pubs.acs.

org/JPCC Article

Electron-Selective Layers for Dye-Sensitized Solar Cells Based on

TiO2 and SnO2
Ladislav Kavan,* Zuzana Vlckova Zivcova, Magda Zlamalova, Shaik M. Zakeeruddin,
and Michael Grätzel
Cite This: J. Phys. Chem. C 2020, 124, 6512−6521 Read Online

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ABSTRACT: Titanium dioxide (anatase, rutile) and quasi-amorphous tin dioxide are
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prepared on F-doped SnO2 in the form of dense thin films, which can serve as electron-
selective layers in perovskite solar cells and dye-sensitized solar cells (DSSCs). The present
study brings new data about electronic and electrochemical properties of these films at the
authentic conditions occurring in a dye-sensitized solar cell (DSSC). Hydrolysis of TiCl4
provides pure rutile TiO2 at low temperatures, but TiO2 (anatase) grows in these layers
upon calcination. In acetonitrile medium, the flat band potential of TiO2 (rutile) is more
negative than that of TiO2 (anatase). This is opposite ordering to that observed in aqueous
media. The energy of conduction band minimum of TiO2 (anatase) equals −4.15 ± 0.07 eV
at the conditions mimicking the DSSC’s environment. Electrochemical reductive doping of
SnO2 provides a material with the most negative flat band potential and the largest overpotential for the reduction of I3−,
Co(bpy)33+, and Cu(tmby)22+. Voltammetric screening of all the electrode materials in six different electrolyte solutions, relevant to
DSSC applications, gives salient information about the mediator type and effects of calcination and the addition of 4-tert-
butylpyridine. These data provide novel inputs for optimization of DSSCs and for perovskite photovoltaics, too.

1. INTRODUCTION Later on, a spray pyrolysis of titanium(IV) diisopropoxide-

The electron-selective layer (ESL; also called electron bis(acetylacetonate) was introduced 14 and further im-
transport, electron extraction, hole-blocking, or buffer layer) proved,15−17 while it became to be the most popular method
is a key component of both the dye-sensitized solar cell for the fabrication of ESL both in DSSCs and PSCs. The next
(DSSC)1−5 and the perovskite solar cell (PSC).6−8 ESL is important method of the ESL growth is the chemical bath
deposited, as the first layer, on the negative electrode terminal deposition from aqueous TiCl4 solutions.18,19 Whereas the
(typically made from F-doped SnO2, FTO, or indium−tin spray pyrolysis provides the anatase form of TiO2,15,17,19 the
oxide, ITO). Its primary role consists of blocking of any growth from TiCl4 can produce rutile18 or anatase18,20
depending on the synthetic details. Sometimes, TiO2 ESL is
electron leakage from FTO to the oxidized form of the
also grown by atomic layer deposition (ALD) providing
electrolyte mediator or holes in the hole-transport medium
perfectly compact films down to several nm thickness21 with
(including the perovskite itself) in the respective devices. ESL
promising performance in DSSC.22
thus enhances the open-circuit voltage, VOC, and fill factor of
The use of ESL is essential in DSSCs with organic dyes,1,4,23
both types of photovoltaics. Additional benefits of ESL follow
novel redox mediators (Co(III/II)19,24 or Cu(II/I)25), and in
from improved physical and electrical contacts between FTO
systems operating at weak illumination, for example, under
and the mesoporous oxide semiconductor (usually TiO2)9 and
ambient lighting.19,26 The ESL must be compact (pinhole-
enhanced optical transmittance.9,10 Specifically, in the I3−/I−-
free), which can be easily tested by cyclic voltammetry of
mediated DSSCs, this layer blocks the reaction of electrons
model redox probes, such as Fe(CN)63−/4−20,21,27 (note
with photo-generated I2−· radical anions, thus enhancing not
however, possible formation of Prussian blue, obscuring this
only the VOC but also the photocurrent.9
test28). Good ESLs must be rectifying, that is, it must exhibit
The traditional DSSCs with Ru sensitizers and the I3−/I−
solely the cathodic wave of ferricyanide reduction at potentials
redox mediator work reasonably well even in the absence of
ESL, which is ascribed to the fact that (i) the Ru dye itself can
effectively screen the electron transfer from FTO to the Received: December 24, 2019
electrolyte and (ii) the I3−/I− exchange current is very small on Revised: February 28, 2020
FTO.1−4 Yet, already the pioneering works11,12 noticed a Published: March 2, 2020
significant performance improvement if few monolayers of
dense TiO2 were electrochemically deposited13 over the FTO/
mesoporous TiO2 in the originally “ESL-free” cell architecture.

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6512 J. Phys. Chem. C 2020, 124, 6512−6521
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negative to the flat band potential but no anodic counterwave.
Lee et al.19 compared the ESL made by spray pyrolysis with
the ESL made from TiCl4. The latter was fabricated by the
usual synthetic protocol, that is, immersion of FTO into an
aqueous 40 mM TiCl4 at 70 °C for 30 min.19,29 However, this
layer provided poor FTO coverage by isolated TiO 2
particles19,30 translating into large proportion of the electro-
chemically detectable pinholes. Yet, the performance of this
“non-ideal” ESL in a Co-mediated DSSC was still acceptable at
solar illumination (1 to 0.1 sun) but not at weak ambient
lighting (251−1001 lux) when solely the spray pyrolysis-made
ESL gave efficient DSSCs.19
The second ESL material, which is employed especially in
perovskite photovoltaics, is SnO2.31,32 It is grown usually by
atomic layer deposition (ALD),27,32−35 sometimes also by
spin-coating from SnCl2 or SnCl4 solutions.35,36 The spray
pyrolysis from butyltin trichloride was complicated by fluorine
migration from FTO into the SnO2 at the temperature of
pyrolysis, but this problem could be circumvented by replacing
FTO with Al-doped ZnO.37
Despite the great efforts invested so far into the ESL
development, a systematic comparison of various materials in
different DSSC’s electrolyte solutions is still lacking. Hence,
the central aim of this study is to acquire accurate data about
electrochemical and electronic properties of the TiO2 and
SnO2 films, which already proved to be useful for ESL
applications. These studies are carried out at the authentic
conditions occurring in dye-sensitized solar cells using
acetonitrile electrolyte solutions and three different redox
mediators. We confirm here the formation of pure rutile in ex-
TiCl4 layers, but quite unexpectedly, also the growth of anatase
in these layers upon calcination. We find serendipitously that a
simple electrochemical treatment of ALD-SnO2 can downshift
substantially the onset potential of dark current, which is
important for solar cells’ optimization.
2. EXPERIMENTAL SECTION
2.1. Preparation of the TiO2 or SnO2 Layers. FTO glass
(NSG10, Nippon Sheet Glass, 10 ohm/sq) was cleaned
ultrasonically using a detergent solution (Deconex) followed
by water, ethanol, and acetone (10 min treatment in each
bath). Thin-film rutile, denoted TiO2(R), was prepared by a
chemical bath deposition method. The FTO substrate was
treated in 200 mM aqueous solution of TiCl4 at 70 °C for 1 h,
producing an ∼25 nm-thick TiO2 film.18 It was subsequently
washed with water and ethanol and dried at 100 °C. The
anatase thin film (ca. 30 nm), denoted TiO2(A), was deposited
by spray pyrolysis (at 450 °C) using oxygen as the carrier gas
and a solution of 0.2 M titanium diisopropoxide-bis-
(acetylacetonate) and 0.4 M acetylacetone in ethanol.15,16
The quasi-amorphous SnO2 films (3−15 nm) were prepared as
in ref 27 by atomic layer deposition (ALD) at 118 °C using
tetrakis-(dimethylamino)tin(IV) (99.99% Sn, Strem Chem-
icals, Inc.) and ozone using Savannah ALD 100 (Cambridge
Nanotech, Inc.) or R200 (Picosun, Finland). The redox
mediators, Co(bpy) 3 (TFSI) 3 , Co(bpy) 3 (TFSI) 2 , Cu-
(tmby)2(TFSI)2 and Cu(tmby)2(TFSI) (bpy = 2,2′-bipyr-
idine; tmby = 4,4,6,6-tetramethyl-2,2′-bipyridine; TFSI =
trifluoromethylsulfonylimide) were purchased from Dyenamo,
Sweden. Table S1 (Supporting Info) summarizes the details
about electrolyte solutions. Other chemicals were from Aldrich
and used as received.
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2.2. Characterization of the Films. The Raman spectra
were acquired with the 514 nm laser excitation on a Labram
HR spectrometer (Horiba Jobin-Yvon) interfaced to an
Olympus microscope (objective 100×). The laser power at
the sample was 2 mW (the spot area was approx. 1 μm2).
Scanning electron microscopy (SEM) images were obtained by
a Hitachi S-4800 microscope. X-ray photoelectron spectros-
copy (XPS) was performed using an Omicron Nanotechnology
instrument equipped with a monochromatized Al Kα source
(1486.7 eV) and a hemispherical analyzer operating in
constant analyzer energy mode with a multichannel detector.
The binding energies were calibrated by evaporated gold (Au
4f7/2 at 84.0 eV) and were referenced to the specimen Fermi
level, which is set as zero. For the work function measurement
(by the secondary electron cut-off), the sample was biased at
−6.3 V. The CasaXPS program was used for spectra analysis.
The spectra were curve-fitted after subtraction of Shirley
background using the Gaussian−Lorentzian line shape.
Quantitative surface analysis employed the relative sensitivity
factors based on the Scofield’s cross sections.
2.3. Electrochemical and Photoelectrochemical Prop-
erties of the Films. Electrochemical experiments were carried
out in a one-compartment cell using an Autolab Pgstat-30
equipped with the FRA module (Metrohm). The counter-
electrode was a platinum mesh, and the reference electrode
was a non-aqueous Ag/AgCl (sat. LiCl in ethanol), which was
interfaced by a bridge with 0.1 M lithium trifluoromethylsulfo-
nylimide (LiTFSI) in acetonitrile. The potential was calibrated
using ferrocene (200 μL of 0.1 M acetonitrile solution per 10
mL of electrolyte solution added and tested using the Pt
working electrode; the potential of this primary standard (Fc+/
Fc) was fluctuating between 0.499 to 0.506 V vs. the non-
aqueous Ag/AgCl). Cyclic voltammetry (in aqueous medium)
was performed in 0.5 M KCl with 0.5 mM K3[Fe(CN)6] and
0.5 mM K4[Fe(CN)6]; its pH was adjusted by HCl to 2.5. In
this case, the reference electrode was aqueous Ag/AgCl (sat.
KCl). The electrolyte solution was purged with Ar, and the
measurement was carried out under Ar in a closed electro-
chemical cell. Impedance spectra were measured in the
frequency range from 100 kHz to 0.1 Hz (modulation
amplitude 10 mV) at varying potentials. Spectra were evaluated
using ZView (Scribner) software by fitting to a Randles-type
circuit (Figure S1, Supporting Info). Here, RCT is the charge
transfer resistance, which is parallel to the constant phase
element (CPE) to account for non-ideal capacitive behav-
ior.21,27 The circuit is completed with a series resistance, RS,
characterizing the ohmic resistance of electrodes, electrical
contacts, and electrolyte solution. The Warburg impedance,
ZW, corresponds to the ionic transport in solution.
The impedance of CPE equals38
ZCPE = B−1(iω)−β (1)
with ω being the EIS frequency and B (admittance prefactor)
and β (exponent) are the frequency-independent parameters of
the CPE (0.8 ≤ β ≤ 1; experimental values were from 0.8 to
0.9). The capacitance, C, is calculated from38
(R CTB)1/ β
C=
R CT (2)
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3. RESULTS AND DISCUSSION
3.1. ESL from TiO2. The chemical bath deposition of TiO2
on FTO by the standard synthetic protocol (treatment in 40
mM TiCl4 at 70 °C for 30 min19,29) gave a poorly blocking film
as illustrated in Figure S2 (Supporting Info). Yella et al.18
reported that a simple enhancement of the TiCl4 concentration
(to 200 mM) gave a more uniform film with excellent
performance in PSC. This observation is confirmed here by a
blocking test (Figure S2), which illustrates (i) efficient
suppression of the ferrocyanide oxidation and (ii) fast
reversible charging/discharging of chemical capacitance with
a characteristic prepeak assigned to surface states.39 This film
(denoted TiO2(R)) was therefore chosen for all additional
studies of the ex-TiCl4 layers.
Raman spectroscopy is a useful technique for the phase
analysis of titania.40,41 Figure 1 shows that a blank FTO has
Figure 1. Raman spectra of the FTO-supported TiO2(R) electrode
(blue curve), blank FTO substrate (turquoise), and TiO2(A)
electrode (black curve). Also shown is the spectrum of an identically
grown titania film [as for TiO2(R)] but with doubled reaction time (2
h instead of 1 h, labeled “2hr”). The symbol HT denotes the
electrodes that were heat-treated at 450 °C for 1 h. Spectra of
reference rutile powder (blue dashed curve) and anatase powder
(black dashed curve) are shown, too. The diagnostic lines for rutile
and anatase are labeled by full and dashed arrows, respectively. The
spectra are offset for clarity, but the intensity scale is identical for all
spectra, except for TiO2(A) and TiO2(A)-HT, which were attenuated
by a factor of 10.
relatively weak Raman features (the main band being A1g mode
of SnO2 at 635 cm‑1 42). They do not interfere with the
diagnostic bands of TiO2 neither in anatase nor in rutile forms.
Hence, the FTO-supported thin TiO 2 films can be
conveniently analyzed by Raman. This is a significant
advantage over X-ray diffraction because the strong FTO
lines dominate the diffractograms of, for example, anatase
made by spray pyrolysis15,19 or by ALD.22 This problem is
further augmented with TiO2 rutile thin films because the FTO
(cassiterite structure) has a very similar diffraction pattern. The
TiO2(A) layer expectedly shows the Raman spectrum of pure
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anatase TiO2 (Figure 1; cf. also ref 17), which is insensitive to
calcination (450 °C, 1 h in air; the standard protocol of the
fabrication of a TiO2 photoanode).
The Raman analysis of ex-TiCl4 titania is less easy due to
low Raman intensities in this particular sample. However, the
presence of rutile is confirmed in a film, which was grown as
the TiO2(R) sample, but with deliberately doubled reaction
time (Figure 1). Hence, we conclude, in accordance with Yella
et al.,18 that our TiO2(R) sample is a rutile thin film with
perfect compactness useful for ESL fabrication. Interestingly,
TiO2(R), which was calcined at 450 °C for 1 h, exhibits a
clearly resolved peak at 141 cm−1, which is assignable to the
diagnostic line of anatase, (Eg(1); see Figure 1). Obviously, the
ex-TiCl4 layer is unique not only by the low-temperature
growth of rutile TiO218 but also by its unexpected trans-
formation to anatase upon calcination. (An alternative
explanation is that anatase crystallizes during calcination
from the originally “amorphous” titania present in the parent
TiO2(R)).
The fast reversible charging/discharging of chemical
capacitance in TiO2(R) (cf. Figure S2) is reproduced in
acetonitrile medium, too. Figure 2 shows the relevant cyclic
voltammograms. Furthermore, Figure 2 illustrates the effect of
4-tert-butylpyridine (TBP) in the electrolyte solution. This
base is ubiquitously used as the standard component of
virtually all electrolyte solutions in DSSCs.43 (However, some
concern exists about the Cu(II/I) mediator, which is affected
by the coordination with TBP44−46). In general, TBP
significantly enhances VOC, which is ascribed to the Fermi
level upshift and longer electron lifetime in the conduction
band of both TiO247 and SnO2.48 Our voltammogram in
Figure 2 confirms that the onset potential of the capacitive
charging is downshifted by ca. 0.2 V in the presence of TBP.
This finding matches qualitatively the observed downshift of
the flat band potential (see section 3.3). Furthermore,
interaction of TBP with titania blocks the surface states
(electron traps) in TiO2 and adsorption sites for Li+ and H+
(e.g., from trace humidity).3,43,47 Hence, the cathodic/anodic
branches of the cyclic voltammogram are more symmetrical in
the presence of TBP because the voltammetric features of
surface states and cation adsorption are effectively blocked by
TBP (Figure 2).
3.2. ESL from SnO2. In contrast to TiO2 films, which
exhibit well-developed reversible charging/discharging of
chemical capacitance at potentials near the flat band (see
section 3.1), thin films of ALD-made SnO2 behave differently.
Figure 3 shows that a purely capacitive (double-layer) charging
occurs in the potential window from 0.5 V to ca. −1 V versus
Fc+/Fc. The corresponding Helmholtz capacitance, CH, equals
JH
CH =
ν (3)
(JH is the current density and ν is the scan rate). Equation 3
provides an estimate of the Helmholtz capacitance of 30 μF/
cm2. (This value would translate, for our compact 4 nm film,
into ca. 10 F/g, which is nearly identical to the specific
capacitance of SnO2 quantum dots in aqueous medium42). The
capacitances are corrected by considering the average rough-
ness factor of 1.3 for these films.27
In addition to capacitive effects, we observe irreversible
cathodic charging at potentials negative to ca. −1 V, which is
more pronounced in virgin films (dashed lines in Figure 3). If
this film was pretreated at −1.5 V for 2 min, then the net
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Figure 2. Cyclic voltammograms of a TiO2(R) thin-film electrode (made by hydrolysis of TiCl4). Electrolyte solution: (A) 0.1 M LiTFSI +
acetonitrile; (B) 0.1 M LiTFSI +0.5 M 4-tert-butylpyridine in acetonitrile. Scan rates of 100, 50, and 20 mV/s for the red, blue, and black curves,
respectively.
Figure 3. Cyclic voltammograms of a SnO2 thin-film (4 nm) electrode
in 0.1 M LiTFSI + acetonitrile, with a scan rate of 0.1 V/s. Dashed
lines are for the virgin electrode, full lines are for the same electrode
that was treated at −1.5 V for 120 s.
cathodic charge of 0.34 mC/cm2 was consumed irreversibly,
and the voltammogram changed as illustrated in Figure 3. We
denote this product as “doped” and symbolize it further
SnO2(D).
The found cathodic charge of 0.34 mC/cm2 would
theoretically correspond to approximately 9.5% conversion of
our SnO2 film into SnO. Additional experiments with varying
film thicknesses (from 3 to 10 nm; data not shown) provided
roughly similar conversion rates, but they dropped for thicker
films (up to 50 nm), clearly indicating that the reductive
doping affects the film down to several nm underneath the
surface. Figures S3−S5 (Supporting Info) show supplementary
details about reductive doping of SnO2. It can simply be
carried out by repeated voltammetric scanning, too. In thicker
films, the doping reaction manifests itself by a peak near −1.2
V (Figure S5).
X-ray photoelectron spectroscopy shows that doping of
SnO2 causes incorporation of ca. 6 at % Li (Figure S6,
Supporting Info). The presence of Sn2+ would manifest itself
by shifting of the Sn 3d5/2 photoemission line to smaller
binding energies (by about 0.7 eV).49 Our found binding
energy of Sn 3d5/2 (486.9 eV) is nearly identical to the value
reported for Li/SnO2 prepared by spin-coating from SnCl2 and
LiTFSI solution (486.8 eV).50 Nevertheless, the contributions
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of SnO and SnO2 strongly overlap, and the deconvolution by
fitting of the overlapping lines is not accurate for the Sn2+
concentrations below ∼10%.
The mechanism of Li doping is still unclear. In contrast to
TiO2 (anatase or rutile, which exhibits simple interstitial Li
insertion), SnO2 accommodates lithium electrochemically by
conversion reactions producing various Sn2+- and Sn0-
containing species.51,52 These reactions proceed at potentials
smaller than ca. 1 V versus Li+/Li (which is approximately
−2.6 V vs. Fc+/Fc). At the potentials that are used for the
growth of SnO2(D) (≥ −1.5 V vs. Fc+/Fc), the conversion
reactions hardly occur at significant speed. Instead, milder
effects are at play, similar to those reported during the growth
of Li/SnO2 from SnCl2 and LiTFSI. In this case, Park et al.50
proposed that Li doping consists of the substitution of Sn4+ by
Li+. As the binding energies of our SnO2 and SnO2(D) are not
affected (±0.1 eV) and close to those of Li/SnO2,50 the
structural perturbations of the SnO2 lattice are small (if any) in
both cases of Li doping, electrochemical and chemical.50 In
accordance with earlier works,27,32,53 we detect trace amounts
of non-carbonaceous impurities (N, Si) but no F 1s from the
FTO substrate.
3.3. Characterization by Electrochemical Impedance
Spectroscopy. Electrochemical impedance spectra were
acquired to determine the flat band potentials (Efb) and the
donor concentrations (ND). The spectra were fitted to an
equivalent circuit with the constant phase element, which
accounts for non-ideal capacitive behavior of polycrystalline
thin films21 (eq 2 and Figure S1). The values of Efb and ND
were extracted from the Mott−Schottky equation21
ij 2 yzij
= jjj zzjjE − E − kBT yzzz + 1
j zzj e z{ C H 2
k eε0εrND {k
1
2 fb
C (4)
e is the electron charge, ε0 is the permittivity of free space, εr is
the dielectric constant (εr values are 173, 55, and 10 for TiO2
(rutile), TiO2 (anatase), and SnO2, respectively21,27,54), E is
the applied voltage, Efb is the flat band potential, kB is the
Boltzmann’s constant, and T is the temperature.21,27,55 The
value of CH is approximately 30 μF/cm2 for SnO2 (cf. eq 3).
The voltammetric determination of CH for TiO2 is less
straightforward (cf. Figure 2), but the experimental Mott−
Schottky plots allow estimation of roughly the same value from
impedances measured at potential negative to the flat band
(Figure 4).
Figure 4 shows the Mott−Schottky plots of our four
representative electrodes in 0.1 M LiTFSI + acetonitrile
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Figure 4. Mott−Schottky plots for different electrode materials as specified in the annotation. The film thickness of SnO2 and SnO2(D) equals 4
nm. The electrolyte solution is 0.1 M LiTFSI + acetonitrile.
medium. To explore these plots at conditions mimicking the
DSSC’s electrolyte solution, we used two other model media:
0.1 M LiTFSI + 0.5 M TBP and 0.1 M LiTFSI + 0.1 M LiI +
0.05 M I2 + 0.5 M TBP. Figure S7 (Supporting Info) shows the
comparative data for a TiO2(A) electrode. The found values of
Efb and ND are collected in Table S2 (Supporting Info). The
flat band potentials are also listed here in the absolute scale,
EF(fb). Under certain approximations (neglecting the potential
drop in the Hemholtz layer, chemisorbed ions, oriented
dipoles, etc.), the energies EF(fb) are equal to the Fermi level
positions and define the work functions (φ = −EF(fb)). Our
values are roughly comparable to the work functions that were
measured by ultraviolet photoelectron spectroscopy (UPS) on
analogously made samples, for example, TiO2(A) (3.65 eV56 or
3.75−3.96 eV57), ALD-SnO2 (4.4653 or 4.20 eV32), and ALD-
SnO2 calcined at 300 °C (4.52 eV32). Our own data from XPS
secondary electron edge (Figure S9, Supporting Info) are 3.9,
3.7, 4.2, and 4.1 eV (± 0.1 eV) for the samples TiO2(A),
TiO2(R), SnO2, and SnO2(D), respectively.
Interestingly, the addition of I3−/I− to the solution has no
effect on the flat band potential and very small effect on the
ND, which is within the experimental error. The addition of
TBP causes downshift of Efb (by ca. 0.1−0.2 V) but again a
negligible change of ND. Obviously, there is no reason that the
donor density in a semiconductor electrode should depend on
the electrolyte solution, but the expected effect of TBP43−48 is
thus confirmed (cf. also Figure 1 and discussion thereof).
The applicability of the depletion layer model for our thin
films is tested by the estimation of the width of the space-
charge layer (W), assuming a parallel-plate model of the
capacitance
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ij 2ε ε yz ij k Ty
W = jjj 0 r zzz jjjE − Efb − B zzzz
j eND z
1/2 1/2
k { k e {
(5)
Equation 5 predicts (for the 1 V band-bending and the
experimentally found ND values) the widths (W) of 14, 25, and
3 nm for TiO2(A), TiO2(R), and SnO2, respectively. However,
as explained in ref 27, the electrochemically found ND values of
SnO2 (Table S2) are overestimated; the Hall measurements on
virtually identical materials gave ND values of the order of 1016
cm−3, which would put the W values of SnO2 to the 102 nm
level. Consequently, the depletion layer safely resides within
our TiO2 films (∼25−30 nm), but in SnO2, it can extend into
the supporting FTO, too. Indeed, the 4 nm SnO2 film exhibits
the second slope (Figure 4) corresponding to ND ≈ 1.2 × 1021
cm−3, that is, the typical donor density of FTO.21,27
The found flat band potential of TiO2(A) in our “DSSC-
like” electrolyte solution (containing TBP and I3−/I−) is
comparable to the value reported by Cameron and Peter2 from
a Mott−Schottky analysis of their spray-pyrolyzed TiO2
blocking layers in thin-layer cells with a similar DSSC
electrolyte. Their value of Efb = −0.76 V versus I3−/I−58
would translate59 into approximately −1 V versus Fc+/Fc,
which is close to our value of −0.90 ± 0.06 V versus Fc+/Fc
(Table S2). On the other hand, our flat band potentials are
larger than those measured spectroelectrochemically on similar
films in dry acetonitrile (−2.4 to −1.3 V vs. Fc/Fc+ depending
on Li+ concentration).60 The difference is explained (besides
very diverse experimental conditions in the reference
studies2,60) by the collective influence of Li+ and humidity,
both upshifting the Efb values significantly.60 Notably, in
contrast to studies of thin-layer cells,2 our approach provides a
well-defined reference electrode and the three-electrode setup
for accurate electrochemical experiments.
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The electrochemical potential corresponding to the
conduction band minimum (ECBM) is
kBT NC*
ECBM = Efb − ln
e ND (6)
where NC* is the effective density of conduction band states
ji 2πme*kBT zyz
2jjj zz
j z
3/2
k {
NC* =
h2 (7)
me* is the effective mass of electron (for TiO2 anatase me* ≈
1.9m0 with m0 being the electron’s rest mass61). Assuming ND
≈ (4.2 ± 1.2) × 1019 cm−3 (Table S2), the calculation gives the
energy of CB minimum equal to −4.15 ± 0.07 eV in the
absolute scale (with the work function of SHE being 4.44 eV).
We should note that the CBM position of TiO2 appears
frequently in the publications discussing energetics of DSSC
but without any clear reference how this CBM was actually
determined.3 Here, we provide the authentic value for TiO2
(anatase) at conditions occurring in the solar cell.
Our Efb for anatase in TiO2(A) is positive by 0.16 ± 0.04 V
against the value for rutile in TiO2(R). This is interesting
because in aqueous media, we observe just an opposite trend:
TiO2(A) (as well as single-crystal anatase) exhibits Efb ≈ −0.15
V versus RHE (reversible hydrogen electrode), whereas rutile
(in various forms) has its Efb near 0 V versus RHE.62 This
finding resonates with the theoretical prediction by Deák et
al.63,64 that the OH−/H+ adsorption is responsible for reversing
the band alignment between rutile and anatase, referring to
clean surfaces in vacuum. In other words, the aprotic
electrolyte solution provides the same ordering of anatase/
rutile like vacuum techniques (XPS)65 and some photocatalytic
studies.66 This finding could obviously help to address the
long-term controversy in the field.62−66
The observed Efb of SnO2 is similar or more negative than
that of titania in both forms (Table S2), which is again
unexpected because in aqueous media, we observe an opposite
trend.27,62 The electrochemical doping of SnO2 (section 3.2)
expectably causes some enhancement of ND and ca. 0.1−0.15
V downshift of Efb (Table S2). The doping-induced enhance-
ment of ND is about 10%, matching interestingly our estimate
that ∼9.5% SnO2 is affected by doping (Section 3.2), but this
coincidence could be just casual, considering the experimental
errors of the ND measurement (Table S2) and the different
information depth of XPS (compared to W, see eq 5). On the
other hand, the doping-induced downshift of Efb is significant
within the experimental accuracy. Our found downshift of Efb
is nearly equivalent to the recently reported change of the
Fermi level position in Ru/SnO267 but contradicts the opposite
effect in Li/SnO2 made by solution processing.50 We have no
simple explanation for these discrepancies, but note that the
mentioned energy shifts were found by UPS and by using
different preparative protocols for the Li/SnO2.50 Of interest is
the significant upshift (by 0.3 V) of Efb caused by heat
treatment (Figure S8 and Table S2). A similar upshift (by 0.5
V) was observed in aqueous medium27 and was assigned to
crystallization of the parent quasi-amorphous SnO2 to
cassiterite, without damaging the compact nature of this
film.27 A recent UPS study by Jeong et al.32 reported a 0.32 eV
downshift of the Fermi level (enhancement of the work
function) in ALD-made SnO2 upon heat treatment at 300 °C.
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This result is in remarkable accordance with our observed 0.3
V downshift of Efb after heat treatment of ALD-SnO2.
To further advance this discussion, Figure S9 (Supporting
Info) shows the XPS spectra of our ESL materials in the
valence band region. The valence band offset (referenced to
the Fermi level position) equals 3.1, 2.9, 3.8, and 3.7 eV (± 0.1
eV) for the samples TiO2(A), TiO2(R), SnO2, and SnO2(D),
respectively. These values are comparable to those reported by
others32,34,57,65,68,69 (although they are also known to depend
strongly on the samples’ preparation history32,57,68). For the
known optical band gaps (Eg) of TiO2 anatase and rutile of 3.2
and 3.0 eV, respectively, and for ALD-SnO2 (Eg = 3.98 eV),32
the corresponding offset of Fermi level from the CBM is quite
small (from ∼0.1 to 0.3 eV) in all our materials. This confirms
their significant n-doping (cf. Table S2 and eqs 6,7). The
valence bands of SnO2 and SnO2(D) have very similar shapes,
which is in accordance with the negligible doping-induced
changes in the spectra of core levels (cf. Figure S6 and
discussion thereof).
3.4. Dark Current on ESLs with Different Redox
Mediators. Finally, we investigated our four generic materials,
that is, TiO2(A), TiO2(R), SnO2, and SnO2(D), either as
grown or upon calcination at 450 °C, together with a blank
FTO and Pt-disc electrode by cyclic voltammetry in six
different electrolyte solutions. Their composition is specified in
Table S1 (Supporting Info). They are actually similar or
identical to the standard electrolyte solutions used in DSSCs.
However, in contrast to the measurement of dark current in
real DSSC devices (which are inherently two-electrode, thin-
film cells), we work here with the standard three-electrode
setup, providing optimum cell geometry and the well-defined
reference electrode. Figures 5, 6, and 7 summarize the relevant
Figure 5. Cyclic voltammograms in I3−/I−-containing electrolyte
solution with addition of TBP (full curves) and without addition of
TBP (dashed curves). Red curves are for oxide layers calcined at 450
°C.
data. Important practical information follows from the onset of
cathodic (dark) current because it controls the accessible
voltage of the solar cell.
The corresponding cathodic overvoltages (η) for the
mediator reduction are summarized in Figure S10 (Supporting
Info). The Pt-disc electrode was selected as the general
reference system for estimation of the η values (Figure S10)
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Figure 6. Cyclic voltammograms in Co(III/II)-containing electrolyte
solution with addition of TBP (full curves) and without addition of
TBP (dashed curves). Red curves are for oxide layers calcined at 450
°C.
Figure 7. Cyclic voltammograms in Cu(II/I)-containing electrolyte
solution with addition of TBP (full curves) and without addition of
TBP (dashed curves). Red curves are for oxide layers calcined at 450
°C. Pt and Pt1 are symbols for a platinum-disc electrode in the
presence and absence of TBP, respectively.
because all our three redox mediators exhibit fast electro-
chemistry at platinum. (For the same reason, Pt is the
ubiquitous electrocatalyst, which is used for the cathodes of
DSSCs with these mediators). All three redox mediators show
sluggish electrochemical kinetics on FTO where the corre-
sponding overpotentials for oxidation/reduction define the
electrochemical window in which the dark-current is negligible.
This window is quite broad for I3−/I− (which is one of the
reasons why these DSSCs work well even without ESL, see
above) but gets narrower for Cu(II/I) and Co(III/II). The Cu
mediator is unique by the strong effect of TBP, which
influences (in contrast to Co and I mediators) also the redox
processes on Pt (Figure 7). This is ascribed to the coordination
of TBP to Cu, as it is detailed in earlier works.44−46
Nevertheless, the overpotential for the reduction of I3− and
Co(III) on FTO is also enhanced by TBP. This provides clear
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evidence for an independent mechanism of the TBP action
(beyond coordination) based on adsorption of TBP to oxidic
surfaces, including also FTO (cf. also Figure 2 and discussion
thereof).
Our different electrode materials combined with three
different redox mediators provide a set of 54 values of η
from which the following general trends are deduced: (i) The
overvoltages increase in the series Co(III/II) < I3−/I− <
Cu(II/I). In all media, they are (ii) roughly comparable for
TiO2(A) and TiO2(R); (iii) the smallest overvoltages are
observed for SnO2; (iv) the largest overvoltages are observed
for SnO2(D); and (v) TBP enhances the overvoltages. The
effect of TBP is further illustrated in Figure S11 (Supporting
Info), which correlates the overvoltages for triiodide reduction
with the corresponding flat band potentials. In addition to the
ubiquitous “TBP enhancement” (of both Efb and η), we
observe a roughly linear correlation of Efb and η. This relation
is surely expectable for the ideally rectifying n-semiconductor/
electrolyte solution interfaces because the cathodic charge
transfer cannot proceed at potentials positive to Efb. However,
simple energetic arguments (the η/Efb correlation) are
insufficient to describe the interface because the kinetic
(electrocatalytic) effects play a role, too. (The electrocatalytic
activity of the n-semiconductor surface for various cathodic
reactions, e.g., for H+ reduction, is known to change
significantly even for different facets of the same crystal.70)
The interplay of thermodynamic and kinetic factors is
obviously responsible for the spread of data in Figure S11.
Figure S10 further surveys the effects caused by calcination
of the ESL materials. The cathodic overpotential is significantly
decreased by heat treatment in most materials although the
undoped SnO2 shows interesting mediator-specific features:
The drop of overpotential is strong for the I3− reduction but
much smaller (if any) for the Co(III) and Cu(II) reductions.
Most importantly, our doped tin oxide, SnO2(D), exhibits the
largest overpotential for all the three mediators. Hence, it
appears to be the best material for blocking of dark current in
DSSCs of all types. Unfortunately, SnO2(D) is, at the same
time, also very sensitive to calcination, which erases its
beneficial properties. Heat treatment brings the high reductive
overpotential of SnO2(D) back to the values characteristic for
undoped SnO2 in all three redox systems studied (Figures 5−7,
Figure S10). This evidences that the chemical or structural
changes caused by doping are erased by thermal treatment.
Yet, SnO2(D) could be applicable for solar cells that do not
require calcination, such as “low-temperature” DSSCs, which
do not require heat treatment of the TiO2 photoanode during
their fabrication. Eventually, SnO2(D) appears to be an
attractive material for PSCs because high temperatures are
normally avoidable in their preparation, and doping of SnO2 is
known to improve the photovoltaic parameters of PSC.31,50,67
The occurrence of anodic current (if any) detects pinholes
in the ESL, similarly to the standard “ferrocyanide” test (cf.
Figure S2 and discussion thereof). These pinholes are clearly
detectable in the I3−/I− medium and in the calcined TiO2(A),
TiO2(R), and SnO2(D) (Figure 5). The corresponding anodic
currents through pinholes are much smaller in the Co(III/II)-
and Cu(II/I)-containing media. We ascribe this difference to
the small ionic radius of I−. Iodide penetrates even across small
pinholes, which are not permeable for bulky molecules of
Co(bpy)32+ and Cu(tmby)2+. (An analogous situation occurs if
we compare oxidation of ferrocyanide and spiro-OMeTAD on
partly cracked films21,41).
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The undoped SnO2 is perfectly intact against thermal
cracking, which confirms earlier electrochemical tests of
blocking quality27,32 and mapping of leakage current by
AFM.32 Interestingly, however, the tin dioxide film loses its
unique thermal stability upon electrochemical doping when
small cracks (transparent selectively for I−) appear in the
SnO2(D) sample upon calcination (Figure 5). These small
cracks manifest themselves solely as the anodic leakage current
of iodide oxidation at the denuded FTO surface (Figure 5).
Absence of these leakage currents for Co(bpy)32+ oxidation
(Figure 6) and Cu(tmby)2+ oxidation (Figure 7) is attributed
to larger molecular volume of these organometallic complexes,
which cannot penetrate the small pinholes in the calcined
SnO2(D). SEM images (Figures S12 and S13; Supporting
Info) show that the morphology of SnO2(D) and blank SnO2
is dominated by the FTO substrate and is virtually intact by
calcination. We observe solely the crystallization-induced
coarsening of the surface,27,32 but the compact nature of
these films is nearly unperturbed (at the resolution of SEM).
At the same time, the high sensitivity of electrochemical
analysis of ultrasmall pinholes in the compact oxide film is thus
documented.
4. CONCLUSIONS
Titanium dioxide (anatase, rutile) and quasi-amorphous tin
dioxide were prepared on F-doped SnO2 (FTO) in the form of
compact, nm-thin films, particularly suitable for the develop-
ment of electron-selective layers in photovoltaics. Hydrolysis of
TiCl4 can provide pure rutile TiO2 at temperatures below 100
°C, but interestingly, TiO2 (anatase) grows in these layers
upon calcination at 450 °C.
In acetonitrile electrolyte solution, the flat band potential of
TiO2 (rutile) is more negative than that of TiO2 (anatase),
which is opposite to the flat band potential ordering of
anatase/rutile in aqueous media. This observation helps to
resolve a long-term controversy in the field. The conduction
band minimum of TiO2 (anatase) equals −4.15 ± 0.07 eV at
the conditions mimicking the DSSC’s environment. This value
is recommended to be the energy reference for the
corresponding DSSC photoanodes.
Simple electrochemical reduction (doping) of tin dioxide in
Li+/acetonitrile medium produces a Li-containing material,
SnO2(D), exhibiting the most negative flat band potential of all
the tested oxide electrodes. At the same time, the SnO2(D) has
also the largest overpotential for the reduction of I3−,
Co(bpy)33+, and Cu(tmby)22+. These beneficial properties
are promising for both the dye-sensitized and perovskite solar
cells. However, SnO2(D) is also quite sensitive to calcination
when these reduction overpotentials strongly drop and
ultrasmall cracks (permeable selectively to I−) appear in the
film.
Systematic screening of all the layers, together with the
reference materials, blank FTO and Pt, was carried out by
cyclic voltammetry in six different electrolyte solutions,
relevant to DSSC applications. It provided detailed informa-
tion about the mediator type, namely, I3−/I−, Co(III/II),
Cu(II/I), and effects of calcination and the presence of 4-tert-
butylpyridine. The latter effect is boosted in Cu(II/I)-
containing solution in which the collective influence of
coordination of TBP to copper and adsorption to TiO2 are
at play.
The overvoltages for cathodic reduction of redox mediators
on TiO2 or SnO2 generally increase in the series Co(III/II) <
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I3−/I− < Cu(II/I). For each particular redox mediator, the
cathodic overvoltages line up in the series FTO < SnO2 <
TiO2(A) ≈ TiO2(R) < SnO2(D). Independent of the electrode
material and mediator type, the overvoltages are always
enhanced in the presence of TBP. The flat band potentials
and cathodic overvoltages tend to scale linearly, but the
material-specific (electrocatalytic) effects can influence this
correlation, too.
■
*
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.jpcc.9b11883.
Equivalent circuit for fitting of electrochemical impe-
dance data, additional electrochemical data (cyclic
voltammograms), Mott−Schottky plots, XPS spectra,
and SEM images (PDF)
■
AUTHOR INFORMATION
Corresponding Author
Ladislav Kavan − J. Heyrovsky Institute of Physical Chemistry,
Czech Acad Sci, Prague 8 182 23, Czech Republic; Laboratory
of Photonics and Interfaces, Institute of Chemical Sciences and
Engineering, É cole Polytechnique Fédérale de Lausanne,
Lausanne 1015, Switzerland; orcid.org/0000-0003-3342-
4603; Email: kavan@jh-inst.cas.cz
Authors
Zuzana Vlckova Zivcova − J. Heyrovsky Institute of Physical
Chemistry, Czech Acad Sci, Prague 8 182 23, Czech Republic
Magda Zlamalova − J. Heyrovsky Institute of Physical
Chemistry, Czech Acad Sci, Prague 8 182 23, Czech Republic;
Department of Inorganic Chemistry, Faculty of Science, Charles
University in Prague, Prague 2 128 43, Czech Republic
Shaik M. Zakeeruddin − Laboratory of Photonics and
Interfaces, Institute of Chemical Sciences and Engineering, É cole
Polytechnique Fédérale de Lausanne, Lausanne 1015,
Switzerland
Michael Grätzel − Laboratory of Photonics and Interfaces,
Institute of Chemical Sciences and Engineering, É cole
Polytechnique Fédérale de Lausanne, Lausanne 1015,
Switzerland; orcid.org/0000-0002-0068-0195
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.jpcc.9b11883
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by the European Union’s Horizon
2020 Research and Innovation Program under grant agreement
no. 826013. LK thanks the Grant Agency of the Czech
Republic (contract no. 18-08959S) for financial support. We
thank Dr. Yameng Ren and Dr. Dan Ren for their help in
preparing some TiO2 and SnO2 films.
■ REFERENCES
(1) Burke, A.; Ito, S.; Snaith, H.; Bach, U.; Kwiatkowski, J.; Grätzel,
M. The Function of a TiO2 Compact Layer in Dye-Sensitized Solar
Cells Incorporating “Planar” Organic Dyes. Nano Lett. 2008, 8, 977−
981.
https://dx.doi.org/10.1021/acs.jpcc.9b11883
J. Phys. Chem. C 2020, 124, 6512−6521
The Journal of Physical Chemistry C
(2) Cameron, P. J.; Peter, L. M. Characterization of Titanium
Dioxide Blocking Layers in Dye-Sensitized Nanocrystalline Solar
Cells. J. Phys. Chem. B 2003, 107, 14394−14400.
(3) Hagfeldt, A.; Boschloo, G.; Sun, L.; Kloo, L.; Pettersson, H. Dye-
Sensitized Solar Cells. Chem. Rev. 2010, 110, 6595−6663.
(4) Cameron, P. J.; Peter, L. M.; Hore, S. How Important is the Back
Reaction of Electrons via the Substrate in Dye-Sensitized Nano-
crystalline Solar Cells? J. Phys. Chem. B 2005, 109, 930−936.
(5) Kavan, L. Electrochemistry and Dye-sensitized Solar Cells. Curr.
Opin. Electrochem. 2017, 2, 88−96.
(6) Correa-Baena, J. P.; Abate, A.; Saliba, M.; Tress, W.; Jesper
Jacobsson, T.; Grätzel, M.; Hagfeldt, A. The Rapid Evolution of
Highly Efficient Perovskite Solar Cells. Energy Environ. Sci. 2017, 10,
710−727.
(7) Stockhausen, V.; Mesquita, I.; Andrade, L.; Mendes, A. Insights
in Perovskite Solar Cell Fabrication: Unraveling the Hidden
Challenges of Each Layer. IEEE J. Photovoltaics 2018, 8, 1029−1038.
(8) Kavan, L. Electrochemistry and Perovskite Photovoltaics. Curr.
Opin. Electrochem. 2018, 11, 122−129.
(9) Nonomura, K.; Vlachopoulos, N.; Unger, E.; Häggman, L.;
Hagfeldt, A.; Boschloo, G. Blocking the Charge Recombination with
Diiodide Radicals by TiO2 Compact Layer in Dye-sensitized Solar
Cells. J. Electrochem. Soc. 2019, 166, B3203−B3208.
(10) Xia, J.; Masaki, N.; Jiang, K.; Yanagida, S. Deposition of a Thin
Film of TiOx from a Titanium Metal Target as Novel blocking Layers
at Conducting glass/TiO2 Interfaces in Ionic Liquid Mesoscopic TiO2
Dye-sensitized Solar Cells. J. Phys. Chem. B 2006, 110, 25222−25228.
(11) Nazeeruddin, M. K.; Kay, A.; Rodicio, I.; Humphry-Baker, R.;
Mueller, E.; Liska, P.; Vlachopoulos, N.; Graetzel, M. Conversion of
Light to Electricity by cis-X2bis(2,2’-bipyridyl-4,4’-dicarboxylate)-
ruthenium(II) Charge-Transfer Sensitizers (X = Cl-, Br-, I-, CN-,
and SCN-) on Nanocrystalline Titanium Dioxide Electrodes. J. Am.
Chem. Soc. 1993, 115, 6382−6390.
(12) O’Regan, B.; Grätzel, M. A Low-Cost, High-Efficiency Solar
Cell Based on Dye-Sensitized colloidal TiO2 films. Nature 1991, 353,
737−740.
(13) Kavan, L.; O’Regan, B.; Kay, A.; Grätzel, M. Preparation of
TiO2 (Anatase) Films on Electrodes by Anodic Oxidative Hydrolysis
of TiCl3. J. Electroanal. Chem. 1993, 346, 291−307.
(14) Kavan, L.; Grätzel, M. Highly Efficient Semiconducting TiO2
Photoelectrodes Prepared by Aerosol Pyrolysis. Electrochim. Acta
1995, 40, 643−652.
(15) Krýsová, H.; Krýsa, J.; Kavan, L. Semi-automatic Spray
Pyrolysis Deposition of Thin, Transparent, Titania Films as Blocking
Layers for Dye-sensitized and Perovskite Solar Cells. Beilstein J.
Nanotechnol. 2018, 9, 1135−1145.
(16) Hurum, D. C.; Agrios, A. G.; Gray, K. A.; Rajh, T.; Thurnauer,
M. C. Explaining the Enhanced Photocatalytic Activity of Degussa
P25 Mixed-phase TiO2 Using EPR. J. Phys. Chem. B 2003, 107,
4545−4549.
(17) Wang, P.; Shao, Z.; Ulfa, M.; Pauporté, T. Insights into the
Hole Blocking Layer Effect on the Perovskite Solar Cell Performance
and Impedance Response. J. Phys. Chem. C 2017, 121, 9131−9141.
(18) Yella, A.; Heiniger, L.-P.; Gao, P.; Nazeeruddin, M. K.; Grätzel,
M. Nanocrystalline Rutile Electron Extraction Layer Enables Low-
temperature Solution Processed Perovskite Photovoltaics with 13.7%
Efficiency. Nano Lett. 2014, 14, 2591−2596.
(19) Liu, I. P.; Lin, W. H.; Tseng-Shan, C. M.; Lee, Y. L. Importance
of Compact Blocking Layers to the Performance of Dye-Sensitized
Solar Cells under Ambient Light Conditions. ACS Appl. Mater.
Interfaces 2018, 10, 38900−38905.
(20) Masood, M. T.; Weinberger, C.; Sarfraz, J.; Rosqvist, E.;
Sandén, S.; Sandberg, O. J.; Vivo, P.; Hashmi, G.; Lund, P. D.;
Ö sterbacka, R.; Smått, J.-H. Impact of Film Thickness of Ultrathin
Dip-Coated Compact TiO2 Layers on the Performance of Mesoscopic
Perovskite Solar Cells. ACS Appl. Mater. Interfaces 2017, 9, 17906−
17913.
6520
pubs.acs.org/JPCC Article
(21) Kavan, L.; Tétreault, N.; Moehl, T.; Grätzel, M. Electro-
chemical Characterization of TiO2 Blocking Layers for Dye-Sensitized
Solar Cells. J. Phys. Chem. C 2014, 118, 16408−16418.
(22) Yum, J. H.; Moehl, T.; Yoon, J.; Chandiran, A. K.; Kessler, F.;
Gratia, P.; Grätzel, M. Toward higher photovoltage: Effect of Blocking
Layer on Cobalt Bipyridine Pyrazole Complexes as Redox Shuttle for
Dye-Sensitized Solar Cells. J. Phys. Chem. C 2014, 118, 16799−16805.
(23) Amini, M.; Keshavarzi, R.; Mirkhani, V.; Moghadam, M.;
Tangestaninejad, S.; Mohammadpoor-Baltork, I.; Sadegh, F. From
Dense Blocking Layers to Different Templated Films in Dye
Sensitized and Perovskite Solar Cells: Toward Light Transmittance
Management and Efficiency Enhancement. J. Mater. Chem. A 2018, 6,
2632−2642.
(24) Yum, J.-H.; Baranoff, E.; Kessler, F.; Moehl, T.; Ahmad, S.;
Bessho, T.; Marchioro, A.; Ghadiri, E.; Moser, J.-E.; Yi, C.;
Nazeeruddin, M. K.; Grätzel, M. Rationally Designed Cobalt
Complexes as Redox Shuttle for Dye-Sensitized Solar Cells to Exceed
1000 mV. Nat. Commun. 2012, 3, 631.
(25) Saygili, Y.; Söderberg, M.; Pellet, N.; Giordano, F.; Cao, Y.;
Muñoz-García, A. B.; Zakeeruddin, S. M.; Vlachopoulos, N.; Pavone,
M.; Boschloo, G.; Kavan, L.; Moser, J.-E.; Grätzel, M.; Hagfeldt, A.;
Freitag, M. Copper Bipyridyl Redox Mediators for Dye-Sensitized
Solar Cells with High Photovoltage. J. Am. Chem. Soc. 2016, 138,
15087−15096.
(26) Cao, Y.; Saygili, Y.; Ummadisingu, A.; Teuscher, J.; Luo, J.;
Pellet, N.; Giordano, F.; Zakeeruddin, S. M.; Moser, J.-E.; Freitag, M.;
Hagfeldt, A.; Grätzel, M. 11% Efficiency Solid-state Dye-sensitized
Solar Cells with Copper(II/I) Hole Transport Materials. Nat.
Commun. 2017, 8, 15390.
(27) Kavan, L.; Steier, L.; Grätzel, M. Ultrathin Buffer Layers of
SnO2 by Atomic Layer Deposition: Perfect Blocking Function and
Thermal Stability. J. Phys. Chem. C 2017, 121, 342−350.
(28) Kavan, L.; Vlčková-Ž ivcová, Z.; Hubík, P.; Arora, N.; Dar, M. I.;
Zakeeruddin, S. M.; Grätzel, M. Electrochemical Characterization of
CuSCN Hole-Extracting Thin Films for Perovskite Photovoltaics.
ACS Appl. Energy Mater. 2019, 2, 4264−4273.
(29) Cao, Y.; Liu, Y.; Zakeeruddin, S. M.; Hagfeldt, A.; Grätzel, M.
Direct Contact of Selective Charge Extraction Layers Enables High-
Efficiency Molecular Photovoltaics. Joule 2018, 2, 1108−1117.
(30) Li, W.; Liu, C.; Zhou, Y.; Bai, Y.; Feng, X.; Yang, Z.; Lu, L.; Lu,
X.; Chan, K.-Y. Enhanced Photocatalytic Activity in Anatase/TiO2(B)
Core−Shell Nanofiber. J. Phys. Chem. C 2008, 112, 20539−20545.
(31) Chen, Y.; Meng, Q.; Zhang, L.; Han, C.; Gao, H.; Zhang, Y.;
Yan, H. SnO2-based Electron Transporting Layer Materials for
Perovskite Solar Cells: A Review of Recent Progress. J. Energy Chem.
2019, 35, 144−167.
(32) Jeong, S.; Seo, S.; Park, H.; Shin, H. Atomic Layer Deposition
of a SnO2 Electron-transporting Layer for Planar Perovskite Solar
Cells with a Power Conversion Efficiency of 18.3%. Chem. Commun.
2019, 55, 2433−2436.
(33) Zhang, G.; Yang, D.; Sacher, E. X-ray Photoelectron
Spectroscopic Analysis of Pt Nanoparticles on Highly Oriented
Pyrolytic Graphite, Using Symmetric Component Line Shapes. J.
Phys. Chem. C 2007, 111, 565−570.
(34) Aygüler, M. F.; Hufnagel, A. G.; Rieder, P.; Wussler, M.;
Jaegermann, W.; Bein, T.; Dyakonov, V.; Petrus, M. L.; Baumann, A.;
Docampo, P. Influence of Fermi Level Alignment with Tin Oxide on
the Hysteresis of Perovskite Solar Cells. ACS Appl. Mater. Interfaces
2018, 10, 11414−11419.
(35) Anaraki, E. H.; Kermanpur, A.; Steier, L.; Domanski, K.;
Matsui, T.; Tress, W.; Saliba, M.; Abate, A.; Grätzel, M.; Hagfeldt, A.;
Correa-Baena, J. P. Highly Efficient and Stable Planar Perovskite Solar
cells by Solution-processed Tin Oxide. Energy Environ. Sci. 2016, 9,
3128−3134.
(36) Tavakoli, M. M.; Saliba, M.; Yadav, P.; Holzhey, P.; Hagfeldt,
A.; Zakeeruddin, S. M.; Grätzel, M. Synergistic Crystal and Interface
Engineering for Efficient and Stable Perovskite Photovoltaics. Adv.
Energy Mater. 2019, 9, 1802646.
https://dx.doi.org/10.1021/acs.jpcc.9b11883
J. Phys. Chem. C 2020, 124, 6512−6521
The Journal of Physical Chemistry C
(37) Roose, B.; Baena, J.-P. C.; Gödel, K. C.; Graetzel, M.; Hagfeldt,
A.; Steiner, U.; Abate, A. Mesoporous SnO2 Electron Selective
Contact Enables UV-stable Perovskite Solar Cells. Nano Energy 2016,
30, 517−522.
(38) Hsu, C. H.; Mansfeld, F. Technical Note: Concerning the
Conversion of the Constant Phase Element Parameter Y0 into a
Capacitance. Corrosion 2001, 57, 747−748.
(39) Berger, T.; Monllor-Satoca, D.; Jankulovska, M.; Lana-
Villarreal, T.; Gómez, R. The Electrochemistry of Nanostructured
Titanium Dioxide Electrodes. ChemPhysChem 2012, 13, 2824−2875.
(40) Frank, O.; Zukalova, M.; Laskova, B.; Kürti, J.; Koltai, J.; Kavan,
L. Raman Spectra of Titanium Dioxide (Anatase, Rutile) with
Identified Oxygen Isotopes (16, 17, 18). Phys. Chem. Chem. Phys.
2012, 14, 14567−14572.
(41) Krysova, H.; Zlamalova, M.; Tarabkova, H.; Jirkovsky, J.; Frank,
O.; Kohout, M.; Kavan, L. Rutile TiO2 Thin Film Electrodes with
Excellent Blocking Function and Optical Transparency. Electrochim.
Acta 2019, 321, 134685.
(42) Bonu, V.; Gupta, B.; Chandra, S.; Das, A.; Dhara, S.; Tyagi, A.
K. Electrochemical Supercapacitor Performance of SnO2 Quantum
Dots. Electrochim. Acta 2016, 203, 230−237.
(43) Wu, J.; Lan, Z.; Lin, J.; Huang, M.; Huang, Y.; Fan, L.; Luo, G.
Electrolytes in Dye-Sensitized Solar Cells. Chem. Rev. 2015, 115,
2136−2173.
(44) Kavan, L.; Saygili, Y.; Freitag, M.; Zakeeruddin, S. M.; Hagfeldt,
A.; Grätzel, M. Electrochemical Properties of Cu(II/I)-Based Redox
Mediators for Dye-Sensitized Solar Cells. Electrochim. Acta 2017, 227,
194−202.
(45) Saygili, Y.; Stojanovic, M.; Michaels, H.; Tiepelt, J.; Teuscher,
J.; Massaro, A.; Pavone, M.; Giordano, F.; Zakeeruddin, S. M.;
Boschloo, G.; Moser, J.-E.; Grätzel, M.; Muños-García, A. B.;
Hagfeldt, A.; Freitag, M. Effect of Coordination Sphere Geometry
of Copper Redox Mediators on Regeneration and Recombination
Behavior in Dye-Sensitized Solar Cell Applications. ACS Appl. Energy
Mater. 2018, 1, 4950−4962.
(46) Ferdowsi, P.; Saygili, Y.; Zakeeruddin, S. M.; Mokhtari, J.;
Grätzel, M.; Hagfeldt, A.; Kavan, L. Alternative Bases to 4-tert-
butylpyridine for Dye-sensitized Solar cells Employing Copper Redox
Mediator. Electrochim. Acta 2018, 265, 194−201.
(47) Boschloo, G.; Häggman, L.; Hagfeldt, A. Quantification of the
Effect of 4-tert-butylpyridine addition to I‑/I3‑ Redox Electrolytes in
Dye-sensitized Nanostructured TiO2 Solar Cells. J. Phys. Chem. C
2006, 110, 13144−13150.
(48) Kim, J.-Y.; Kim, J. Y.; Lee, D.-K.; Kim, B.; Kim, H.; Ko, M. J.
Importance of 4-tert-butylpyridine in Electrolyte for Dye-sensitized
Solar Cells Employing SnO2 Electrode. J. Phys. Chem. C 2012, 116,
22759−22766.
(49) Kwoka, M.; Ottaviano, L.; Passacantando, M.; Santucci, S.;
Czempik, G.; Szuber, J. XPS Study of the Surface Chemistry of L-
CVD SnO2 Thin Films after Oxidation. Thin Solid Films 2005, 490,
36−42.
(50) Park, M.; Kim, J. Y.; Son, H. J.; Lee, C. H.; Jang, S. S.; Ko, M. J.
Low-temperature Solution-processed Li-doped SnO2 as an Effective
Electron Transporting Layer for High-performance Flexible and
Wearable Perovskite Solar Cells. Nano Energy 2016, 26, 208−215.
(51) Park, J. W.; Park, C. M. A Fundamental Understanding of Li
Insertion/Extraction Behaviors in SnO and SnO2. J. Electrochem. Soc.
2015, 162, A2811−A2816.
(52) Dixon, D.; Á vila, M.; Ehrenberg, H.; Bhaskar, A. Difference in
Electrochemical Mechanism of SnO2 Conversion in Lithium-Ion and
Sodium-Ion Batteries: Combined in Operando and Ex Situ XAS
Investigations. ACS Omega 2019, 4, 9731−9738.
(53) Baena, J. P. C.; Steier, L.; Tress, W.; Saliba, M.; Neutzner, S.;
Matsui, T.; Giordano, F.; Jacobsson, T. J.; Kandada, A. R. S.;
Zakeeruddin, S. M.; Petrozza, A.; Abate, A.; Nazeeruddin, M. K.;
Grätzel, M.; Hagfeldt, A. Highly Efficient Planar Perovskite Solar
Cells Through Band Alignment Engineering. Energy Environ. Sci.
2015, 8, 2928−2934.
6521
pubs.acs.org/JPCC Article
(54) Kavan, L.; Grätzel, M.; Gilbert, S. E.; Klemenz, C.; Scheel, H. J.
Electrochemical and Photoelectrochemical Investigation of Single-
Crystal Anatase. J. Am. Chem. Soc. 1996, 118, 6716−6723.
(55) Moehl, T.; Suh, J.; Sévery, L.; Wick-Joliat, R.; Tilley, S. D.
Investigation of (Leaky) ALD TiO2 Protection Layers for Water-
Splitting Photoelectrodes. ACS Appl. Mater. Interfaces 2017, 9,
43614−43622.
(56) Schulz, P.; Edri, E.; Kirmayer, S.; Hodes, G.; Cahen, D.; Kahn,
A. Interface Energetics in Organo-metal Halide Perovskite-based
Photovoltaic Cells. Energy Environ. Sci. 2014, 7, 1377−1381.
(57) Kashiwaya, S.; Morasch, J.; Streibel, V.; Toupance, T.;
Jaegermann, W.; Klein, A. The Work Function of TiO2. Surfaces
2018, 1, 73−89.
(58) Balajka, J.; Hines, M. A.; DeBenedetti, W. J. I.; Komora, M.;
Pavelec, J.; Schmid, M.; Diebold, U. High-affinity Adsorption Leads to
Molecularly Ordered Interfaces on TiO2 in Air and Solution. Science
2018, 361, 786−789.
(59) Boschloo, G.; Hagfeldt, A. Characteristics of the Iodide/
triiodide Redox Mediator in Dye-sensitized Solar Cells. Acc. Chem.
Res. 2009, 42, 1819−1826.
(60) Redmond, G.; Fitzmaurice, D. Spectroscopic Determination of
Flatband Potentials for Polycrystalline Titania Electrodes in Non-
aqueous Solvents. J. Phys. Chem. 1993, 97, 1426−1430.
(61) Jung, H. S.; Kim, H. Origin of Low Photocatalytic Activity of
Rutile TiO2. Electron. Mater. Lett. 2009, 5, 73−76.
(62) Kavan, L. Conduction Band Engineering in Semiconducting
Oxides (TiO2, SnO2): Applications in Perovskite Photovoltaics and
Beyond. Catal. Today 2019, 328, 50−56.
(63) Kullgren, J.; Aradi, B.; Frauenheim, T.; Kavan, L.; Deák, P.
Resolving the Controversy About the Band Alignment Between Rutile
and Anatase: the Role of OH‑/H+ Adsorption. J. Phys. Chem. C 2015,
119, 21952−21958.
(64) Deák, P.; Kullgren, J.; Aradi, B.; Frauenheim, T.; Kavan, L.
Water Splitting and the Band Edge Positions of TiO2. Electrochim.
Acta 2016, 199, 27−34.
(65) Scanlon, D. O.; Dunnill, C. W.; Buckeridge, J.; Shevlin, S. A.;
Logsdail, A. J.; Woodley, S. M.; Catlow, C. R. A.; Powell, M. J.;
Palgrave, R. G.; Parkin, I. P.; Watson, G. W.; Keal, T. W.; Sherwood,
P.; Walsh, A.; Sokol, A. A. Band Alignment of Rutile and Anatase
TiO2. Nat. Mater. 2013, 12, 798−801.
(66) Quesada-Cabrera, R.; Sotelo-Vazquez, C.; Bear, J. C.; Darr, J.
A.; Parkin, I. P. Photocatalytic Evidence of the Rutile-to-Anatase
Electron Transfer in Titania. Adv. Mater. Interfaces 2014, 1, 1400069.
(67) Akin, S. Hysteresis-Free Planar Perovskite Solar Cells with a
Breakthrough Efficiency of 22% and Superior Operational Stability
over 2000 h. ACS Appl. Mater. Interfaces 2019, 11, 39998−40005.
(68) Kashiwaya, S.; Toupance, T.; Klein, A.; Jaegermann, W. Fermi
Level Positions and Induced Band Bending at Single Crystalline
Anatase (101) and (001) Surfaces: Origin of the Enhanced
Photocatalytic Activity of Facet Engineered Crystals. Adv. Energy
Mater. 2018, 8, 1802195.
(69) Pfeifer, V.; Erhart, P.; Li, S.; Rachut, K.; Morasch, J.; Brötz, J.;
Reckers, P.; Mayer, T.; Rühle, S.; Zaban, A.; Mora Seró, I.; Bisquert,
J.; Jaegermann, W.; Klein, A. Energy Band Alignment Between
Anatase and Rutile TiO2. J. Phys. Chem. Lett. 2013, 4, 4182−4187.
(70) Nebel, R.; Macounová, K. M.; Tarábková, H.; Kavan, L.; Krtil,
P. Selectivity of Photoelectrochemical Water Splitting on TiO2
Anatase Single Crystals. J. Phys. Chem. C 2019, 123, 10857−10867.
https://dx.doi.org/10.1021/acs.jpcc.9b11883
J. Phys. Chem. C 2020, 124, 6512−6521