charge transfer
processes monitored by ultrafast carrier dynamics. (b) Characteristic
experimental TG response of a P20 sample sensitized with CdSe grown by
SILAR (dots) and the fitting to a biexponential decay (solid line).
17
Table 1
Table 1. BET surface area, porosity and total area of the electrodes with the
different TiO2 structures (geometrical area of the electrodes is 0.24 cm2).
TiO2 morphology
BET (m2/g)
Porosity
82.84
0.90
268a
P20450
27.33
0.29
250
P250
10.15
0.31
92
P20
73.82
0.40
675
18
Table 2
Table 2. Photovoltaic parameters of the tested solar cells under 1 sun AM1.5G
illumination.
QD deposition
Voc (V)
Jsc (mA/cm2)
FF
(%)
SILAR
0.51
2.33
0.47
0.56
CBD
0.60
2.56
0.46
0.72
P20450
SILAR
0.56
6.98
0.52
2.05
P20450
CBD
0.65
7.59
0.56
2.80
P250
SILAR
0.57
5.00
0.52
1.48
P250
CBD
0.64
5.45
0.58
2.04
P20
SILAR
0.50
9.86
0.46
2.28
P20
CBD
0.50
7.84
0.51
2.10
F + P20
SILAR
0.52
8.04
0.57
2.38
F + P20
CBD
0.60
7.33
0.58
2.57
SILAR
0.43
2.66
0.51
0.59
CBD
0.62
2.12
0.35
0.47
19
Table 3
Table 3. Summary of the fitting parameters for the transient grating response of
the P20 and F structures sensitized via both SILAR and CBD using a
biexponential decay function.
Sample
1 (ps)
2 (ps)
A1
A2
P20
SILAR
6.0 0.4
660 36
0.33 0.01
0.52 0.01
P20
CBD
6.6 0.9
442 38
0.34 0.02
0.55 0.01
SILAR
0.3 0.1
12.9 0.9
0.60 0.07
0.42 0.02
CBD
0.5 0.1
4.9 0.9
0.72 0.08
0.33 0.06
20
Figure 1
21
Figure 2
22
Figure 3
23
Figure 4
24
Figure 5
25
Figure 6
26
Figure 7
27
Figure 8
28
Figure 9
29