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Characterization techniques for dye-sensitized

solar cells
Cite this: Energy Environ. Sci.,
2017, 10, 672
Meysam Pazoki,a Ute B. Cappel,b Erik M. J. Johansson,a Anders Hagfeldtac and
Gerrit Boschloo*a

Received 20th September 2016,
Accepted 23rd December 2016
DOI: 10.1039/c6ee02732f
rsc.li/ees
Dye-sensitized solar cells (DSCs) have been widely studied in the last two decades and start to be
commercialized in the photovoltaic market. Comprehensive characterization is needed to fully understand
and optimize the device performance and stability. In this review, we summarize different characterization
methods for dye-sensitized solar cells with liquid redox electrolytes or solid state hole transporting
materials, most of which can also be used for similar devices such as perovskite based thin film solar cells.
Limitations and advantages of relevant methods for studying the energy levels and time scales involved
in charge transfer processes as well as charge transport related characteristic lengths are discussed.
A summary of recent developments in DSCs and the importance of measured parameters for the device
optimization procedure are mentioned at the end.

Broader context
Solar energy is a potential candidate to supply the future energy demands with low environmental impact. Dye-sensitized solar cells (DSCs) are a class of solar
cells which are highly efficient in low light and under indoor conditions, with the possibility for low cost fabrication, utilization of flexible substrates and for
colorful and transparent devices. Due to the different working principles in comparison to other solar cell technologies, many techniques have been used to
characterize the function of DSCs and to understand their properties. However, the understanding of the working mechanism of DSCs is not complete yet, and
further improvement of device efficiencies requires a deeper understanding of the materials and processes in DSCs. Therefore, new methods are continuously
being developed for the characterization of DSCs to understand how further improvements can be achieved. In this review paper, we summarize the
characterization techniques for DSCs in a pedagogical way and also include newly developed techniques that are important for the future development of DSCs.

1. Introduction
Dye-sensitized solar cells have been widely studied in the last
two decades and start to be commercialized in the photovoltaic
market. Stability, performance, production cost and colour are
the main factors that are considered for the commercialization
of dye sensitized solar cells (DSCs).1 The number of registered
patents in the DSC field grew exponentially year by year reaching
the number of 400 in year 2010.2 So far the topic of new
materials has received the most attention in DSC related patents;
materials of interest have been tested in order to improve the
stability and efficiency and reduce the production costs.3–7
A full understanding of the processes occurring in DSCs
is necessary for further optimization and stabilization of the
a
Department of Chemistry Ångström Laboratory, Uppsala University, Box 523,
SE 75120 Uppsala, Sweden. E-mail: gerrit.boschloo@kemi.uu.se
b
Division of Molecular and Condensed Matter Physics, Department of Physics and
Astronomy, Uppsala University, Box 516, 751 20 Uppsala, Sweden
c
Labratoary of Photomolecular Science, École Polytechnique Fédérale de Lausanne,
SB-ISIC-LSPM, Chemin des Alambics, Station 6, CH G1 523, CH-1015 Lausanne,
Switzerland
device while the current picture is far from complete and still
there are un-answered questions especially in the dye/electrolyte/
semiconductor interface6,8–10
Implementation of standard characterization methods is
inevitable to elucidate and understand the impacts of each
device component on the photovoltaic performance, and also
elaborate the processes occurring in the stability tests such
as ongoing chemical reactions under long term heating or
light illumination conditions. Considering the DSC as a mole-
cular device, energy levels and time scales of electron transfer
processes are crucial parameters for estimation of device
operation and performance. Besides, optimization of device
components towards the best stabilities and efficiencies, also
understanding of how overall device efficiency is related to each
component and how each component can affect the others
can be only accomplished through proper characterization of
the device.
Characterization methods for DSCs have been developed
from the first years of their invention by Michael Grätzel and
Brian O’Regan,11 however limitations and reliability and the degree
of non-destructivity of each method have not been comprehensively

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explored yet. A review of the DSC characterization methods is
the topic of the present paper.
There are few reviews about the characterization of DSCs in
the literature in which much attention is devoted to a special
technique in detail.12–18 Snaith and Yang et al. have reported
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separately about reliable solar cell efficiency measurements.12,13
Takagi et al. have reported about the IPCE and current–voltage
characteristics.14 Barnes et al. have published a review about the
photo voltage/current transient and charge extraction methods15
and a review about electrochemical impedance spectroscopy in
dye-sensitized solar cells has been published by Fabregat et al.16
Moreover, Johansson et al. have reviewed the application of X-ray
photoelectron spectroscopy (XPS) in DSC characterization17 and
Katoh et al. wrote a review about electron injection efficiency
measurements in DSCs.18 In this review we will give an overview
and comparison of all the most relevant characterization tech-
niques and how to apply them to obtain relevant information for
device optimization. The emphasis of the presented content is
on the device characterization, reliability of each method and
optimization of the related energy levels/charge transfer time
scales. The outline of the paper is as follows: in Section 2 we have
a short summary of liquid DSC working conditions, compo-
nents, energy levels and timescales and introduce the important
processes which should be characterized. Almost the same
arguments can be used for ssDSCs considering in mind that
hole conduction occurs within the hole conductor rather than
the liquid electrolyte. Section 3 describes the general techni-
ques for material characterization of DSC components such as
electron microscopy, X-ray photoelectron spectroscopy, scanning
tunnelling microscopy, UV-Vis, Raman and FTIR spectroscopies,
conductivity measurements and electrochemical methods.
Section 4 represents the most important characterization methods
for solar cells: voltage–current and IPCE. Special points for
From right: Erik M. J. Johansson, Meysam Pazoki,
Gerrit Boschloo and Ute B. Cappel
Dr Gerrit Boschloo has more than 20 years of research experience in dye-sensitized solar cells. He leads a research group on hybrid solar cells
within physical chemistry at Uppsala University. Besides DSCs, his research topics include advanced photoelectrochemical characterization
of semiconductors and perovskite solar cells. He authored more than 190 publications. Dr Ute Cappel received her PhD in Chemistry at
Uppsala University in 2011. Following a Marie-Curie fellow at Imperial College London, she is currently a researcher at the Department of
Physics and Astronomy at Uppsala University. Her research focuses on the characterization of molecular solar cells, in particular by time-
resolved and X-ray based spectroscopies.
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proper evaluation of the efficiency are mentioned subsequently.
Photo-induced spectroscopy and voltage/current modulation
techniques are investigated in Sections 5 and 6. Section 7 is
devoted to final remarks about the DSC (liquid, quasi solid
state and solid state) development trends and a summary and
conclusion is mentioned at the end in which some stability
measurements are also discussed.
2. Dye-sensitized solar cells
2.1 Device components
The conventional liquid electrolyte based DSC is a two electrode
electrochemical cell in which the counter electrode is fluorine
doped tin oxide conductive glass (FTO) coated with a thin layer of
the platinum catalyst. The working electrode is a mesoporous
layer of titanium dioxide nanoparticles coated on FTO onto which
a monolayer of dye molecules is adsorbed. A blocking layer of
dense TiO2 may be pre-coated on the FTO to prevent recom-
bination at the FTO substrate/electrolyte interface. The two
electrodes are sealed together by polymer sealants and a liquid
electrolyte, consisting of the redox mediator, additives and the
solvent fills the space between the electrodes.11 Incoming visible
light is transmitted by the transparent FTO and wide band gap
TiO2 films, but absorbed by the dye molecules. The excited dye
molecules inject electrons into the TiO2 conduction band (CB).
The oxidized dye molecules are subsequently regenerated by
electron transfer from the redox mediator to dyes. Electrons
in the mesoporous TiO2 and positive charges (‘holes’) in the
electrolyte diffuse to the FTO back contact and counter electrode,
respectively. The difference between the Fermi levels of the
working and the counter electrode (the latter is defined by the
redox potential of the redox mediator at the counter electrode
interface and the former is defined by the TiO2 Fermi level at
From right: Dr Erik Johansson received his PhD degree in Physics
at Uppsala University in 2006. After postdoctoral work at Lund
University, he was an assistant professor at Uppsala University. He
is currently an associate professor in Physical Chemistry at Uppsala
University. His research field is nanostructured solar cells including
perovskite, quantum dot and dye-sensitized solar cells. His research
is spanning from understanding the fundamental processes and the
atomic scale structure in these solar cells to the function of the full
devices. Dr Meysam Pazoki completed his PhD in Physics at Sharif
University of Technology in 2012. He then moved to Uppsala
University, where he has held postdoctoral positions in the group
of A. Hagfeldt and G. Boschloo. Currently he is a researcher in the
Chemistry department at Uppsala University. His experimental–
theoretical research focuses on photo-physics, device characterization
and DFT calculations of dye and perovskite solar cell materials.
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Fig. 1 Schematic diagram of the DSC device.
the FTO interface) under illumination results in the electric
potential difference between the electrodes by which one can
operate electronic devices.6 Fig. 1 shows the schematic of a
liquid based device based on the cobalt redox mediator. In solid
state dye-sensitized solar cells (ssDSCs), a solid hole conductor
replaces the liquid electrolyte, regenerates the dye molecules
and conducts the holes to the back contact of the solar cell
which is a metallic layer of silver or gold.19,20 The Fermi level
difference between the working electrode and back contact
is equivalent to the potential difference of two electrodes in
ssDSCs. In quasi solid state dye solar cells (qssDSCs),21–23 a
polymer or a gel electrolyte is implemented instead of a liquid
electrolyte in order to improve the long term stability of the
device. The same concepts, the energy levels, and charge transfer
phenomena are valid for qssDSCs as well.
2.2 Device operation and timescales of the processes
Different operational processes in DSCs are illustrated in Fig. 2.
Favourable processes such as dye photon absorption resulting
in the excitation of an electron from the highest occupied
molecular orbital (HOMO) to the lowest unoccupied molecular
orbital (LUMO) (1), electron injection from the LUMO to the
Anders Hagfeldt is a Professor
in Physical Chemistry at EPFL,
Switzerland. He obtained his PhD
at Uppsala University in 1993 and
was a post-doc with Prof. Michael
Grätzel (1993–1994) at EPFL. His
research focuses on the fields of
dye-sensitized and perovskite solar
cells, and solar fuels. He has pub-
lished more than 400 articles with
over 36 000 citations (h-index 95).
He is a member of the European
Academy of Sciences, Royal Swedish
Anders Hagfeldt
Academy of Sciences, Royal Society
of Sciences in Uppsala, and the Royal Swedish Academy of Engineering
Sciences. He is a visiting professor at Uppsala University and Nanyang
Technological University, Singapore.
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Fig. 2 Schematic of the electron transfer processes in a liquid electrolyte
DSC.
TiO2 CB (2), dye regeneration by the redox mediators (or hole
conductor) (3) and electron/hole transport in the TiO2/electrolyte
(or hole conductor layer) (4) should therefore be optimized in
terms of energy levels and timescales. There are unfavourable
processes (shown by red arrows) consisting of electron recombi-
nation to the oxidized species of the dye (5) and the electrolyte
(or the oxidized hole conductor) (6) and de-excitation of the dye
excited state (7). Minimization of the unfavourable processes
is also vital for optimization of device performance. All these
processes are coupled together and therefore replacement of one
component can have simultaneous impacts on different favour-
able or unfavourable processes. Description of these processes
and their relation to the device component energy levels have
been investigated previously and are summarized in several
comprehensive reviews.6,24,25
Under operating conditions there are competitions between
the favourable and unfavourable processes:
(1) Electron injection competes with de-excitation of the
dye. Different dyes have different time constants for injection/
luminescence phenomena. Shorter injection times and longer
luminescence life times are favourable for better device perfor-
mance. The position and the nature of dye LUMO levels and
TiO2 CB states, length and nature of the dye acceptor ligand, the
adsorption mode of the dye on the TiO2 surface, the presence of
adsorbed species at the interface i.e. Li+ ions and the dye/TiO2
surrounding medium can affect the injection rates from the dye to
the TiO2 CB according to the Marcus theory.26–29 The nature and
position of dye HOMO/LUMO levels and the surrounding medium
of the dye can affect the transition probabilities for de-excitation of
the dye.30,31 In typical DSCs, electron injection occurs on the time
scale of femto to pico seconds, while luminescence life times of
typical ruthenium18 and organic32 sensitizers are in the range of
nanoseconds and sub nanoseconds, respectively. The injection
efficiency (jinj) can thus be determined from the injection (kinj)
and relaxation (k0) rates as described in eqn (1).
kinj
jinj ¼ (1)
kinj þ k0
For simplicity of the discussion of all kinetics, all rate constants
are assumed to be (pseudo) first order, even though the true
kinetics may be more complex.
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(2) Electron collection versus electron recombination
Injected electrons inside TiO2 diffuse to the working elec-
trode contacts; it can be modelled by the random walk model.33
Typical diffusion coefficients in the mesoporous films depend
on the Fermi level position and are reported to be in the order
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of 103 to 106 cm2 per sin DSCs.34 Crystallite size, trap density
and its energy level position/physical location, porosity and
degree of disorder in the working electrode affect the effective
electron diffusion coefficient (and the corresponding transport
time).32–37 On the other hand recombination of electrons to the
oxidized dye or the oxidized redox mediator in the electrolyte
results in lowering the Fermi level and decreasing the current
and potential of the device. The time scale of the electron
collection inside the mesoporous TiO2 film is in the order of
milliseconds, while the recombination to the electrolyte under
open circuit conditions is in the order of a few ms.6 Faster
collection and slower recombination are favourable for better
device performances.
Depth and density of electronic traps in TiO2 and density of
electron acceptors in the electrolyte are important factors for
determination of the back reaction rate.38–41 Bisquert and co-
workers have performed detailed studies on the recombination
processes and their corresponding rates in DSCs.40,41 Recom-
bination of electrons to the oxidized dye is also important,
however it is less investigated.42–46 At the steady state, both
reactions (recombination versus collection) take place and depending
on the difference of these two rates, the device PCE would
change. The charge collection efficiency (jcol) depends on
the transport (ktr) and recombination (krec) rates and can be
defined as:
ktr
jcol ¼ (2)
ktr þ krec
The other important factor for charge collection is the dye
regeneration process which competes with oxidized dye recom-
bination. The time scale of dye regeneration is in the order of a
few microseconds and for electron recombination with the
oxidized dye is in the order of several hundred microseconds.
The regeneration rate (kreg) of the dye obeys the Marcus theory47
and is dependent on the nature and position of energy levels
of the dye as well as the electrolyte redox mediator and also
the surrounding solvent medium.48–51 For an efficient device,
regeneration efficiency (jreg) should be more than 95% and can
be defined as:
kreg
jreg ¼ (3)
kreg þ krec
Higher regeneration rates and lower recombination rates are
favourable for better device performance. Short circuit current
density ( Jsc) of DSCs is proportional to the product of injection,
collection and regeneration efficiencies (see Section 4.2). DSC
open circuit voltage (Voc) has a logarithmic dependence on the
steady state concentration of electrons40 which is dependent
on the regeneration and injection efficiencies.25 By detailed
characterization of the device and using eqn (1)–(3), one
can relate the estimated electron transfer rates of processes
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directly to current–voltage and power conversion efficiency (PCE)
of the device.25
2.3 Energy levels and the multi trapping model
A DSC is a molecular device in which the PCE depends a lot on
the energy levels of its components. The efficiency of the above
mentioned electron transfer processes depends on the energy
levels of donor and acceptor compounds. In the presence
of a liquid electrolyte the energy levels of the dye and excited
state dye molecules as well as redox mediators have Gaussian
shape distributions (shown in Fig. 2) which is described by the
Gerischer model52 (see Section 3.9). The electron diffusion
coefficient and transport inside the TiO2 mesoporous film
depend strongly on the density, location and position of the
semiconductor energy levels.53–55 Fig. 2 shows the typical energy
levels in the liquid based DSCs. Dye HOMO and LUMO energy
levels have key roles in the light absorption and efficiency of the
device. Considering the Shockley–Queisser limit for the photo-
voltaic absorbers, the efficiency of the device strongly depends on
the band gap of the absorber.56 Here, optical E0–0 transition of the
dye corresponds to the Eg fundamental gap of the semiconductor.
A smaller E0–0 distance leads to more light absorption by the dye
sensitizer. However, there are limitations for the dye energy
levels: in order to have an efficient and rapid electron injection
into the TiO2 CB and also rapid dye regeneration by redox
mediators, an over-potential of several hundreds mV between
the acceptor–donor species levels is needed. Therefore HOMO–
LUMO levels should be kept apart sufficiently.6,57 Marcus
theory can describe the electron transfer rates in the injection
or regeneration processes on which exponential dependence
of the electron transfer rate on the free energy difference of
acceptor/donor levels is expected.26 Description of Marcus theory
and its relation to DSCs (for example electron injection,28
recombination41 and dye regeneration58) is beyond the scope
of this article and further relevant information can be found
somewhere else.26,59,60
The TiO2 CB can be shifted and in fact tuned by interface
dipoles of surface treated films,61 the adsorbed dye molecule
dipoles62 and surface adsorbed charges or molecules from the
electrolyte.63 By shifting the TiO2 CB, the dye LUMO level should
be tuned respectively in order to have an efficient electron
injection. Moreover, electrolyte redox potential (E0) depends
strongly on the nature of redox mediators and the surrounding
ligands in the case of metal organic complexes. For having a
high open circuit potential, the dye HOMO level should be tuned
according to redox potential or vice versa in order to satisfy the
criterion of a high dye regeneration rate as well.57 Reported by
Feldt et al.,64 typical energy level values in standard cobalt
electrolyte based DSCs are +0.56, +1.04 and 1.14 V vs. NHE
for the redox potential of the cobalt bpy mediator, E0(D+/D) and
E0(D+/D*) energy levels of the D35 organic dye respectively. The
CB edge of TiO2 is considered as 0.5 V vs. NHE.65
Electron diffusion inside the mesoporous nanoparticles
obeys the continuous time random walk theory (CTRW). Jenny
Nelson has used the CTRW for DSCs for the first time to explain
the light intensity dependence of electron transport inside the
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TiO2 mesoporous films.33 In this theory the semiconductor

particles have intra band gap trap states placed in different
positions/locations in the energy/space. The traps have expo-
nential distribution of states below the CB:
 
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E  Ec
gðE Þ ¼ g0 exp  (4)
m c kB T

g is density of trap levels with energy level E, mc is trap depth

and Ec is the conduction band energy level.
Electrons will experience a random walk in between the traps
and diffuse to the working electrode contacts. After trapping
in trap states, electrons wait for a certain waiting time and are
de-trapped to the CB until they can be trapped again.33
Density and depth of the traps depend on the morphology
and preparation procedure of semiconductors66,67 and are
the determining factors for the electron transport inside the
film as well as for the electron lifetime and DSC open circuit
voltage.40,68–70 Lower trap densities cause less trapping–detrapping
processes and faster transport inside the film and thus allowing
the electrons to reach the electrode contacts efficiently before they
experience recombination processes.
Regarding the device efficiency, there are few studies about
estimation of maximum achievable efficiency for DSCs.25,71 The
33.7% upper limit of efficiency for thin film solar cells was
proposed initially by Shockley and Queisser (SQ) in 1961 by
considering the absorption of light and excitation of electrons
between the semiconductor energy levels, electron hole recom-
bination and the thermalization of hot charge carriers.56 Snaith
has estimated the highest obtainable efficiency for DSCs to
be 21%,71 lower than the SQ-limit because of the necessity of
over-potentials for efficient dye injection and regeneration.
Strategies of further improvements of the PCE from the current
record value of 14.7%72 can be pursued and are discussed in
Section 7.
3. Materials characterization
3.1 Electron microscopy
The mesoporous morphology of the working electrode is very
important for the device performance.5 Dye adsorption and
electron recombination are proportional to the working elec-
trode surface area. Electron transport and the effective diffusion
coefficient depend on the underlying structure of the working
electrode. One dimensional structures and branched structures
may have faster electron transport compared to nanoparticulate
films73–75 however the interface grain boundaries may limit the
conductivity.76
Scattering of high energy electron beams from the surface of
nanomaterials is the concept of scanning electron microscopy
(SEM) to study the surface morphology of nanostructures.77
SEM is the conventional and standard method for microscopy
studies of nanostructure film morphologies such as DSC working
and counter electrodes.78,79 Fig. 3 shows a typical SEM image of a
DSC mesoporous TiO2 film. Porosities of 50–65%, pore diameters
of 15–20 nm and particle sizes of 20–30 nm are typical and
convenient values for DSC working electrodes.80
Fig. 3 Typical SEM image of TiO2 mesoporous films in the DSC working
electrode. The mean pore size and particle size are 15 and 25 nm
respectively. Reprinted from Michael Grätzel, Journal of Photochemistry
and Photobiology C: Photochemistry Reviews, 2003, 4, 145. Copyright
(2003), with permission from Elsevier.
Thicknesses of the layers in a DSC can be measured by cross
sectional SEM which is the standard method to estimate the
thickness of solid state device layers.19 In solid state devices
the thickness of every layer such as the TiO2 porous film, the
blocking layer, the metal back contact and the hole conductor
capping layer directly affects the photovoltaic performance. The
dependence of open-circuit voltage (Voc) and hole conductivity
of ssDSCs on the thickness of TiO2 films was investigated by
Snaith et al.81,82 Both Voc and hole conductivity are reduced by
increasing the TiO2 film thickness while increasing the dye
loadings. Therefore high extinction coefficient dyes are employed
in the record efficiency ssDSCs.83 A typical cross sectional SEM
of a ssDSC is shown in Fig. 4. Furthermore, pixel contrast
histograms in cross sectional SEM images have also been used
for studying the pore filling of spiro OMeTAD (spiro) in ssDSCs;
sharper particle edges and pixels with more contrast show
uncovered TiO2 particles.84 Cross sectional SEM is still the most
common tool for estimation of pore filling and the thickness of
hole conductor capping layers; it can also be considered as a
method for evaluation of other relevant parameters for pore
filling studies in ssDSCs.82,85–87
Compared to the working electrode, the porosity of the
counter electrode is less important but in turn affects the
efficiency of the device. For example, using different electro-
chemical deposition routes for a PEDOT (poly(3,4-ethylene-
dioxythiophene)) counter electrode, Ellis et al. have obtained
Fig. 4 SEM cross section image of a typical ssDSC device showing the
layers of FTO/blocking layer (BL)/TiO2–dye–hole conductor/hole conductor
capping layer (CL)/silver back contact (SC). The scale bar is 1 micrometer.

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Fig. 5 EDAX analysis of the solid state device showing the uniform pene-
tration of perovskite hole conductor to the whole thickness of the film.
Reprinted by permission from Macmillan Publishers Ltd, Nature (485, 486),
Copyright (2012).
different porosities (investigated by SEM) and investigated
possible changes in electro-activity of the PEDOT counter electrode
in the device.88
Elemental analysis of the films can be done by energy
dispersive X-ray analysis (EDAX) along the whole thickness
of the films. Doping of the semiconductor, composition of
composites, co-sensitization of the different dyes along the
film thickness, pore filling of the hole conductor in ssDSCs
and coverage of perovskite absorber thin films can be studied
by EDAX analysis of the working electrode.89–91 Typical resolu-
tion of EDAX is in the order of several hundred nanometres.
Fig. 5 shows the EDAX analysis of a solar cell showing the
uniform penetration of a perovskite hole conductor in the
film.89
In transmission electron microscopy (TEM), the energy
of the electron beam is higher than in SEM and the electron
beam is transmitted through the sample which can be used to
determine detailed information about a material.92 Features as
small as a few nanometers can be observed using TEM. High
resolution transmission electron microscopy (HRTEM) can be
used to observe even finer details (single crystalline domains
and the lattice plane distances) of film crystalline planes as
low as a few Angstroms. Other methods such as atomic force
microscopy (AFM) are able to investigate the surface morphol-
ogy of a material but are not as common as SEM or TEM for the
DSC research field.
If the wavelength of the electron wave function is short
enough (in the case of a high energy electron beam) and in the
order of the sample lattice spacing, a diffraction pattern can be
formed by which one can study the reciprocal lattice of the
sample (called selected area electron diffraction, SAED). If the
sample is single crystalline, a series of dots will appear showing
the reciprocal lattice of the sample. If it is poly-crystalline, a
series of rings will appear. Information about the sample
crystal structure is therefore obtained from this technique.92
Fig. 6 shows the TEM picture of mesoporous microbeads as
well as the SAED pattern.93 Crystallite sizes and preferential
crystalline planes have crucial importance and impacts on
electron transport and adsorption of dyes on the particles.37,94
The effective catalytic activity of the counter electrode materials
depends strongly on the surface area and the details of
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Fig. 6 HRTEM graphs of the mesoporous microbeads and their SAED
patterns. Reprinted with permission from (Journal of American Chemical
Society, 132, 4438). Copyright (2010) American Chemical Society.
crystalline planes and defects on their surface have been
investigated using HRTEM and TEM.78,95
The TEM sample preparation method can have destructing
effects on the sample. In order to be investigated by TEM, the
nanostructured films should be scratched from the substrate
and therefore possible mechanical damage can be imposed on
the sample or new surface defects can be formed.
3.2 Brunauer–Emmett–Teller (BET) method
The BET method is the standard technique for estimation of
the mesoporous film porosity, pore size distribution and its
surface area per gram.96 BET theory is based on the physical
adsorption/desorption of the gas molecules (N2 inert gas as a
standard for this method) and determines the sample surface
area and pore volume. Studied by BET, it has been proposed that
more organised pore sizes enhance the efficiency of DSCs.97 BET
is the conventional method for evaluation of the surface area of
new particles/pastes for DSCs as well as new working electrode
preparation conditions.93,98,99 Dehong Chen et al. have synthe-
sized mesoporous microbeads with a high surface area and
porosity.93 The surface area per gram of the material can be
controlled by using different molar ratios of precursors in the
sol–gel step or by using different concentrations of ammonia in
the solvothermal step. BET has been used to characterize the
specific surface area per gram of the as synthesized materials.
By engineering the microbead pore size, Dehong Chen et al.
overcame the diffusion limited current in bulky cobalt electrolyte
based DSCs.100 Furthermore, Zhang et al. have studied the effect
of pore size distribution on the performance of polymer based
solid state DSCs in which the pore size has a direct effect on the
formation of in situ polymerized hole conductor layers in the
device.101 This method requires a large area of the material for
example some hundred milligrams of powder to be characterized
by BET.
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3.3 Scanning tunneling microscopy (STM)
In STM, 102,103
the sample is voltage-biased with respect to the
instrument tip which stands above the sample at a certain
distance. Scanning the sample by the tip and measuring the
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tunneling current between the tip and the sample give informa-
tion about the surface of the sample. Quantum mechanical
tunneling current is sensitive to the distance between the tip
and the sample surface on the sub nanometer scale. STM can
be used for observing the surface or adsorbate molecules (the
tunneling current will be different if the electron comes from
adsorbed molecules or the metal/semiconductor substrates) as
well as estimation of surface density of states.104
There are a few investigations of the dye adsorption on the
TiO2 surface reported using STM.105–110 Boschloo et al. have
investigated the surface coverage and adsorption of the N719
dye on the TiO2 surface. The dye covered the TiO2 surface
completely but the aggregation of the N719 dye was apparent as
spherical clusters of 2–4 nm size.107 Ikeda et al. investigated the
black dye adsorption on the TiO2(110) surface. Comparing the
adsorbed dye heights measured by STM with single dye heights
estimated by density functional theory (DFT) calculations, they
conclude two possible adsorption modes of the dye on the
surface.111
There are reviews about studying the adsorption modes of
the dye on different crystalline surfaces of TiO2 including the
theoretical investigations by DFT.110,112–114 The adsorption
mode of the dye is important not only from the stability issues
but also from the device performance point of view. Dyes with
bidentate adsorption mode are more difficult to be desorbed
from the TiO2 surface, if compared to monodentate mode with
the same anchoring group.115 Different binding modes result
in different bond lengths from the dye binding group to the
surface which affects the electron injection rate. Orientation of
the dye is also important for the cobalt electrolyte based DSCs
in terms of the electron lifetime within the device.116
Sasahara et al. studied the N3 dye adsorption on the TiO2(110)
crystal. Adsorption configurations with two carboxylate groups
bound to the surface are in agreement with the measured STM
image heights (Fig. 7).108
Fig. 7 STM images of pivalate precoated TiO2 films immersed in the
solution of the N3 dye for 1 and 10 minutes together with related dye
height distributions. Reprinted with permission from (Journal of Physical
Chemistry B, 110, 4751). Copyright (2006) American Chemical Society.
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K. Sakamaki et al. have used STM for studying the surface
density of states (SDOS) of the single crystalline TiO2(110) surface
and found a band gap of 1.6 eV for the rutile (110) surface.104 By
changing the bias voltage, from the current–voltage graph of
tunnelling current, (dI/dV)/(I/V) expression is responsible for the
SDOS of the film and it is independent of the tip to sample
distance. Song et al. have measured the SDOS of single TiO2
nanoparticles and explored its dependency on the particle size.117
One limitation of this method is the need for high vacuum
and very clean surfaces that necessitate a different adsorption
method for dye loading on the surface of TiO2, which is usually
accomplished by other methods than conventional solution
based methods.106 Also only a small area of a film is investigated.
Recently a new technique called scanning electrochemical
microscopy (SECM) has been used to study the dye regeneration
in liquid DSCs. SECM has a STM tip which is connected to a
potentiostat and the current of the STM tip can be coupled to
electrochemical measurements.49 Photo-assisted spatially resolved
STM has also been used for investigation of nanoporous traps and
their relevant effects on the current of DSC devices.118
3.4 Raman and FTIR spectroscopy
FTIR and Raman spectroscopy techniques are other methods for
studying the dye adsorption mode in which each dye binding
group has its own finger prints in the FTIR or the Raman
spectrum.119–121 Raman and FTIR methods can be utilized
for characterization of surface modifications or probing the
presence of any absorbed molecules on the surface of TiO2
electrodes122,123 or the characterization of the counter electrode
materials.124,125 They have been previously implemented to
monitor the evolution of surface adsorbate species during the
stability tests.126,127
By a relevant method called ultra high vacuum tip-enhanced
Raman spectroscopy, Raman spectra of a few single mole-
cules and even a single molecule adsorbed on a surface can be
acquired.128
3.5 X-Ray diffraction (XRD)
XRD is the conventional method for exploration of the crystal-
line structure of nanomaterials. The crystalline phase and
details of the working electrode semiconductor film lattice
structure are determined by XRD. The XRD spectrum presents
intensity versus 2-theta (the angle of X-ray to the sample). In
X-ray diffraction, an incident beam of X-ray is scattered from the
surface and a diffraction pattern is formed as a consequence
of the scattering of short wavelength X-ray photons by an
electronic cloud of highly ordered positive ion centers within
the material. Regularity and ordering of the ions forming a lattice
in the sample can be detected as well.129 The Bragg formula
d sin y = nl is used for determination of lattice spacing in which
d is the distance between special crystal planes, y is the angle of
the X-ray beam to the sample, n is an integer number and l is
the wavelength of the X-ray beam (1.54 eV for the standard
copper-a beam). Peak broadening can be related to a small
crystal size, which was analysed using the Scherrer formula,
t = Kl/b cos y, in which y is considered for a specific XRD peak,
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K is a dimensionless shape factor close to 1, b is full width at
half maximum of the peak and t is the mean crystallite size for
the specific crystal plane of the peak. For example, the effect of
doping on the crystallite size of the as grown TiO2 nanoparticles
has been investigated.130,131
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The TiO2 crystallite size can affect the diffusion coefficient of
the electrons inside the mesoporous film.37 Besides, the interface
crystalline surfaces affect the dye adsorption to a large extent94
and adsorption of different dyes on the different crystalline
planes of anatase TiO2 has been studied.110
Anatase TiO2 is the most commonly used material for DSC
photoanodes, it has an indirect band gap of 3.2 eV, which is a
little higher than that of the rutile phase of TiO2; allowing more
photons to be absorbed by the dye.132 Dye adsorption and
electronic transport of rutile and anatase nanocrystals are
different.133,134 The CB position and single crystalline conduc-
tivity are higher in the anatase compared to the rutile phase.6
In terms of device efficiency, the energy levels of anatase are
more appropriate for the superior device efficiency. Rutile is the
most stable TiO2 phase; at higher temperatures (more than
600 1C) anatase converts to rutile.132,135 Moreover, the crystalline
phase of new counter electrode materials is typically evaluated
by XRD.78,95,136
3.6 X-ray photoelectron spectroscopy (XPS)
By illumination of the surface with high energy photons
(X-rays), electrons can be ejected from the material according
to the photoelectric effect. The kinetic energy of the ejected
electrons (EK) is measured using photoelectron spectroscopy
(PES or XPS) and is equal to the difference in the photon energy
(hn) and the energy of the electrons in the material, i.e. the
binding energy (EB) and the work function (F) of the material.
This is described in eqn (5).
EB = hn  EK  f (5)
Binding energies of energy levels from atom-like orbitals (core
levels) are characteristic of each element and therefore one can
obtain information about the elemental composition of surface
atoms by XPS. XPS is also sensitive to chemical shifts, i.e. to the
electronic surroundings of specific atoms and therefore can
give information about the chemical state of the material.
The intensity of the measured electrons depends on the
cross section for photon absorption by the specific orbital, on
the surface density of the elements and on the mean free path
of electrons in the material. The mean free path depends on the
kinetic energy of the escaping electron and is usually quite
short making XPS usually a highly surface sensitive technique.
Furthermore, this makes it a requirement for measurements to
be carried out under vacuum conditions so that electrons can
reach the detector without collisions with molecules in the gas
phase. Although XPS is generally a very surface sensitive technique,
XPS with very high photon energies (Hard X-ray Photoelectron
Spectroscopy, HAXPES) can be used to study the atomic composi-
tion deeper inside a material, even for hundred nanometer film
thicknesses.17 Another way to analyse deeper into a material is to
use sputtering and subsequent XPS analysis.
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Different DSC components (i.e. thin films, dye molecules
adsorbed on the electrode surfaces or molecules solvated in the
electrolyte) can be studied by means of XPS. This information
for example can be used for studying the elemental composi-
tion of device components, and binding of dye molecules to the
electrode. The valence energy levels can also be measured using
XPS, which gives further understanding of the energy levels
involved in the electron transfer processes in solar cells. It is
also possible to study the orbital composition of the valence
levels using resonant photoelectron spectroscopy, which is also
important for the fundamental understanding of the light to
electricity conversion process.17 XPS can also be used for atomic
composition analysis of any new implemented DSC compo-
nents, for example, Shi et al. have used XPS to investigate a new
counter electrode material.136
With new technologies it is also possible to use the XPS
technique to study liquid systems, in liquid jet XPS, liquid jets
are passing the vacuum with very high speeds and therefore it is
possible to study the binding and composition of atoms in the
liquid electrolyte.137,138
Ericsson et al. have for example studied the formation of
new bonds between the tri-iodide and water in water based
electrolytes. For the case of water based iodide electrolytes, the
XPS measurements show an asymmetry in the I3 solvated ions,
hydrogen bond interactions are responsible for the symmetry
breaking.137 In DSCs, activation of the I3 ion in asymmetric
environments is important for its function through interactions
with surfaces and dye molecules.
Another new possibility is to use time resolved photo-
electron spectroscopy using pulsed X-rays from free electron
lasers or higher harmonic generation light sources for studying
the conversion process at an atomic scale with ultrafast
time-resolution.17
3.6.1 Core level analysis. Different atom-like orbitals and
core levels can be specifically useful for studying the elemental
composition,86,122,139–141 dye binding configuration and surface
coverage116,139,140,142–146 and possible chemical bindings of
atoms in electrolytes or on the semiconductor surface.122,137
The dye configuration at the surface may for example be
studied for dye molecules containing chemically different
atoms of the same element. In that case the surface sensitivity
can be used to determine which of the atoms are located closest
to the surface and thereby the orientation of the molecule at the
surface. This approach has for example been used to study the
orientation of organic triarylamine based dye molecules con-
taining nitrogen atoms with different chemical surroundings,
which gives different separated N 1s peaks in the measured
spectra. By comparing the intensity of the different nitrogen
atoms it is then possible to determine the orientation of the
molecule on the TiO2 surface.143,144
Since PES is a very surface sensitive technique, the estimation
of the dye coverage is true for the outermost surface of the TiO2
film. The orientation and coverage of the dye is very important on
the electron lifetime and device performance of cobalt electrolyte
based DSCs. The blocking effect of the dye and its effect on
electron lifetime have been studied by several groups.147–150
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The chemical bond between the dye and the semiconductor
surface may also be studied using XPS. The binding group of
the dye to the TiO2 surface is usually a carboxylic group and by
studying the O 1s core level, it is possible to investigate the dye
binding. However, since dye-sensitization in the solar cell is
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usually not made in a perfectly clean environment (not ultra-high
vacuum), contaminants that contain oxygen are also present on
the surface, which makes the analysis more difficult. The binding
of the carboxylic group to the TiO2 surface has therefore been
studied in a UHV for a model-system only containing the ligand
with the carboxylic group and a very clean TiO2 surface. The results
suggest that the molecule binds with both oxygen atoms in the
carboxylic group on the TiO2 surface in a 2-bidentate mode.145,146
The amount of any dopant/surface adsorbate, the percentage
of the Ti4+ species and formation of new species in stability tests
on the working electrode can be investigated by XPS86,122,139–141,151
3.6.2 Valence electron and molecular orbital analysis. The
valence electronic structure is involved in the electron transfer
reactions occurring in the solar cell, and is therefore of parti-
cular interest for the function of the device. For example the
highest occupied molecular orbital (HOMO) of a dye molecule
and the valence band of TiO2 can be measured by photoelectron
spectroscopy. The relation between the energy levels of the dye
and the semiconductor surface can therefore be determined by
this method.17,140,152 The redox potentials of dye molecules are
usually determined using electrochemistry and it is usually
difficult to determine the energy levels of the semiconductor
(TiO2) when the dye is attached to the surface. This may be a
problem since the dye may affect the position of the energy
levels of the semiconductor and the combined system may
therefore show different energy levels compared to the separate
materials. By photoelectron spectroscopy it is possible to deter-
mine the energy levels of both the dye and the semiconductor
simultaneously, which may be advantageous to understand the
possible electron transfer reactions.16
Using photoelectron spectroscopy it is also possible to study if
there are any filled states within the band gap of the semiconductor,
which can be important for electron transport and recombination
of the photogenerated charges.17,153 Recently we have reported on
the application of mesoporous microbead films in liquid and solid
state based DSCs which show higher open circuit voltage and
a faster transport time compared to conventional DSCs.154,155
Photoelectron spectroscopy measurement of the films shows that
microbead films have less intra band gap states which in part can
explain the behaviour of the device in comparison to standard Dye
sol paste films (Fig. 8). Intra band gap states are very important for
the electron transport, lifetime and device performance of the solar
cell. More numerous and deeper traps can slow down the electron
transport and increase the back reaction of electrons and act
as recombination centres. This will therefore decrease Jsc and
Voc of the device. The nature of these traps is not completely
understood9,156–158 but the preparation method of semiconductor
films affects the density of traps66,156 and consequently chemical
capacitance and recombination resistance of the films.67
It is also possible to measure the elemental composition of
the molecular orbitals in the valence electronic structure using
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Fig. 8 Measured intra band gap sates of microbead and nanoparticulate
films by XPS. Reproduced from ref. 155 with permission from The Royal
Society of Chemistry.
resonant PES or measurements with different X-ray energies.
For example the elemental contribution in the highest molecular
orbitals of ruthenium dyes was determined using resonant PES
and also by different photon energies, which enhance or sup-
press the signal from different elements in the spectra.152,159,160
From the results the contribution from the ruthenium metal
centre and the ligand to the highest occupied orbitals can be
quantified experimentally.
3.7 UV-Vis absorption spectroscopy
Steady-state absorption spectroscopy of dye-sensitized solar
cells can be used to determine the band gap of the different
materials, the light harvesting efficiency of the solar cell, a
material’s concentration within the device and the extinction
coefficients of dyes.
The absorbance of a sample (A(l)) as a function of the
wavelength (l) is defined by the logarithmic ratio of the incoming
light intensity (I0(l)) and the transmitted light intensity (It(l))
through a sample:
I0 ðlÞ
AðlÞ ¼ log10 ¼  log10 TðlÞ (6)
It ðlÞ
where T(l) is the transmittance of a sample. Absorption spectra
are therefore usually obtained by measuring the light trans-
mitted through the sample and the light transmitted through a
non-absorbing reference in the same set-up.
The extinction coefficients (e(l)) or concentrations of dyes in
solution (C) can be estimated using the Beer–Lambert law:
A(l) = e(l)Cl (7)
where l is the optical length of the used cuvette (usually 1 cm). For
accurate determination of the extinction coefficient, C should be
rather low to prevent light scattering and aggregation in the
solution. Furthermore, it should be noted that the error in the
measurement becomes very large at high absorbance values
when the intensity of transmitted light becomes very small.
When measuring the solid samples, the absorption coeffi-
cient a tends to be used instead of the extinction coefficient,
which is defined as:
1 I0 ðlÞ
aðlÞ ¼ ln (8)
d It ðlÞ
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where d is the thickness of the solid sample. The bandgap
energies of semiconductors (Eg) can be determined from measure-
ments of the absorption coefficient. For direct bandgap semi-
conductors, the absorption coefficient is related to the photon
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
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energy (Eph) near the absorption edge by: a / Eph  Eg .
For indirect bandgap semiconductors this relation is:
 2
a / Eph  Eg .52 Plots of a2 and a1/2 vs. Eph can therefore be
used to determine whether a semiconductor has a direct or an
indirect bandgap and to determine the bandgap from a straight
line interpolation to the intercept.
For dye molecules, one typically considers the zero–zero
transition energy between the ground and excited electronic
states in the lowest vibrational level (E0–0). This energy can be
determined from the crossing point of the normalised absorption
and emission spectra. Alternatively, an approximate value can be
obtained by determining the onset energy of absorption.161
Comparison of the simulated absorption spectra of dyes
obtained from DFT calculations with experimental UV-visible
absorption data can give insights into what specific transitions
are involved in the absorption spectra.157–158,162
The dye coverage on metal oxide surfaces can be estimated
using absorption measurements. If dyed films are measured
directly the absorbance can be related to the surface coverage
(G) in units of mol cm2 using eqn (9):163
A = 1000  G  e
The extinction coefficient usually has to be determined from
measurements of the dye in solution and this method therefore
relies on the dye’s extinction coefficient and the absorption
spectrum not changing upon adsorption to a metal surface.
This is often not the case and therefore alternative methods
of determining the surface coverage of dyes involve dye
desorption from the surface often with basic solutions66 or
measurement of the dye bath’s concentration before and after
dye adsorption.161 If the surface area of the electrode is known
(from the particle size, porosity and film thickness), one can
calculate the area of the adsorption site of single dye molecules
on the particles.147 Alternatively, if this parameter is known, the
measurements may be used to estimate the effective surface
area of the electrode.66
Desorption measurements can also be used to estimate
the dye adsorption isotherm147 which is important for the
evaluation of competitive dye adsorption in the cocktail co-
sensitization method.164,165 Other methods such as quartz
balance, neutron impact collision ion scattering spectroscopy
(NICIS) and photocurrent measurement techniques can also
be used for this purpose for which special instruments are
required.166–168
A comparison between the absorption spectrum of a dye in
solution and the absorption spectrum when it is adsorbed to a
semiconductor surface can give insights into the impact of
binding on the dye molecules. For example, if binding to the
surface is accompanied by a large change in the dye structure,
this might result in a shift of the dye’s absorption spectrum.161
Furthermore, dye aggregation in solution or on the surface can
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be observed by absorption spectroscopy. Recording the traces
of electrolyte/electrode absorption changes during the stability
tests is a tool for understanding possible device changes during
aging.169
The light harvesting efficiency (LHE) or absorptance of a
solar cell electrode, i.e. the fraction of absorbed photons, can be
estimated from its absorbance using the following equation:
LHE(l) = 1  10A(l) (10)
However, as this equation neglects any reflection losses or
diffuse transmission, a better measurement of this parameter
can be obtained when using an integrating sphere.163–165 In
this case, the total transmittance and the total reflectance (R)
of a film can be measured and LHE can be calculated using:
LHE(l) = 1  T(l)  R(l).
The light harvesting efficiency is an important parameter for
calculating the APCE of a solar cell (see Section 4.2) as well
as for scaling the measurement results such as those from
transient absorption spectroscopy (see Section 5) by the number
of absorbed photons at the excitation wavelength.
A further application of absorption spectroscopy has been to
estimate the pore filling of the mesoporous electrodes by a hole
conductor in solid state DSCs. This can be achieved by dissolu-
tion of the hole conductor from the pores and determination
of the hole conductor’s amount by absorption measurements.
This method requires knowledge of the hole conductor’s extinc-
(9)
tion coefficient, the porosity of the mesoporous film and the
thickness of the hole conductor’s capping layer on top of the
semiconductor film.86
A second method for the estimation of pore filling uses the
interference patterns observed in the transmission spectra of
thin films. From these patterns, the effective refractive index of
the films can be determined and using the Bruggeman effective
medium approximation the volume fractions of all components
and therefore the pore filling can be estimated.87
3.8 Conductivity measurements
Conductivity of each DSC component is important and the
influencing parameter for the optimization procedure of the
device PCE is related for sure to the fundamental understanding
of the device behaviour.170–186 The thickness of each device
component is typically optimized in terms of contribution to
the total device series resistance. For example increasing the
thickness of the PEDOT counter electrode on glass enhances the
conductivity of the film, and in turn limits the transparency of
the electrode.88,170 The same argument is true for other device
components, i.e. conductivity of metal back contact versus its
light scattering properties in ssDSCs that should be optimized
regarding the metal contact thickness. In ssDSCs, the hole
conductivity is a limiting factor for device PCE and higher
conductivities are desired. Conductivity measurements for DSCs
include investigation of the hole conductor, the mesoporous
semiconductor and redox mediators in the electrolyte as well as
the counter electrode.
Applying a voltage on the two (or four) contacts of the
material and recording the current is a conventional way for
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measuring the conductivity. A simple resistor model can be
used to estimate the conductivity from current–voltage data in
the dark or in different light intensities (i.e. measuring the photo
doping effects). Special care should be taken about the length of
the top metal contacts and how the total current will distribute
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to the semiconductor (it defines the effective thickness and
area of the semiconductor engaged in electronic conduction).
Depending on the metal work function and the position of the
Fermi level in the semiconductor, we have contact resistances
which can be of the ohmic or Shottky type. Metal contacts should
be chosen appropriately to make ohmic contact with the semi-
conductor and their corresponding contact resistances should be
taken into account in the measurement. In the two point probe
measurements, this can be estimated by measuring through
different channel lengths. However by using the four point
probe technique, one applies the current from two contacts and
measures the voltage from another two contacts. In this way,
the contact resistance is removed from the measurement.
Due to its crucial importance to the device efficiency,
hole conductor conductivity has been widely investigated for
ssDSCs.172–174,180 Typically two gold electrodes are evaporated
on the film (Fig. 9a) and the voltage–current characteristics are
recorded. A simple resistor model can be used to determine
the conductivity (s): s = L/Rwd. L is the channel length, R is
resistance obtained from the I–V curve, d is the thickness of the
film and w is the channel width.172 As is shown in Fig. 9, the
absence of FTO is necessary here to measure the contribution
of only the hole conductor and moreover the presence of a
mesoporous scaffold is necessary to take into account the film
porosity in the real device.
Conductivity (s) of a semiconductor is related to the resistivity (r)
and mobility (m) through:
1 Sensitization of films by dye significantly affects the charge
s¼ ¼ nem (11)
r
n is the charge density and e is the fundamental charge of an
electron. Using the Einstein relation one can relate the mobility
of a semiconductor to the diffusion coefficient (D) of electrons
(holes):
eD
m¼ (12)
kB T
For spiro, the photo doping effect cannot change the Fermi level
noticeably since it is usually p-doped in the device.
Fig. 9 (a) Schematic of the conductivity measurement used for solid state
DSCs. Reprinted with permission from (Journal of American Chemical
Society, 130, 12912). Copyright (2008) American Chemical Society.
(b) Schematic of a coplanar configuration for conductivity measurement
in liquid electrolyte DSCs.
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Conductivity measurement of a mesoporous TiO2 film is
not a simple task. The presence of trap levels with different
energies leads to the Fermi level dependent diffusion coefficient of
the electrons which can be explained by the random walk and
multiple trapping models (Section 2.3). Then conductivity depends
on the light intensity and the amount of electrons present in
the film.33
Electron transport time measurements for the complete
solar cell (see Section 6.2.2) can give the effective diffusion
coefficient of the electrons inside the film (eqn (50)). Measuring
the transport time in different light intensities gives a description
of conductivity inside the mesoporous film (eqn (11) and (12)).
Furthermore, the transport resistance of the mesoporous TiO2
film can be estimated by EIS.181
Terahertz spectroscopy is a powerful tool for measuring the
real and imaginary parts of the frequency/light intensity depen-
dence of conductivity in mesoporous semiconductor films and
studying the charge transport in the film on a short length
scale.175,176 In this method there is no electrical contact to the
sample and time resolution can be in the order of sub pico seconds.
Transmission of far-infra red pulses from the dyed/bare sample
is measured after a delay to a visible excitation pulse (in different
probe frequencies and pulse intensities). The transmission differ-
ence ratio (DT(l)/T(l)) of the far infrared light at the wavelength
l from the sample depends on the conductivity (sn(l)) of the
sample through:178
DTðlÞ
¼ Dnt sn ðlÞd (13)
TðlÞ
Dnt is the excess injected charge and d is the thickness of the
film. Nemec et al. have studied the charge transport in the
mesoporous TiO2 and ZnO films by terahertz spectroscopy.
transport due to dye cation/injected electron electrostatic
interactions in ZnO films.176 Tiwana et al. have compared
electron conductivity in dyed mesoporous films with undyed
films for ssDSCs using terahertz spectroscopy.177 Hendry et al.
have studied the electron mobilities in bulk and meso-
porous TiO2 films and the effect of local electric fields using
terahertz conductivity measurement.187 This technique allows
the determination of the electron mobility after carrier therma-
lization with the lattice but before equilibration with defect
trapping states and therefore represents upper limits for
conductivities.187
Snaith et al. have used photo-induced charge-conductivity
(PICC) modulation spectroscopy to study and model the charge
transport in a dyed mesoporous TiO2 film.188 A pulsed laser
beam excites the dye molecules that inject electrons inside
TiO2. Probing the oxidized dye absorption versus time monitors
the density of injected electrons inside the film. Simultaneously
a voltage current characteristic of the film through two metallic
contacts can be recorded from which conductivity and mobility
are estimated.179,188
There are other methods which are common for semi-
conductors and organic hole conductors such as the Hall effect
and time of flight (TOF) method. In TOF the film is sandwiched
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between two metallic electrodes, and a pulse of charge carriers
is created by a voltage pulse or a laser pulse at one electrode;
and the travelling time of created charge to the second electrode
is measured. Eqn (14) relates the travelling time to the drift
velocity and the mobility:189,190
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d d2
m¼ ¼ (14)
E  ttr V  ttr
d is the film thickness, ttr is the transit time, E is the electric
field and V is the voltage. Halverson et al. investigated the
proton intercalation effects on electron-transport of mesoporus
TiO2 films in a neat electrolyte using the TOF method.158 Jäger
et al. studied doping effects on the conductivity of a triphenyl-
diamine hole conductor in ssDSCs.189
In space charge limited current (SCLC) measurement, the
same configuration setup (simple deposited contacts – Fig. 14a)
is used to measure the limiting current of the hole conductor
film (suitable for semiconductors with ohmic contacts).182
Using eqn (15) one can estimate the mobility (m) of the charges
in the sample:183,191
9V 2
J ¼ mee0 (15)
8d 3
Contact resistances should be considered here because only
two contacts are used rather than four. J, V and d are the limited
current density, voltage and thickness of the film, e and e0 are
relative and absolute vacuum dielectric constants.
In microwave conductivity measurement (MC) DP(t)/P is the
relative change of the microwave power (P) reflected by the
sample induced by a photogenerated change of the conductivity
(Ds(t)) during the time (t).184 The change of the photo-
conductivity is proportional to the reflected microwave signal:
DP(t)/P = ĀDs(t), where Ā is the proportionality factor.
Dunn et al. have measured the trap densities of the TiO2 meso-
porous film using the photo induced microwave reflectance
method.34,185
Using a coplanar configuration (Fig. 9b) the conductivity of
TiO2 porous films was measured using a bi-potentiostat. The
TiO2 film sintered on an interdigitated electrode forms two gold
supported nanoporous electrodes that are electrically contacted
by the TiO2 layer present in the gap between the two gold
contacts. The measurement is based on a simultaneous scan of
the two nanoporous working electrodes (between 0.0 V and
0.9 V (vs. Ag/AgCl)) while a small constant potential difference
between them is maintained. The current flowing across the
gap through TiO2 is proportional to its conductivity at each
potential.192
Changes in the device temperature should be taken into
account during long conductivity measurements especially for
methods in which electrical contact is needed (the sample will
be heated because of its resistance).
In some materials such as metal–organic perovskites, dielectric
constant and consequently conductivity have great dependency on
temperature and also applied bias.193
For DSCs with liquid electrolytes, the diffusion of the redox
couple is an important and rather rate limiting process for the
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cell performance. In an electrolyte containing ionic concen-
tration of C, one can define ionic conductivity (kEL) as:194
F2 X
kEL ¼ Di Ci jZi j2 (16)
RT i
F is the Faraday constant, R is the gas constant, T absolute
temperature, Z and D are charge and diffusion coefficients
of the ion. The summation is over ions which contribute to
electrochemical current. Cyclic voltammetry and EIS are the
main methods to measure the diffusion coefficient of the redox
mediators in liquid dye-sensitized solar cells or quasi-solid-state
DSCs195,196 (Sections 3.9.1 and 6.1). Low diffusion coefficients lead
to mass transport limitations in the bulky redox mediators.
3.9 Electrochemical measurements
3.9.1 Cyclic voltammetry. The Nernst equation describes
the electrode potential in the solution which depends on the
population of acceptor/donor species when an electrochemical
electrode is in contact with the electrolyte:
 
Cox
E ¼ E0  kB T ln (17)
Cred
E is the electrode potential energy (equal to elemental charge
times the potential), E0 is the redox formal energy which depends
on the nature of redox species, kB and T are the Boltzmann
constant and absolute temperature and Cred and Cox are concen-
tration of reduced and oxidized species. Cyclic voltammetry (CV) is
the most well-known electrochemical technique and is widely used
in DSC research for characterization of dyes, redox mediators and
charge transfer processes at interfaces. By scanning the voltage
and monitoring the current in a forward and a reverse scan, the
formal redox potential, as well as interface charge transfer rates
and the diffusion coefficient can be estimated.194 If the scan is
begun at a potential well positive of E0, only capacitive current
flows until in the vicinity of E0 that the reduction begins and the
faradaic current starts to flow. As the electrode potential continues
to grow more negative the current increases until the surface
concentration of the electroactive species drops nearly to zero,
the mass transfer to the surface reaches a maximum rate and
then it declines as the depletion effect sets in. The observation
is therefore a peaked current–potential curve like that depicted
in Fig. 10.
CV is the standard method for measuring the dye formal
redox potentials from which the HOMO and LUMO levels of the
dye in the solution can be estimated (see Fig. 2). By using a
three electrode electrochemical cell one can record the cyclic
voltammogram of the dye on the electrode or in the solution.
The average of peak (Vp,a)(Vp,c) voltages gives the formal potential
of the dye in the solution:121,197–202
Vp;a þ Vp;c
VðDþ=DÞ ¼ (18)
2
If the working electrode is an under-layer free dye loaded
mesoporous film on FTO, the CV current corresponds to the
hole hopping current (see Section 3.9.2). Moderate scan rates of
10 to 50 mV per second are implemented for evaluation of hole
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Fig. 10 Cyclic voltammograms of cobalt–phen complexes in acetonitrile.
Reprinted with permission from (Journal of Physical Chemistry C, 115,
21500). Copyright (2011) American Chemical Society.
hopping in this experiment. The conventional solvent is aceto-
nitrile which is commonly used for the DSC electrolytes con-
taining 0.1 M supporting salt. Other solvents are also used
which can modify the position of dye energy levels to some
extent.203 In most of the cases calibration of the reference
electrode is needed by adding ferrocene to the electrolyte and
measuring the CV spectra of the solution again.121,204 Due to its
solvent independence redox potential and high electroactivity,
ferrocene is widely used for the calibration of reference electrodes.
Dye de-loading from the working electrode (WE) can occur during
the CV measurement in the case of very positive or negative
applied potentials. This should be taken into account during the
measurement. Furthermore in the same way, redox potential of
the electrolyte redox mediator is achievable from its CV spectrum
in the solution (eqn (18) and Fig. 10)205
The diffusion coefficient of the redox mediators in different
solvents can be obtained by CV. A low concentration of redox
mediators – for example Co(II)(bpy)3(3PF6)2 – is dissolved in a
desired solvent and CV is recorded with different scanning rates.
The diffusion coefficient for reversible systems is obtained using
the Randles–Sevcik equation:206
pffiffiffiffiffiffiffi
ip ¼ ð2:69  105 Þn3=2 Aelectrode C Dn (19)
Aelectrode is the electrode surface area, C is the concentration of
the species under study, n is the number of transferred electrons
in the redox reaction, D is the diffusion coefficient and n is the
scanning rate.
Using microelectrodes in CV, one can obtain the diffusion
coefficient (D) from the diffusion limited current (Ilim) observed
in the voltammogram according to eqn (20):57
Ilim = 4FnDCr (20)
F is the Faraday constant, C is the concentration, n the number
of transferred electrons (1 for the case of a cobalt electrolyte)
and r is the radius of the microelectrode.57 Furthermore, in the
Pt sandwich cell filled by the electrolyte, the resultant limiting
current ( Jlim) from CV can be used to estimate the diffusion
coefficient (D): Jlim = 2FDC/dsealant. C, F and dsealant are concen-
tration of the acceptor redox mediator, the Faraday constant
and the sealant thickness, respectively.207
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Papageorgiou has studied the effect of TiO2 film porosity on
the diffusion of iodide mediators by measuring CV of the cell.
Different sandwich cells of flat Pt with/without mesoporous
TiO2 have been filled by the iodide electrolyte and the CV data
have been fitted by the proposed diffusion model and the
concentration profile of I and I3 in the electrolyte has been
estimated.208
The Fermi level of the electrolyte (the redox potential) is held
between the acceptor and donor states in the electrolyte. The
distribution of acceptor (Nox)/donor species (Nred) in the electro-
lyte (shown in Fig. 2) can be described by:6
 ðE  E F  L Þ2
Nred ¼ N0 exp
4kB TL
(21)
ðE  EF þ LÞ
Nox ¼ N0 exp
4kB TL
E is energy, EF redox potential, L reorganization energy,
kB Boltzmann constant and T is absolute temperature. Fig. 16
shows the typical CV spectra of famous cobalt(phen) complexes
measured in acetonitrile. In certain DSC devices, photocurrent
decreases and photovoltage increases by decreasing the redox
potential.57
CV has been used for determination of trap density of states
(DOS) in the semiconducting electrodes.209 Bisquert et al. intro-
duced a model for describing charge accumulation in meso-
porous electrodes in contact with the electrolyte, and interpreted
the experimental CV data using the model. Information about
the density of states and energy levels could be obtained.209
In the CV spectrum of a bare TiO2 electrode, the changes in the
stored charge (dQ) due to the changes in the Fermi level (dV)
can be described by:210
dQ NA
¼ DOS  & dQ ¼ ð1=nÞ  I ðV ÞdV (22)
dV F
I, V and n are the current, voltage and scanning rate in CV
measurement. NA and F are the Avogadro number and the
Faraday constant respectively.211
Gao et al. have used the CV method to monitor the changes
in electron transfer rates from the electrode to the electrolyte
acceptor species for Mg(OOCCH3)2 coated WEs.212
CV can be used for the characterization of counter electrodes
as well. By measuring the CV of the counter electrode in the
presence of a redox mediator, one can study the electrocatalytic
activity and estimate the effective surface area of the counter
electrode using the peak current separations and magnitudes
or by exchange current density analysis in conventional Tafel
plots of symmetrical cells.170,213,214
Low peak separation and higher peak currents are indicative
of higher electrocatalytic activity of the counter electrode. It can
be interpreted as a higher surface area of the counter electrode
or its higher charge transfer rate.
Electrochemical characterization of blocking layers of FTO
can be done by measuring the CV of the Ferrocene acceptor
ions in liquid electrolytes.215–217 CV data are plotted in the con-
ventional Tafel plots and compared to bare FTO: magnitude of
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current is indicative of the blocking effect for back charge
transfer from the electrode to the electrolyte.217 All the measured
energy levels and electron transfer rates in the CV are of crucial
importance for device optimization.
3.9.2 Spectroelectrochemistry. In spectroelectrochemistry
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the optical changes of the device components (typically dye
covered TiO2 electrodes) under different electrochemical condi-
tions are recorded. The setup consists of a three electrode electro-
chemical cell in which UV-Vis absorption of the electrode is
simultaneously monitored during the electrochemical reactions.
Using different applied bias voltages on the dyed electrode in the
neat electrolyte, one can alter the populations of the dye/oxidized
dyes or hole conductor oxidized molecules according to the Nernst
equation (eqn (17)) and monitor the changes in the absorption
spectra of the electrode.218,219
By applying a step potential (positive enough to oxidize dye)
to the dyed electrode and simultaneously monitoring the
oxidation current and absorption changes, coloration efficiency
(CE(l)) and delta extinction coefficient (De) can be estimated.85
These data will be of essential importance for transient kinetic
absorption spectroscopy in which the fingerprints of the oxidized
dye and its extinction coefficient are necessary to quantify the
charge recombination and dye regeneration kinetics after the
excitation of the dye (see Section 5.1).220
The TiO2 working electrode should be thin enough to
minimize the optical reflections and potential drops in the
electrode. If the applied potential became too positive, it is
possible that each dye is oxidized with more than one electron
or even desorbed from the surface that should be taken into
account. The extinction coefficient of the reduced dye (which is
different from the excited state dye) can be measured in the
same way as described above by using a negative reduction
potential.
DFT calculations can be combined with spectroelectro-
chemistry to find out the origin of different absorption changes
of the dye in terms of orbital energies and physical locations of
donor/acceptors in the dye structure.197,221
Hole hopping is a lateral diffusion of holes in between the
dyes in DSC working electrodes. Charge collection efficiency of
solid state solar cells can be improved by the hole hopping,222
also the Stark effect is strongly dependent on that (Section 5.3).
It can be measured by laser spectroscopy163 and cyclic voltam-
metry or spectroelectrochemistry.223 Using no under layer on
the FTO and measuring the cyclic voltammogram of the dyed
electrode, current peak in positive potentials corresponds to the
hole hopping current (in positive potentials the TiO2 film is an
insulator and the measured current is just from hole hopping
between the dyes). The hole hopping rate and its corresponding
activation energy, reorganization energy and diffusion coefficient
can also be measured by CV.223
In the case of nanostructured semiconducting electrodes
with a distribution of intra band gap states below the CB edge,
scanning the applied bias from positive to negative potentials,
the trap states of un-dyed films will be filled by the electrons.
Injected charge to the electrode (from integration of current
versus time) in each potential is proportional to density of trap
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states of un-dyed films in that particular potential.209 Monitoring
the absorption spectra changes gives information about the
energy position and the extinction coefficient of electrons in
those states studied by spectroelectrochemistry.224 For light
scattering samples one can use electrolyte electroreflectance
(EER) spectroscopy instead.225 Spectroelectrochemistry has also
been used to rationalize the Stark effect and oxidized dye
contribution in photoinduced spectroscopy of DSCs (see also
Section 5.3).226
3.10 Isoelectric point and the zeta potential measurements
Measurements of surface charge and interface potential drops
for semiconductor nanoparticles have been implemented to
further understand the device performance of liquid electrolyte
DSCs. The surface charge of nanoparticles and the so called
Helmholtz layer surrounding the particle in contact with the
electrolyte cause a certain potential difference between the
particle surface and the electrolyte environment. The inter-
action with the electrolyte results in a potential of the nano-
particle called zeta potential. The zeta potential cannot be
directly measured however can be estimated from electrophoretic
mobility measurement.227 The isoelectric point is defined as the
pH at which the particle statistically has no net surface charge.
Zeta potential measurements have been used to evaluate the
anion uptake of magnesia (MgO) nanoparticles and their effect
on the electron recombination kinetics in the liquid electrolyte
DSCs.228 The zeta potential for nanoparticles of a certain metal
oxide depends on the electrolyte environment, surface defects,
oxygen or metal richness of the surface as well as the preferential
crystal planes on the nanoparticle surface. It can directly affect
the Helmholtz capacitance and the photoinduced Stark effects
(Section 5.3).
A higher isoelectric point of the particle means a more basic
surface and the ability of higher dye uptake229,230 (for dyes with
carboxylic or phosphonic anchoring groups). The cation and
anion uptake for alumina, magnesia and silica nanoparticles
and their dependency on the particle isoelectric point in the
quasi solid state DSCs have been reported by Mohanty et al.231
4. Device characterization
4.1 Current–voltage measurements
Solar cells are evaluated by power conversion efficiency (PCE)
which is calculated from the current–voltage spectrum of the
device. PCE is proportional to the amount of delivered electri-
city and important commercial and also economical para-
meters of the photovoltaic devices are declared by PCE i.e.
efficiency per mass, area or cost. By illuminating the solar
cell, scanning the voltage and measuring the current using a
potentiostat/sourcemeter, we can plot the current–voltage curve
of the cell. The photovoltage at zero current and photocurrent
at zero voltage are called open circuit voltage (Voc) and short
circuit current ( Jsc). PCE of the solar cell is the ratio of
maximum solar cell power to the intensity of incoming light.
The maximum power point is defined in the point that has a
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Fig. 11 Typical IV curve of a DSC.
maximum value for the product of current and voltage (Fig. 11).
Under standard AM 1.5 conditions we have 100 mW cm2
power of incoming light and PCE is defined by:
Pout Pmax½mW cm2 
Z¼ ¼ (23)
Pin 100
Pmax is the product of current and voltage at the maximum
power point (MPP). The fill factor (FF) of the device is the ratio
of Pmax to the product of Jsc and Voc:
Pmax Z to go down. Near the Jsc point the recombination rate is much
FF ¼ ¼ (24)
Voc  Jsc Jsc  Voc  100
Under open circuit conditions there is no current, and electrons
have filled the trap states of TiO2 up to the Fermi level and
trapped electrons are in equilibrium with conduction band
electrons.40 Equilibrium density of electrons depends on the
recombination rate krec;232 in Voc, electron generation rate G is
equal to the recombination rate. Considering first order kinetic
recombination, krec depends on the density of electrons n, and
the electron lifetime t:
krec = n/t, & krec = G (25)
The higher the lifetime is, the higher the density of electrons
in the film will be. Open circuit voltage of the device is the
difference between the Fermi levels of counter and working
electrodes, in order to have higher Voc we can reduce the recombi-
nation rate or lower the Fermi level of the counter electrode (which
is almost equal to the electrolyte Redox potential). For example the
redox potential of electrolytes with cobalt complex redox couples is
usually more positive than the redox potential of the standard
iodide based electrolyte. The electrolytes with cobalt complexes
therefore usually result in higher voltages of the solar cell devices.
In low surface area working electrodes (nanostructures with
dimensions larger than 30 nm) it is possible to have band
bending on semiconductor nanostructures in which resulting
electric fields can reduce the recombination rate and increase
Voc.74,233,234 Equivalently, keeping the recombination rate fixed
and increasing the electron generation rate (G) Voc will be
increased.
Under short circuit conditions the Fermi level at the con-
tacts is basically the same. Theoretical calculations and experi-
mental measurements show that in short circuit there is a
gradient of the Fermi level position within the TiO2 film thick-
ness.24,235 The Fermi level difference is a driving force for the
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electron collection considering that the recombination rate
in the short circuit is an order of magnitude lower than open
circuit conditions. Here the generated electrons will diffuse to
the working electrode and holes to the counter electrode.
Diffusion is the rate limiting process in the electronic trans-
port and depends on the light intensity.33 Stronger light harvestings
and higher light intensities result in more generated electrons
and more filled traps, which means faster transport in DSC
working electrodes. The effective diffusion coefficient in the
film (Dn) depends on the diffusion coefficient of free electrons
in TiO2 (D0) and the trapping rate between trapped and free
electrons.40 Lower trap densities and one dimensional struc-
tures promote faster transport and higher Fermi levels at the
same charge density.75 The most important factor for achieving
high current is high light harvesting efficiency; and in efficient
nanoparticulate based liquid DSCs the collection efficiency is
near 100%.10
The FF depends on the resistance of the device which is
mainly composed of series resistance, diffusion resistance and
shunt (recombination) resistance. High diffusion and series
resistances and lower recombination resistances cause the FF
lower than that at Voc and the series and diffusion resistances
are dominant. Near the Voc point the current is low (low series
potential loss) and the dominant resistance is the recombination
resistance which can be basically calculated from slope of the
tangential line from the current–voltage curve.
4.1.1 Importance of the mask, light source and scan rate.
For proper evaluation of the efficiency, the size of the mask
should be the same as the active area.12,13 The three dimensional
hetero-structure of the DSCs can absorb light equally from
different incident directions and DSCs are not sensitive to the
direction of incoming light. If the incoming light is not 100%
perpendicular to the surface, bigger masks allow penetration
of excess light (including ambient diffusive light) into the DSC
and overestimation of efficiency. A smaller mask can also under-
estimate the efficiency. In this case, after the dye excitation
followed by injection of electrons, the Fermi level in the whole
device area is not the same; covered parts can suck some
percentage of electrons and lower the efficiency.
Another important factor for the measurement is the light
source; the spectrum of the light source should be exactly the
same as the solar spectrum. Usually a xenon lamp together
with optical filters can simulate the solar spectrum. A stable
reference silicon diode with a known spectral response can be
used for the calibration of the intensity of the sun simulator.
A correction factor is needed to account for the photocurrent
differences between reference and test cells.12 There are some
edge effects on the edge of the mask and a slightly smaller mask
than the active area is the best choice for the IV measurements.12
In the current measurement, voltage is increased step by step
with a certain scan rate. After applying a step to increase the
voltage, there is a waiting time for the device to reach the current
equilibrium. Delay of the scanning rate is very important to be
long enough in order to reach equilibrium in the current (due to
increasing the voltage). Dependence of cell parameters on the
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scan rate is discussed in ref. 12. If the scan rate is too fast, there
is no time for the photocurrent to be stabilized after the voltage
increase and leads to some uncertainties.12 The scan rate
of IV measurement is of crucial importance for correct evalua-
tion of perovskite based solar cells which show anomalous
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hysteresis.236
4.1.2 Dark current measurement and diffusion limited
current. Under dark conditions, by scanning from zero to negative
potentials, after a while and in certain potential (in which DOS of
filled traps and electrolyte acceptor states intercepts), the back
recombination of electrons to the electrolyte is started and one
can see the increase of the dark current. The shape of this curve
determines the FF of the device. Back reaction current density ( Jr)
can be described as:39
Jr = eketCm
ox(n
ua
nua
0 ) (26)
e is the elementary charge of an electron, ket is the back reaction
rate, Cox is the concentration of the oxidized species of the
electrolyte, n and n0 are the electron concentration at voltage
V and voltage 0 in the dark; m, a and u are the reaction rate for
the oxidized species and electrons and the electron transfer
coefficient respectively. By combining eqn (26) (which comes
from the Butler–Volmer equation in electrochemistry194) with
the diffusion equation of the electrolyte acceptors, we can express
recombination current in terms of the diffusion coefficient and
short circuit current of the cell39
Higher acceptor densities near the particle interface, higher
electron concentration together with higher surface areas lead
to a higher recombination rate. Dark current measurement can
be employed for comparison of the back recombination rate
of different solar cells.237 Different trends in the dark current
lifetime and the photovoltage transient lifetime can give informa-
tion and insights about the light induced recombination paths
i.e. insufficient pore filling of hole conductors in ssDSCs.155
In the light the photocurrent ( Jph) is described by:
Jph = Jinj  Jr (27)
The addition of the dark current with injection current ( Jinj)
gives the photocurrent. The IV curve will shift to lower poten-
tials (compared to dark current) by considering the product of
Jsc and the cell series resistance which is an ohmic loss under
working conditions.238
Going further from zero to positive potentials, we can have
reverse current to get electrons from the electrolyte donors
(which are more abundant compared to acceptor species i.e.
concentration of Co(II) compared to Co(III)) back to TiO2. By
increasing the voltage to more positive potentials, electrons will
come to the film from the electrolyte and the limiting current
can be reached at which diffusion of electrolyte species cannot
proceed faster than a special rate, which depends on the porosity
of the film, the sealant thickness, concentration of the electrolyte
redox mediator and its diffusion coefficient.239 For cobalt com-
plexes, mass transport can be a problem in high current
devices.100,154,240,241 Comparison of dark limiting current can
be a tool for determination of current limitations and evaluation
of recombination in different devices. For comparison of
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limiting current we should have in mind that the dye affects
the measured current in positive potentials. Indeed it is
possible that we oxidize the dye and electron transfer takes
place between the dye and the electrolyte. Comparison of IPCE
integrated current and short circuit current is another way to
study the mass transport limitation in the cobalt electrolyte
based cells. In the case of non-limited current DSCs, Jsc should
be linear versus light intensity and equal to integrated IPCE
current:
ð
Jsc ¼ G  jLHE  jinj  jcol dl (28)
Light harvesting efficiency (jLHE), collection efficiency (jcol)
and injection efficiency (jinj) are almost independent of light
intensity. Charge collection efficiencies can be however depen-
dent on the light intensities for very high recombination
rate devices (for example in the case of ferrocene based
electrolytes122,242) but on the other hand for iodide and cobalt
complexes they are almost independent of light intensity. In the
case of diffusion limiting current, the linear curve of J versus G
will be flattened in high light intensities and cannot be higher
than limiting current (Fig. 12). Then we can see a big difference
in efficiency when we measure the IV in 1 Sun or in 20% of 1 Sun.
Usually density filters can simply be used to simulate different
light intensities.
4.1.3 Simulating the IV curve. DSC acts as a hetero-structured
p–n junction (there is no space charge layer in DSCs) and its
current–voltage characteristics obey the diode equation:238,243
   
eV
I ¼ I0 exp 1 (29.1)
nkB T
 
1 eV
/ exp (29.2)
R nkB T
kB is the Boltzmann constant, T is the absolute temperature
and n is the diode ideality factor. I, V and R are current–voltage
and resistance of the cell. Simulating the experimental data
by these equations, one can distinguish series or recombina-
tion resistances of the device and compare them for different
cells.238,243,244
Fig. 12 Jsc versus light intensity for different films used for the optimiza-
tion of film porosity in cobalt electrolyte DSCs. Reproduced from ref. 241
with permission from The Royal Society of Chemistry.
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Fig. 13 An equivalent circuit for DSCs.
Fig. 13 shows the typical equivalent circuit used for DSCs.244
Rs, D, and Rsh are contact resistance, diode element and shunt
resistance.
Iph  Ish  Id = 0
Vd = Vsh = Vs + V(t) (30)
Iph, Ish and Id are photocurrent, shunt current and load current
(delivered current).
Rsh is employed to denote the interfacial charge recombi-
nation losses to both the dye cation and the redox electrolyte
(in the case of ssDSCs: it denotes the hole conductor recombi-
nation, oxidized dye or under layer recombination). Shunt
resistance Rsh takes into account all parallel resistive losses
across the photovoltaic device including the leakage current.
The photo-generated current Iph is in parallel with the rectifying
diode.243
Fitting the IV curve by a model, one can compare different
devices in terms of recombination resistance, contact resistance,
etc. There are more models for simulating the DSC IV curve
in which different components such as the counter electrode
and electrolyte Warburg impedance are considered separately
in the model.25,238,244 Halme et al. and Fabregat-Santiage et al.
proposed separate models and related the device parameters
(FF, Voc and Jsc) to different characteristic times and lengths of
DSCs and simulate the current–voltage curve and impedance
spectra of the device.25 Ni et al. and Park et al. have used the
thermionic emission theory for description of the FTO/blocking
layer interface and performed IV curve fitting to elaborate
device energy losses in liquid based DSCs.245,246 Boschloo et al.
have used the mesoporous microbeads in working electrodes of
solid state DSCs. If there is no thick spiro capping layer, high
roughness of the sub-micron microbead films causes a big shunt
resistance between the silver and uncovered TiO2 and reduces
the device FF. Using a graphite back contact will decrease the
shunt resistance and increase the device FF. Shunt resistance
of the device has been obtained by fitting the IV curve of the
device.155
Moreover, He et al. have used IV fitting for studying the
dependence of device shunt resistance on the bending degree
of a flexible DSC.247
4.2 IPCE measurements
The spectral response of a solar cell to the incoming light in
terms of current is called IPCE. IPCE stands for incident photon
to current conversion efficiency. In the DC IPCE method,
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Fig. 14 (a) Typical IPCE spectra of DSCs measured for the D35 organic
dye. Normalized IPCE shows that the thicker working electrodes have
more light scattering. Reprinted with permission from (Journal of Physical
Chemistry C, 118, 16472). Copyright (2014) American Chemical Society.
(b) Schematic of an IPCE setup.
the wavelength of incoming monochromatic light is changed
step by step and the current of solar cell is measured at each
step (shown schematically in Fig. 14b). Device IPCE can be
calculated by:248
rate number of collected electrons
IPCEðlÞ ¼
rate number of incident photons
Jmeasured e mA cm2 C1
¼  
Pin ðlÞ mW cm2 (31)
hc=l eV
Jmeasured
¼ 1240 
Pin ðlÞ  l
Intensity of incoming light usually is calibrated to 1 Sun and a
standard Si detector is used to measure Pin. Usually the main
beam is split into two equal beams, one goes to the Si detector
and another goes to the test sample. The same situation of
masking for current–voltage measurement needs to be considered
here. Temperature control of DSCs for long measurements is
essential to measure the correct data in the DC method.248
If the intensity of incoming light is calibrated to 1 Sun (with the
same spectra), we can estimate the short circuit current of the
cell by the integrated IPCE current.
X
nearIR ð nearIR
JIPCE ¼ Jmeasured ðlÞ ¼ IPCEðlÞ  e  Fin ðlÞdl
nearUV nearUV
(32)
Fin and e are incident photon flux and electron elementary
charge. If the integrated IPCE current is not the same as Jsc,
one may conclude some ideas about the mass transport limita-
tion inside the cell. In the bulky redox mediators it is possi-
ble that IPCE integrated current be higher than Jsc. In the
IPCE we have just a portion of real current at each moment
and we integrate the current steps to have the total current.
But under the sun illumination we just have all the current
(resulting from different wavelengths) at the same time and
diffusion limitation of the electrolyte can arise and limit the
cell current.
On the other hand in the solid state devices with spiro
OMeTAD hole conductors, usually we can observe shorter inte-
grated IPCE current compared to short circuit current. In spiro
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based devices the nonlinearity of current versus light intensity
causes disagreement of integrated IPCE current and Jsc.188 To
fix the problem, the AC method can be implemented. In this
method there is a white bias light keeping the Fermi level at the
same level of short circuit conditions, then a chopped light with
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different wavelengths will be applied to the cell step by step and
the current will be measured. The measured current has a DC
component which comes from bias light and an AC component
which is from chopped light.248 Fig. 14a shows the typical IPCE
spectrum of a DSC, measured for organic dye D35 on TiO2. In
most of the dyes, absorption in the green wavelengths is much
better than the red wavelengths that makes the IPCE spectrum
in the green region flat (showing the maximum absorption of
green photons along the film thickness and limited by the FTO
transmittance and charge collection efficiency). Normalizing
IPCE to its maximum, one can compare the red wavelength
response of the cells and compare the light scattering efficiency
within the WEs.154,249,250
Measured current in the IPCE is a product of the charge
collection efficiency, electron injection and light harvesting
efficiency (eqn (33)). Scattering layers can increase light harvesting
efficiency of liquid DSCs.251 The IPCE spectrum mainly indicates
any change in DSC light harvesting efficiency caused by any
device optical modifications252 such as photonic crystals,249
surface plasmon layers,253 co-sensitization,90,254 diffuse or back
scattering layers255–257 as well as tandem cells.258 Absorbed
photon to current conversion efficiency (APCE) is the ratio of
IPCE and light harvesting efficiency and is an estimate of how
the absorbed photons convert to current (eqn (34)). For q-dot
sensitized solar cells APCEs higher than 100% are observed
due to multi electron injection from one single photon. If the
thickness of the film is higher than the diffusion length, by
measuring APCE from the counter electrode side with different
film thicknesses, one can see the red shift of the peak by
increasing the thickness; indicating the diffusion limitations
in the device.259
Isc ðlÞ
IPCEðlÞ ¼ ¼ jLHE ðlÞ  jinj ðlÞ  jcol ðlÞ (33)
efðlÞ
IPCEðlÞ
APCEðlÞ ¼ ¼ jinj ðlÞ  jcol ðlÞ (34)
jLHE ðlÞ
Light harvesting efficiency can be calculated according to
optical transmission, absorption and reflection coefficients
of device components. IPCE is different when you illuminate
the cell from working (jLHE–WE) or counter electrode (jLHE–CE)
sides.259
Measuring the IPCE from working or counter electrode
sides, and considering the diffusion equation in the DSC for
TiO2 electrons, we can estimate the collection efficiency according
to the method of Södergren et al.259,260
This method is appropriate for transparent devices without
highly scattering films. There is disagreement when you measure the
diffusion length using IPCE or transient photovoltage/photocurrent
methods.261,262 (See also Section 6.2.2.)
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5. Photo-induced spectroscopy
In this section, we will summarize the techniques which measure
optical responses of the system following a perturbation by light.
We have roughly sub-divided this section into techniques which
use short laser pulses for excitation (pulsed laser spectroscopy)
such as transient absorption spectroscopy (TAS) and time-resolved
fluorescence spectroscopy and techniques, which used an on/off
modulated source (photo-induced absorption spectroscopy). We
also include the discussion of the Stark effect and electroabsorp-
tion spectroscopy in this section as understanding this effect is
important for the interpretation of transient and photo-induced
absorption spectroscopies.
5.1 Pulsed laser spectroscopy
Pulsed laser techniques are typically used to measure the kinetics
of the electron transfer reactions (see Section 2.2) within the solar
cell. Electron injection, recombination and dye regeneration
times, also dynamics of other photo-induced processes such as
the Stark effect can be monitored by these types of methods.
The underlying concept of laser spectroscopy is to use a laser
pulse to excite the sample (the pump pulse) and then to follow
the induced changes in the sample over time. In time-resolved
fluorescence spectroscopy, the emission from a sample is moni-
tored over time (see Section 5.1.3). In transient absorption
spectroscopy, the absorption of a second light beam (the probe)
by the sample is monitored. The change in absorbance (DA(l))
is then calculated from the intensity of the transmitted probe
beam in the presence of the pump (I(l)pumped) and the intensity
of the transmitted probe beam in the absence of the pump
(I(l)unpumped) according to:
DA(l) = log(I(l)pumped/I(l)unpumped) (35)
For dye-sensitized solar cells, DA may contain contributions
from various transient species and processes, such as ground-
state bleaching of the dye, absorption of the excited or the
oxidised state of the dye, absorption of electrons in TiO2 and
holes in the electrolyte/hole conductor, stimulated emission
from the excited state of the dye and finally shifts of the ground
state absorption spectrum of the dye due to the Stark effect263,264
(Section 5.3). Which species and processes are observed depend
on the time scale of the measurement, and TAS can be sub-
divided into ultrafast TAS and nano-microsecond TAS.
In ultrafast transient absorption spectroscopy, both pump
and probe pulses are generated from the same (femtosecond)
laser and time resolution is achieved through the variation
of the relative arrival times of the pulses at the sample
(Section 5.1.2). A continuous probe beam can be used for
measurements on longer time scales and is typically combined
with a nanosecond pulsed laser as the pump (nano-millisecond
TAS, Section 5.1.3).
5.1.1 Time resolved fluorescence spectroscopy. In time-
resolved fluorescence spectroscopy, a short light pulse is used
to excite the sample and the resulting emission of the sample is
measured as a function of time. For dye-sensitized solar cells,
it is typically of interest to measure the excited state lifetimes of
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the sensitizer either in solution or attached to films by moni-
toring its emission. Depending on the desired time-resolution,
there are different methods for detecting the fluorescence. For a
time resolution of up to nanoseconds, fast-detection electronics
can be used.
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Time-Correlated Single Photon Counting (TCSPC) is a tech-
nique for measuring fluorescence lifetimes with a picosecond
time resolution.265 In this technique, only one emitted photon
can be analysed per laser pulse and histograms of the various
arrival times of the emitted photons make up the fluorescence
decay curve. The count rate of the measurement has to be kept
low, in order to ensure that the decay does not become biased
by early arriving photons.
Fluorescence up-conversion spectroscopy can be used to
measure fluorescence with sub-picosecond time resolution266
and has been used to study electron injection rates in DSCs.267
In this technique, the sample is excited with a femtosecond laser
pulse. The fluorescence of the sample is then frequency mixed in
a nonlinear crystal with a probe pulse from the same laser to
generate frequency mixed radiation, which is then detected. The
frequency mixing only occurs when the probe is present in the
crystal and therefore time resolution of the measurement is
within the laser pulse width. By varying the arrival time of the
probe pulse at the crystal in relation to the excitation, the kinetics
of emission can be measured.
Emission from the sensitizers’ excited state is together with
non-radiative decay back to the ground state: one of the loss
mechanisms competing with electron injection in dye-sensitized
solar cells. Emission intensities can therefore be taken as a
measure of the excited state concentration at a particular time
and emission rate constants (kobs) can be related to injection
rates (kinj) by:
kobs = kinj + k0 (36)
where k0 is the rate of excited state relaxation (of both radiative
and non-radiative relaxation combined).
k0 can be determined by measuring the emission of the dye
on a substrate in which it cannot inject. For these purposes,
typically the wide band gap oxides Al2O3 and ZrO2 have been
used.29,268
In principal, the injection efficiency can be calculated from
kinj and k0 using:18
kinj
jinj ¼ (37)
kinj þ k0
which can be re-written in terms of the fluorescence lifetimes
(tf = 1/k) determined for the dye on TiO2 and ZrO2 or Al2O3 as
tobs
jinj ¼ 1  (38)
t0
In practice it often makes more sense to calculate injection
yields from the integrated area under the decays, as the fluores-
cence decays of the dyes used in DSCs are seldom mono-
exponential. In this case, the magnitude of the reduction in
emission area on TiO2 relative to the inert substrate is taken as
the injection yield.29
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5.1.2 Ultrafast transient absorption spectroscopy. Ultrafast
transient absorption spectroscopy (ufTAS) can be used to
monitor processes occurring in a dye-sensitized solar cell following
from femtoseconds to a few nanoseconds after excitation. Typically,
the main process studied in this time regime is electron injection
from the dye to the metal oxide18,30,269–271 but also fast regeneration
by electrolytes272 or solid state hole conductors220,273,274 has been
measured.
A schematic diagram of the main components of a typical
ufTAS set-up is shown in Fig. 15. The pulses from a femtosecond
Ti-sapphire laser are split into two separate beams to create the
pump and the probe for measurement. Typically, an optical
parametric amplifier (OPA) is used to change the wavelength of
the fundamental laser to a wavelength desired for sample excita-
tion. The pump pulse can then be sent through a chopper before it
hits the sample in order to reduce its repetition rate by half, so that
there is only a pump pulse at the sample for every second probe
pulse. Either the pump or the probe (shown as the probe in Fig. 15)
will have a delay state in its path so that the relative arrival times of
the two pulses at the sample can be varied. Before reaching the
sample, the probe pulse is focussed on a crystal (for example made
of sapphire or calcium fluoride) where a white light continuum is
generated. What wavelength range is generated depends on the
set-up but is most commonly in visible or near infrared wave-
lengths and could also be infrared for infrared transient absorp-
tion spectroscopy or the terahertz frequency regime for terahertz
transient absorption spectroscopy. Finally, the transmitted probe
light is detected with a suitable detector after the sample and the
difference in absorption is calculated from the probe pulses where
the pump was presented on the sample and where it was not. By
measuring transient absorption spectra at different pump–probe
delay times, DA can be determined as a function of both wave-
length and time. The time resolution of the experiment is deter-
mined by the cross-correlation of the pump and probe pulses and
can therefore be very high.
There are different contributions, which can be observed in
the ufTAS spectra of dye-sensitized solar cells:
(1) Bleaching of the dye’s ground state due to the depopula-
tion of the ground-state
(2) Absorption of the dye’s excited state due to the popula-
tion of the excited state by the pump pulse
(3) Stimulated emission from the dye’s excited state back to
the ground state. Photons from the probe pulse can induce this
Fig. 15 Schematic diagram of the main components in an ultrafast transient
absorption set-up.
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process and therefore the emitted photon will travel in the
same direction as the probe pulse and be detected. This signal
shows up as negative DA in the ufTAS spectra with approxi-
mately the same shape of the dye’s emission spectrum and
gives a measure of the concentration of the excited state.
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(4) Absorption of the products formed in electron transfer
reactions. These are the oxidized dyes and electrons in TiO2 for
electron injection into TiO2. If electron injection is followed by
ultrafast regeneration, also the oxidised species of the redox
electrolyte or the hole conductor could be observed.
(5) A shift in the ground-state absorption spectrum due to
the Stark effect226,263,264 (DA) has the shape of the first deriva-
tive of the dye’s absorption spectrum (see Section 5.3).
Fig. 16 shows an example of the ultrafast transient absorption
spectra of the N3 dye on TiO2.270 In these spectra, positive signals
are observed due to the triplet and oxidized state of the N3 dye.
Over time, the amount of triplet dye decreases and the amount of
oxidized dye increases due to electron injection. In the case of N3,
complete intersystem crossing to form the triplet excited state as
well as some electron injection occurs within 0.5 ps after excita-
tion, as both species are observed in the first spectrum shown.
When analysing electron injection kinetics using ufTAS data,
care has to be taken when selecting a wavelength for showing
the kinetics of the oxidized dye.275 For many dyes, there may be
significant overlap between the absorption spectrum of the
excited and the oxidized dye. Selecting a wavelength where both
species absorb could lead to misinterpretation of injection
kinetics. A further issue of transient absorption spectroscopy
can be that measurements are carried out under different
conditions compared to the working conditions of dye-sensitized
solar cells. Many of the studies showing ultrafast electron injection
into TiO2 were carried out on dyed films in the absence of an
electrolyte. Recent studies have shown that injection times
observed for such films do not correspond to electron injec-
tion times observed in the presence of an optimized DSC
electrolyte.272,275,276 A further drawback of ultrafast transient
absorption spectroscopy can be that the peak powers used are
orders of magnitude higher than 1 Sun illumination. These
high laser powers can influence recombination kinetics and
thus lead to a skewing of results.
Fig. 16 TAS spectra of N3 dye on TiO2 at time delays of 0.5 (’), 10 (J),
and 150 ps (m) between the pump and probe pulses. Inset: Transient
absorption kinetics at 860 nm.270 Reprinted with permission from (Journal
of American Chemical Society, 124, 489). Copyright (2002) American
Chemical Society.
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Instead of generating visible or NIR light to be used as
probe light, terahertz or mid-IR pulses have been generated and
used as probe pulses in transient absorption experiments.
Terahertz radiation is absorbed by free charges and terahertz
spectroscopy can therefore be used to study the time-resolved
conductivity of a sample (Section 3.8). It has been used to
study the electron injection of dyes into TiO2 and other
semiconductors.277,278
Mid-IR probes can be used to study molecular vibrations279
as well as the concentration of injected electrons at wavelengths
where molecular vibrations are absent due to the broad absorp-
tion of conduction band electrons in the mid-IR region.272,276,279
5.1.3 Nano- to millisecond transient absorption spectro-
scopy. For transient absorption measurements where a time-
resolution of up to nanoseconds is sufficient, kinetics can be
measured electronically using fast detectors. Therefore, pump
and probe pulses can be generated using separate light sources
and delay lines are not required to achieve time resolution. In
nano- to millisecond TAS, pump pulses are typically generated
by nanosecond lasers such as Nd:YAG lasers or nitrogen-laser
pumped dye lasers. The probe light is often provided by a
continuous white light source employing monochromators
before and/or after the sample. Typical detectors for measure-
ments of time traces are silicon photodiodes or photomultiplier
tubes (PMTs).
When measuring the kinetics of dye-sensitized samples
on a nanosecond or a longer timescale, electron injection is
usually completed and therefore one of the main signals
observed in nano- to millisecond TAS are those arising from
the oxidized dye.
For sensitized samples in the absence of a redox electrolyte
or a hole conductor, TAS has therefore been used to study
the kinetics of electron/oxidized dye recombination and the
electron injection yields. It has been shown that the kinetics of
dye recombination strongly depend on the conduction band
position and electron concentration in TiO2 and therefore on
the laser power in a TAS experiment.38
The recombination kinetics of the oxidized dye often do not
follow simple exponential decays and therefore decay times are
often analysed using half times (thalf), i.e. the time where the
initial amplitude has dropped to half or alternatively by fitting
data to stretched exponentials according to:
 t b
DAðtÞ ¼ DAto e t (39)
where b is the exponential stretch factor.
Electron injection yields can be determined from the initial
amplitude of nano- to millisecond TAS traces from sensitized
samples in an inert electrolyte or without electrolyte if one
assumes that no recombination of injected electrons occurs
prior to the nanosecond timescale. The injection yield is then
given by the ratio of the number of oxidized dye molecules to
the number of absorbed photons and can be calculated using
the following equation:18
DAðlÞ
jinj ¼ (40)
eox ðlÞ  fLHE  Iex  1000
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where l is the probe wavelength, Iex is the intensity of the pump
laser in mol cm2 and jLHE is the light harvesting efficiency of
the sample at the excitation wavelength. eox is the extinction
coefficient of the oxidized dyes.
The regeneration kinetics of oxidized dyes by redox electro-
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lytes and yields have been widely studied by nano- to millisecond
transient absorption spectroscopy by monitoring the oxidized
dye kinetics upon addition of a redox electrolyte48,50,51,57,280 or a
polymer electrolyte.21 In this case, the rate of decay (kredox) is
given by:
kredox = krec + kreg (41)
where krec and kreg are the rate of recombination between electrons
and oxidized dyes and the rate of oxidized dye regeneration. While
krec can be determined from the decay time of the oxidized dye
measured for a dyed film in a supporting electrolyte containing all
the components but the redox couple as described above, kredox
can be determined from the decay time measured for the same
dyed film in the presence of a full redox electrolyte (tredox). The
regeneration efficiency can then be determined from eqn (3),
which can be rewritten as:
kreg krec tredox
jreg ¼ ¼1 ¼1 (42)
kreg þ krec kredox trec
In cases where regeneration is faster than the time scale of the
measurements, which can be for solid state hole conductors,
regeneration yields can be calculated from the amplitudes of the
TAS traces of samples with and without hole conductors and
using the extinction coefficients of the oxidized dye and hole
conductor at the probe wavelength.222,281–283 A common mistake
when using this method has been to choose a wavelength of
analysis where the hole conductor has an absorption peak and
the dye shows ground-state bleaching.222,281,282 At such a wave-
length, also the Stark shift of the dye is likely to be present,263,264
leading to an underestimation of regeneration yields.
5.2 Photo-induced absorption spectroscopy
Photo-induced absorption spectroscopy is a relatively simple
method, which can be used to qualitatively assess injection and
regeneration efficiencies of dye-sensitized solar cells.284 Rather
than using a short laser pulse as the pump in the experiment, a
monochromatic light source with an on–off modulation is used
to excite the sample. The change in absorption of a probe light
by the sample is measured following this on–off modulation,
resulting in the determination of the quasi-steady state spectra
of the transient species under illumination. The PIA spectra of
complete devices can show what transient species are present
during solar cell operation, if pump intensities providing a
similar amount of absorbed photons as 1 Sun illumination are
used. A schematic diagram of a typical PIA set-up is shown in
Fig. 17. The pump light is usually either provided by an LED or
by a continuous wave laser, which can be frequency modulated
using a frequency generator or a mechanical chopper. A white
probe light, which is typically broad enough so that both visible
and near-infrared wavelengths can be measured, is transmitted
through the sample and focussed into a monochromator,
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Fig. 17 Schematic diagram of a PIA setup.
where a wavelength for analysis is selected and focussed on a
detector (for example a silicon detector). The signal from the
detector is amplified and then analysed in a lock-in amplifier at
the frequency of the on–off modulation. Using this method, only
the signal with the same frequency as the modulation is analysed
allowing for highly sensitive detection of absorption changes of
only 106. The signal output from the lock-in amplifier is complex,
i.e. it contains information about the amplitude of the absorption
changes as well as of the phase relative to the modulation. This
is most commonly expressed by an in-phase (real) as well as a
90 degrees out-of phase (imaginary) part of the change in absor-
bance, which is related to the overall amplitude of DA by:
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
DA ¼ sgnðDAre Þ DAre 2 þ DAim 2 (43)
In a PIA measurement, the change in absorption is therefore
determined as a function of wavelength and modulation fre-
quency. Similar to transient absorption spectroscopy, DA can be
described by a sum of the absorbance of the different transient
species (s):
X X
DA ¼ DAs ¼ ½sDes þ DAStark (44)
where [s] is the concentration of s and Des is the difference in
the extinction coefficient between the transient species and the
corresponding ground-state species. DAStark is the change in
absorbance caused by the Stark shift of the dye’s absorption
spectrum (discussed in Section 5.3).
In contrast to the initial concentration in a TAS experiment,
the concentration of the transient species detected in the PIA
experiment will depend on both their generation and recombi-
nation rates. Equations for the concentration and therefore the
PIA signal of a dyed TiO2 electrode in the absence of redox
electrolytes and their derivations can be found in ref. 284 and 285.
In general, a species with a longer lifetime will show a much
higher PIA signal than a species with a short lifetime. Therefore,
a dyed electrode in the absence of a redox electrolyte will show
the peaks relating to the oxidized dye absorption and ground-
state bleaching. Peaks of excited dye molecules will not be
observed due to the short lifetime of the excited dye and there-
fore low steady-state concentration. Whether oxidized peaks are
observed can therefore be a qualitative assessment of efficient
electron injection. Fig. 18a shows an example of this for a
terrylenemonoimidemonoanhydride (TMIMA) dye on TiO2 with
redox-inactive electrolytes containing different sizes of cations.
The magnitude of the oxidized dye peaks observed in the PIA
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Fig. 18 PIA spectra of the terrylenemonoimidemonoanhydride dye on TiO2
(a) in the presence of different cations in a supporting electrolyte solution
consisting of 0.5 M (Li, Na, or TBA) triflate in acetonitrile and (b) in the
presence of 0.5 M Li triflate, or 0.5 M LiI + 0.05 M I2 in acetonitrile. Reprinted
from Chemical Physics, 124, Tomas Edvinsson et al., Photoinduced electron
transfer from a terrylene dye to TiO2: quantification of band edge shift
effects, 357, Copyright (2009), with permission from Elsevier.290
spectrum increases with decreasing cation size. This result is
explained by a positive shift of the conduction band, which
enables electron injection, when smaller cations are present in
the electrolyte.286
Similarly, the efficiency of dye regeneration can be assessed
with PIA. If dye regeneration is fast and efficient, the concen-
tration of the oxidized dye should become very low and only
signals due to electrons injected into TiO2, the oxidized redox
species/holes in the solid state hole conductor and the Stark
effect should be observed. Fig. 18b shows an example of the
regeneration of TMIMA by iodide. In the presence of a redox
electrolyte, the oxidized dye peaks are no longer observed and
instead a broad positive signal is observed which is assigned to
the absorption of conduction band electrons in titanium dioxide.
In the case of incomplete regeneration, signals due to the
oxidized dye will still be observed in the PIA spectrum.122,287
For this reason, PIA has also been used as a method to study
dye regeneration and pore filling in ssDSCs by hole conductors
and conducting polymers.82,85,288,289
5.3 The Stark effect and electroabsorption spectroscopy
The Stark effect occurs when an electric field is applied across
a material and is observed as a change in transition energies
(DE),291–293 given by the following equation:
1 surface (most common, top) and towards the surface (bottom). Reproduced
mdm  F~  Dapol  F~
DE ¼ D~ (45.1)
2 from ref. 297 with permission from The Royal Society of Chemistry.297
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where F~ is the electric field vector and D~mdm and Dapol are the
change in the material’s dipole moment and polarisability due
to the transition.
In dye-sensitized films, electrons injected into the semi-
conductor can cause an electric field normal to the surface and
a Stark shift of the dye molecules’ absorption spectrum.226,263,264
Dye molecules adsorbed to the surface experience this field
on average in the same direction relative to their orientation
on the surface and therefore eqn (45.1) can be used in a one-
dimensional form (along the z-direction here) to predict the
absorption changes, which can then be expressed as:264
 
dA 1 d2 A 2 dA
DA ¼  mz Fz þ Dmz  Dapol Fz2 (45.2)
dE 2 dE 2 dE
In particular organic dyes used in DSCs tend to have a large
change in the dipole moment between the ground and the excited
state which points away from the TiO2 surface. This leads to the
observation of a Stark effect due to the first term of eqn (45.2),
which has the shape of the first derivative of the absorption
spectrum and increases linearly with electric field strength. Fig. 19
shows a schematic representation of the Stark effect behaviour for
dye molecules adsorbed to TiO2 with the change in the dipole
moment along the z-axis in opposite directions.
The Stark effect of DSC dyes can be observed in electro-
absorption spectroscopy, in spectroelectrochemistry and in transient
and photo-induced absorption spectroscopy.
In electroabsorption spectroscopy, the Stark effect is measured
by applying an external electric field across a sample and
monitoring the resulting change in absorption. Fig. 20 shows
the electroabsorption spectrum of the D149 dye adsorbed to a
flat TiO2 layer.264 It can be seen that this spectrum follows the
shape of the derivative of the absorption spectrum (Fig. 20b)
and it is therefore the first order Stark effect, which is observed.
The Stark effect can also be observed in spectroelectro-
chemistry of dyed, mesoporous TiO2 films. In this case a potential
can be applied to the electrode at which electrons are injected
into TiO2 bandgap states or the TiO2 conduction band, which
cause a Stark shift of the adsorbed dye molecules. The electric
field at the TiO2 surface and therefore the change in absorbance
are then proportional to the charge injected into the electrode.
The presence of ions in the supporting electrolyte and how they
shield the electric field experienced by the dye will have an
Fig. 19 Schematic representation of the Stark shift of dye molecules on a
TiO2 surface when the change in dipole moment points away from the
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Fig. 20 Stark effect of the D149 dye. (a) Electroabsorption spectrum.
(b) Absorption spectrum (A) and the first derivative of the absorption
spectrum. (c) PIA spectrum in air and in the presence of a redox electrolyte.
Reprinted with permission from (Journal of American Chemical Society,
132, 9096). Copyright (2010) American Chemical Society.264
impact on the magnitude of the observed Stark effect.285 Studying
the Stark effect by spectroelectrochemistry is therefore a way of
determining at what distance from the TiO2 surface the electric
field drops and where counter ions to electrons injected into TiO2
are located in relation to the dye layer.
Finally, the Stark effect is observed in photo-induced and
transient absorption spectroscopy. Here, electrons injected
from excited dye molecules into the TiO2 due to the pump
pulse will cause a Stark effect of dye molecules remaining in the
ground state. This occurs both in the presence and absence of a
redox electrolyte (Fig. 20c). The Stark effect can therefore mask
other signals at wavelengths where the ground state dye absorbs.
In the presence of an electrolyte the Stark effect can be partially
screened by the ions in the electrolyte. The dynamics of the
Stark effect observed in transient and photo-induced absorp-
tion spectroscopy can therefore inform about the charge com-
pensation in liquid electrolyte DSCs.226,294,295 Furthermore, the
ultrafast dynamics of the Stark effect have been used to study
charge migration in solid state DSCs.296
6. Voltage/current modulation
techniques
6.1 Electrochemical impedance spectroscopy
Electrochemical impedance spectroscopy (EIS) is one of the
most frequently used characterization techniques for DSCs.
In this method a small sinusoidal voltage modulation (dV,
typically B 10 mV) is superimposed on the potential that is
applied to the DSC by a potentiostat. The resulting current
modulation (di) is monitored with respect to both amplitude
and phase shift. The complex impedance is defined as z = dV/di;
z = z 0 + iz00 , where z 0 and z00 represent the real and imaginary
parts of the impedance. The real part reflects the resistance,
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while the imaginary part is affected mainly by capacitance
(negative z00 ) and inductance (positive z00 ). A wide range of
frequencies, typically in the range of 105 to 102 Hz, is measured
to create an impedance spectrum. The impedance spectrum is
plotted as a Nyquist plot, (z00 vs. z) or as a Bode plot wherein the
parameters (z 0 , z00 , |z|, phase) are plotted versus logarithm of
frequency. Equivalent circuits, corresponding to a typical DSC,
are used to analyze the impedance spectrum and extract the
related information i.e. charge transport or recombination resis-
tances. They are composed of standard electrical components,
such as resistors (R) and capacitors (C), as well special compo-
nents, such as the Warburg impedance that describes diffusion
processes.
EIS measurements on DSCs are performed under dark or
illumination conditions. Parameters such as the series resistance,
chemical capacitance, transport resistance, recombination resis-
tance, counter electrode charge transfer resistance and capaci-
tance, as well as Warburg impedance can be obtained from the
EIS spectra.67,298–300 Fig. 21 shows a typical EIS spectrum of a
liquid electrolyte DSC. If the characteristic time constants of the
different processes are well separated, resistances and time
constant can be obtained graphically from the EIS spectrum.
Usually, fitting with an equivalent circuit is performed for
further analysis of DSC parameters. Suitable equivalent circuits
have been derived for liquid electrolyte and solid-state DSCs, as
well as for perovskite solar cells, which can be used to char-
acterize and simulate device behavior according to its virtual
electrical components.301–304 Any virtual electrical component
is related to a particular parameter (i.e. a reaction rate or
density of states) in the device. The standard model used for
fitting of the data is the transmission line model for DSCs, see
Fig. 22.305–308 This model can be more simplified when using
certain conditions, such as open circuit conditions under illumi-
nation. Fabregat et al. have written a comprehensive review about
EIS of DSCs, explaining the interpretation of data for different
materials in DSCs.16
In the transmission line model, the contact and substrate
resistances are modelled by a simple resistor Rs, the FTO/
blocking layer interface with electrolyte is modelled by a parallel
capacitor|resistor combination, in which the capacitor (CBL) is
representative of the Helmholtz double layer at the interface and
Fig. 21 Typical EIS spectrum for liquid electrolyte based DSCs. Reprinted
with permission from (Journal of Physical Chemistry B, 110, 13872).
Copyright (2006) American Chemical Society.
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Fig. 22 Transmission line model for liquid electrolyte based DSCs. Repro-
duced from ref. 309 with permission from the PCCP Owner Societies.
RBL is the charge transfer resistance from the blocking layer to
the electrolyte. The mesoporous TiO2 structure is modeled by
a series of interconnected nanoparticles, each has a parallel
capacitor|resistor element (cm|rrec) to the electrolyte and a
transport resistance (Rtr) in between. The superposition of all
these elements gives the mesoporous TiO2 chemical Cm, its
recombination resistance Rrec and its transport resistance Rtr.
The diffusion impedance of the redox mediator in the electrolyte
is given by the Warburg impedance element (Zd), and the counter
electrode is simulated by another parallel resistor/capacitor
(CCE|RCE) combination, which is an indicator of the capacitance
and charge transfer resistance at the counter electrode (see
Fig. 22). The total impedance of the mentioned model can be
described in terms of the above mentioned parameters.298
Several important properties can be calculated from the EIS
fit parameters, such as the electron lifetime (te), the effective
diffusion coefficient for the electrons in the mesoporous TiO2
(Dn) and the electron diffusion length (Ln):40,298
te = Rrec  C (46.1)
d2
Dn ¼ (46.2)
Rtr Cm
rffiffiffiffiffiffiffiffi
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi Rrec
Ln ¼ Dn  t e ¼ d (46.3)
Rtr
d is the TiO2 film thickness. Since different processes in DSCs
are assigned to electrical components, it would be possible to
compare different devices in terms of recombination resistance,
series resistance, capacitance, diffusion coefficients of electrons
and redox mediators, etc. Dedicated programs are available to
analyze and simulate the EIS data. Special care should be taken
to check the validity of the fitted parameters, i.e. comparison of
the relative error and fitted value. Further details can be found
elsewhere.298,300,305,310–315 The importance of the measured para-
meters for the device performance is mentioned in Section 1 and
in ref. 25.
By repeating the EIS measurement at different applied
potentials, trends in the recombination resistance and chemical
capacitance (density of states) of devices as a function of Fermi
level can be studied and compared, and possible band shifts can
be pin pointed.305,314 For determination of any band shift, the
potential drops due to resistance in the conducting glass, at the
counter electrode and in the electrolyte part of the device
should be determined and the fitted parameters should be
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corrected accordingly.314 Series and counter electrode resistances
measured using EIS are normally independent of the applied
potential on the DSC, but the chemical capacitance, recombination
resistance and transport resistance of mesoporous TiO2 electrodes
have exponential dependence on the applied potential37,67 The
transport resistance was found to be inversely proportional to the
density of carriers at the transport level which is governed by
the Boltzmann distribution.67
The recombination resistance is different in dark and
light:44,66,316 in the dark there is no recombination to oxidized
dye molecules, and the recombination processes are between the
TiO2 electrons and electrolyte oxidized species only. Furthermore,
under light conditions, regeneration of the dye by the redox
electrolyte will change the concentration of oxidized species
compared to dark conditions. Effects of the working electrode
morphology, electrolyte compositions and the dye on the electro-
nic lifetime and transport have been studied with EIS by several
groups.317–323 Further details about the concepts and interpreta-
tion of EIS for DSCs are beyond the present review and can be
found elsewhere.298,300,305,310–313
A slight modification of the transmission line model can be
applied to solid state DSC devices324,325 and perovskite solar
cells.326 Importantly, the transport resistance of the hole con-
ductor is included in these models. A negative impedance was
observed for perovskite devices at very low frequencies. The
origin of this effect is unclear.326 Fabregat-Santiago et al. studied
solid-state DSCs with spiro-OMe-TAD hole transporting materials
using EIS.181 They found that a high recombination rate in these
devices and the high resistivity of the spiro layer are the factors
that reduce the FF and efficiency of the device.181
The origins of high open circuit voltage in polymer electrolyte
DSCs have been investigated recently by Kim et al. using EIS.327
They conclude that the capture of Li+ ions by the electrolyte
polymers and the formation of a polymeric passivation layer on
the TiO2 nano particle surface cause a CB downward shift and
retarded electron recombination kinetics resulting in a high
open circuit voltage.
EIS is also a useful method to study the performance of the
counter electrode in DSCs. Different counter electrodes show
different charge transfer resistances for different redox mediators.
To simplify EIS analysis, sandwich cells consisting of two counter
electrodes with redox electrolytes in between are frequently used.
The equivalent circuit of such a system is shown in Fig. 23,170,328
together with a typical EIS spectrum.213 For porous counter electro-
des it is possible to have another semicircle in high frequency parts
which belongs to second Nernst diffusion impedance of porous
layers in the counter electrode.170,328
EIS analysis of the TiO2 blocking layer in liquid electrolyte
DSCs was performed by Cameron et al.329 Thicker blocking layers
can reduce the current (due to higher device series resistance)
and lower the back recombination rate.330 For compact semi-
conductor films, Mott–Schottky analysis can be used: the capaci-
tance of the semiconductor electrode is measured as a function
of applied voltage. When a high modulation frequency is used
(i.e. 1 MHz to 10 kHz), the measured impedance may be analyzed
using a simple RC circuit.331 Using the Mott–Schottky equation
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Fig. 23 (a) Equivalent circuit (where CPE is a non-ideal capacitor) and (b)
typical EIS spectra of a counter electrode sandwich cell with a redox
electrolyte. Reprinted with permission from ACS Appl. Mater. Interfaces, 6,
2074. Copyright (2014) American Chemical Society.
and from a plot of 1/C2 versus potential, the flat band potential332
and the doping density of the semiconductor can be obtained.333
However, it should be noted that Mott–Schottky analysis is not
valid for mesoporous semiconductor electrodes, as it relies on
band bending in the semiconductor, which is usually not present
in mesoporous electrodes. Larger particles, branched nanostruc-
tures and FTO substrates on the other hand can have space charge
layers and thus can be analyzed by the Mott–Schottky method. The
maximum attainable photovoltage in DSCs can be affected by the
band bending and charge accumulation at the FTO/TiO2 interface
that can be characterized by the Mott–Schottky or interference
reflection method.334
The ionic conductivity of the electrolyte can be obtained
from the diffusion coefficient using eqn (16)335 and the ionic
conductivity of gel/polymer electrolytes in the quasi-solid state
DSCs is usually obtained from an AC impedance spectrum of
the gel/polymer electrolyte sandwiched in a symmetrical cell.196
6.2 Small light perturbation photovoltage/current response
Small light perturbation techniques, where a small square-wave,
sine wave or pulse of light is added to a much larger constant bias
light intensity, and the resulting photovoltage or photocurrent is
monitored, offer rapid insight into some of the most important
electron transfer reactions in DSCs. If the perturbation is small
(o10% of the bias light), electron concentration in the meso-
porous TiO2 can be treated as being constant, and electron
transfer reactions appear to have simple first order kinetics.
Initially, sine wave modulation was mostly used, and the response
was analyzed in the frequency domain, similar to EIS. These
techniques are known as intensity-modulated photovoltage and
photocurrent spectroscopy, IMVS336,337 and IMPS,337,338 respec-
tively. Data are analyzed in a similar way to that in EIS. Usually
one or more semicircles are found when the imaginary part of the
signal is plotted against the real part. From the frequency ( f ) at
the maximum of the semicircle the characteristic time constant
is calculated:
1 dark and light conditions can give information about the recom-
t¼ (47)
2pf
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Later, time domain techniques, monitoring the pulse or step
response, have become more popular, because of their much
faster measurement speed.339,340 In this case the response is
fitted using an exponential function and a single pseudo first
order rate constant k or time constant t is extracted (t = 1/k).
Compared to EIS, these techniques are more straight-forward
and rapid, without further need of models and data fitting.
Usually a white LED or a series of white LEDs are used for the
bias light. Modulation is provided by the same LED or separate
LEDs that can have different color. Uniform light absorption in
the whole film is preferred, since this results in the simplest
electrical response. Non-uniform excitation results in some
initial effects in the photocurrent response due to fast charge
reorganization.341 Repeating the measurements at different
light intensities and/or at different Fermi levels gives more
complete information about the device. By changing the
temperature, the activation energy of electron transport in the
DSCs can be calculated.342 Influence of cations on charge
collection of DSCs,343 the effect of anions in ionic liquid based
DSCs,337,344 additives,316 stability under UV irradiation,345 light
soaking,346 surface modification of electrodes,123,287 different
working electrode morphologies or doping levels,35,66,141,154,347 the
reduction mechanism of iodide,348 dye coverage effects147,149,349 as
well as different processes of solid state dye sensitized155,288,346,350
and perovskite based351 solar cells have been studied using
photovoltage/current transient techniques. O’Regan et al. have
written a comprehensive review about transient techniques.15
6.2.1 Electron lifetime measurements. For electron lifetime
measurements, the photovoltage response of a DSC in a small
light perturbation measurement is monitored under open-circuit
conditions, or alternatively under any other constant current
conditions using a galvanostat. The resulting photovoltage
response time is equal to the lifetime of electrons in the
mesoporous TiO2, since electron recombination to the redox
electrolyte is the only way for the system to adjust its Fermi level
to the altered illumination condition. Effects of different
electrolyte additives in DSCs,316 different redox mediators352,353
as well as surface modification of electrodes287, different dye
structures and coverages147,150 and the working electrode
morphology35 have been studied using electron lifetime
measurements. Longer lifetimes are always preferred because
this will result in higher Voc and FF of DSCs.
An alternative measurement to obtain the electron lifetime
is from a Voc decay measurement: the DSC is kept under open-
circuit conditions and under illumination and the output
voltage is measured as a function of time when the light is
turned off. Analysis of the decay gives the electron lifetime:354
 
kB T dVoc 1
te ¼ (48)
e dt
It is possible to measure Voc decay in the dark by means of an
initial applied potential.355 As mentioned in Section 6.1 lifetimes
in the dark and light conditions are different, and comparison of
bination rates to the oxidized dye.44 Voc decay measurements
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have been used to fit the Marcus theory equation and obtain
detailed information about electron recombination rates.41
6.2.2 Electron transport time measurements. The photo-
current response rate constant, determined from small light
perturbation measurements, has contributions from electron
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transport and electron recombination in DSCs. Under short
circuit conditions when the modulation light is switched off,
excess electrons have two routes in order to keep the current
constant: recombination to acceptors in the electrolyte (ke = 1/te)
or transport to the FTO contact (ktr). The photocurrent response
rate constant (kpc) can be described as:356
kpc = ktr + ke (49)
Under short-circuit conditions the Fermi level in DSCs with
iodide/triiodide electrolytes was found to be about 200 mV
lower than that under open circuit conditions, resulting in
much longer lifetimes compared to the transport time.357 In
that case the photocurrent response time is almost equal to the
transport time (ktr c ke, so that kpc E ktr). As electron transport
in mesoporous TiO2 is driven by diffusion, the transport time
(ttr) is related to the effective diffusion coefficient (Dn) of
electrons by:70
ktr d 2
Dn ¼ (50)
2:4
where d is the thickness of a mesoporous film. The factor 2.4 is
an approximate value, coming from the geometry of the system.
A typical value of Dn in a mesoporous TiO2 of a DSC under
1 Sun illumination is B104 cm2 s1, which is many orders
of magnitude lower than that found in TiO2 single crystals.
Furthermore, Dn is found to decrease at lower light intensities,
which can be explained using the multiple trapping model. The
electron diffusion length can also be determined using transient
techniques:
sffiffiffiffiffiffiffiffiffiffiffi
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi ktr
Ln ¼ Dn  te ¼ L (51)
2:4ke
The electron diffusion length remains rather constant as a func-
tion of light intensity, since transport rates as well as recombina-
tion rates change by approximately the same amount as a function
of light intensity. Ln can also be determined from steady-state
techniques: it can also be extracted from IPCE measurements,260
and from photocurrent measurements of mesoporous films
on patterned FTO substrates with different gap sizes.358 There
appears, however, to be a difference in values calculated from
steady-state IPCE and modulation methods, the latter over-
estimating it by a factor of 2.359 This can be explained by non-
linear recombination kinetics in DSCs.360
The charge collection efficiency (jcol) can be calculated as
follows:
ktr kpc  ke ke
jcol ¼ ¼ ¼1 (52)
ktr þ ke kpc kpc
It too may be overestimated using small transient techniques.359
The charge collection efficiency can also be estimated using the
IPCE data (Section 4.2).259 In liquid electrolyte DSCs, however,
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charge collection is almost independent of the light intensity
which can be seen from the linear dependency of Jsc on the light
intensity.8 Charge collection efficiencies in high efficient cells
are close to 100%.10
All the above techniques are usually performed under two
different specific conditions: open-circuit and short-circuit.
It is possible to measure the lifetime or transport time in real
working points of the solar cell such as the maximum power
point.341,356 Using 1 Sun illumination intensity and coupling
the potentiostat/galvanostat to the cell, we can keep the cell in a
certain potential or current corresponding to a certain working
point from the IV curve. Applying the modulation light to the
cell under potentiostatic/galvanostatic conditions will perturb
the current/voltage of the cell and its rise and decay times
corresponding to the photocurrent response time/electron life-
time of the DSC.
6.3 Large light perturbation photovoltage/current techniques
Additional information on DSCs is obtained from the large
light perturbation method, where the light is switched on or off.
6.3.1 Charge extraction. Duffy et al. introduced the charge
extraction method for DSCs: the cell is illuminated (keeping
under certain open (short) circuit conditions) and then the light
is switched off, while the cell is switched to short circuit condi-
tions and its current is integrated versus time to give the extracted
charge under open (short) circuit conditions (QOC or QSC).361 The
amount of stored charge in the working electrode is indicative
of the density of states in the mesoporous semiconductor.
Comparative studies can indicate band shifts that are important
factors for the evaluation of the cell performance.123,357,362,363
Under UV irradiation, photo-induced positive states are formed
at TiO2, which can shift the TiO2 CB band as well.286
For charge extraction measurements, recombination of
electrons to electrolyte species is a source of error, which can
be significant. Because of the high recombination rates for
solid-state DSCs, this method is not reliable. A capacity method
as developed by Snaith et al. can be used instead: the capacity
versus voltage is measured under working conditions and by
integration of capacitance versus voltage the charge is calculated.37
Here, the extracted charge is usually exponentially dependent
on the potential of DSCs, which reflects the exponential distribu-
tion of trap states in the mesoporous TiO2 electrode:347
ð EFn    
EFn  EF0
QOC ¼ gðE ÞdE ¼ mc g0 exp 1 (53)
EF0 m c kB T
The trap distribution parameter mc, which is equal to the
average trap depth, can be obtained from this equation and
is an important parameter in characterization and comparison
of different DSCs.
Short circuit charge of the working electrode has a power law
dependence on the short circuit current density.69 Further-
more, mc can be obtained from the slope of the logarithmic
plots of QSC (charge under short circuit conditions) versus light
intensity and the logarithmic plot of transport time versus light
intensity (the corresponding slope values are equal to kBT/mc
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and (kBT/mc  1) respectively).69 Peter et al. introduced a new
method for charge collection efficiency estimation, which is
calculated from the ratio of light intensities giving the same
charge under OC and SC conditions.261
We can measure mc from logarithmic plots of Voc versus light
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intensity using eqn (4). Finally, near-infrared transmission
measurements can be performed to determine the total electron
concentration in mesoporous dye-sensitized solar cells.364
6.3.2 Measurement of the Fermi level in mesoporous elec-
trodes. Under short circuit conditions there is a non-uniform
distribution of electrons in the film thickness, which results in
a Fermi level gradient. This Fermi level is around 200 mV lower
than open circuit conditions.357 By using a switching method,
the approximate average Fermi level can be determined: the cell
is first kept under short circuit conditions under light, then,
simultaneously, the light is witched off and the cell is switched
to open circuit conditions. This gives a time dependence of the
potential that was built up from the remaining electrons in
mesoporous TiO2, from which VSC, and average of the Fermi level
in the mesoporous electrode for DSCs, kept under short circuit
conditions, can be determined.342,347,357 Higher VSC, at the same
current density, can be explained by a higher specific surface
area of the particles, a lower electronic diffusion coefficient or
because of band bending in bigger particles.
An alternative method for measuring VSC requires the deposi-
tion of an additional titanium electrode on top of the meso-
porous TiO2 films. The surface of the metal is passivated by
thermal oxidation and does not lead to an additional recombina-
tion pathway for electrons in TiO2. The potential of the additional
electrode can be measured under operating conditions and
directly gives the quasi-Fermi level at the outside of the meso-
porous TiO2 films.365 Both methods give similar results.
Simulations of small/large modulation of light intensity
experiments with electron diffusion equations/random walk
models have been performed by several groups to understand
and rationalize the device performance and its changes under
different conditions.8,15,69,235,360,366–368 Most of the described
techniques in the present Section 6 are coupled to simulations
and models in order to further elucidate information about
the DSC parameters (such as reaction orders and activation
energies).
7. Remarks on DSC characterization
7.1 Remarks on solid state DSCs
Introduced by Grätzel and Bach, solid state DSCs have an
important architecture, which eliminates the need of a liquid
electrolyte in the device. In fact, recently developed highly
efficient perovskite solar cells are derived from the ssDSC archi-
tecture. There are several review reports on the optimization of
device components such as the hole conductor, back contact and
the dye.19,369–372 For ssDSCs, the same presented characterization
methods can be employed for evaluation of LHE, injection and
regeneration efficiencies as well as charge collection efficiency
in the device. Due to a higher recombination rate in ssDSCs,
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special care is needed for measuring the transport time in these
devices – see Section 6.2.2. ssDSCs are more sensitive to the
thickness and conductivity of each component compared to
liquid electrolyte based DSCs. Pore filling of the hole conductor,
interface recombination and conductivity of the hole conductor
are still the main issues to be considered towards fabrication of
highly efficient devices.77,370
In ssDSCs, FF losses are because of series resistance (con-
ductivity) of components or recombination losses, while potential
losses are mainly due to the overpotential needed for electron
injection/dye regeneration; moreover the photocurrent losses
stem from limited LHE/photon absorption by the device.369 Since
the recombination rate is higher in solid state DSCs, the role
of blocking layers is more prominent than in liquid DSCS.
Furthermore as a result of a higher recombination rate and
poor pore filling of a hole transporter within the mesoporous
film, the limited device thicknesses necessitate the use of very
high extinction coefficient dyes.83 Thus LHE is an issue which
is limited by the device thickness.
Under short circuit conditions, device efficiency is limited by
the diffusion length of electrons therefore new TiO2 structures
with higher conductivities and larger crystallite sizes together
with higher surface areas37,373 are under investigation. On the
other hand in the higher charge densities the conductivity of spiro
can be a limiting factor and doping of spiro with chemical dopants
or employing the photodoping ability of Li is implemented by
several groups to achieve high efficiencies.171,174,181,374–376
New dyes with a higher extinction coefficient and broader
spectra83 and new hole transport materials are on the way to
increase the LHE and lower the overpotential voltage losses in
the device.346,350,377 Recently polymer based hole transporters
are reaching 6.8% efficiency by using PEDOT polymers.378
Utilizing thicker TiO2 films became possible by means of
in situ light driven polymerization of EDOT on the dye sensi-
tized films.379
The best reported ssDSC efficiency so far is 7.7% in which
spiro is the hole conductor doped with an additive dopant.380
Studying and optimizing the device continue while the ssDSC
concepts are considered as insightful to help obtain higher
efficiencies for perovskite solar cells.
7.2 Remarks on liquid–electrolyte DSCs
The only class of DSCs which are really commercialized in the
market are liquid–electrolyte DSCs; they have a range of colours
and transparencies and benefit from long term stability/high
efficiencies in the low light intensities.1,6
The efficiency improvement rate during the last 10 years was
so slow although the expected theoretical efficiency for liquid
DSCs is about 20% with supposed 920 mV Voc and 30 mA cm2
Jsc.71 Engineering the dyes and electrolytes to reduce the
potential losses and employing new redox mediators with more
positive redox potentials are the main strategies to further
increase the voltage. Voc values of more than 1 volt have been
reported and are easily attainable with new metal complex redox
mediators,71 although the corresponding potential loss is still too
much, i.e. for the record cell dye in the cobalt electrolyte based
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device it is about 900 mV. At the moment the highest obtained
efficiency is 14.7%.72
Improving the TiO2 Fermi level using novel nanostructures
with lower trap densities, decreasing the dye regeneration
overpotential by either using new redox mediators or dye
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molecules, reduction of recombination losses by modification
of dye linker units, decreasing the thickness of TiO2 films using
the higher extinction coefficient dyes are among the recent
efforts and strategies to improve the open circuit voltage of the
device.
On the other hand, employing new dyes with higher light
absorption and higher injection efficiency is the main strategy
to improve the photocurrent. Hence, tuning the optical band
gap of the dye to harvest enough light and keep Voc high enough
is vital. Photocurrent densities of more than 20 mA cm2 are
reported using Ruthenium dyes but for the record efficiency
porphyrin dye, Jsc is still below 20 mA cm2.71 Decreasing the
oxidized dye recombination, modification of the dye with
electron deficient moieties, harvesting of more photons by
changing the E0–0 values of the dye and having the colourful
dyes for transparent market applications are some of the hot
topics for dye engineering in the DSC field.
Due to the recent success of cobalt complexes as redox
mediators in DSCs, the research on other metal complexes381
with less optical absorption, a smaller molecular size and more
positive redox potential becomes more prominent recently. The
larger size of these complexes compared to iodide necessitates
the optimization of working electrode porosity to avoid mass
transport limitation in the device.
Nevertheless there is still some ongoing research on the novel
metal oxide architectures and advanced photonic managements
of the scattering layer, so far the initial mesoporous titanium
dioxide films have the best performance and have been used in
all reported record efficiencies. IPCEs of close to 90% and
charge collection efficiencies of close to 100% are achieved
by mesoporous TiO2 nanoparticles, leaving the main bottle
neck of efficiency more towards the dyes and redox mediator
side.3,5,6,382–390
7.3 Remarks on quasi solid state DSCs
The device structure and the concepts of quasi solid state DSCs
(qssDSCs) are similar to liquid DSCs; and in principle similar
characterization techniques have been used to investigate and
improve the device performance of qssDSCs.391 In qssDSCs,
a higher thermal stability is obtained due to the negligible
electrolyte vapour pressure and better device stability is
achieved through the addition of an inert polymer or a polymer
Table 1 Characterization techniques for the time scales of different DSC processes
DSC processes Measurement methods
Electron injection Femtosecond laser/terahertz spectroscopy
Oxidized dye recombination PIA, nanosecond laser spectroscopy small light modulation, EIS in light and dark
Dye regeneration Nanosecond laser spectroscopy, SECM
Electron recombination lifetime EIS, small light modulation, laser spectroscopy
Electron transport time EIS, small light modulation
Stark effect Timed/frequency PIA, EA, nanosecond laser spectroscopy
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matrix such as poly(methyl methacrylate) (PMMA)392 or poly-
(vinylidene fluoride-co-hexafluoropropylene) (PVDF–HFP),393 and/or
addition of metal oxide nanostructures such as silica,394 or
alumina395 in the liquid electrolyte or gelation of ionic liquid
electrolytes.396
The same bottle necks for the device PCE of liquid DSCs are
valid for qssDSCs as well. However the maximum reported
efficiency of 9.61%397 and maximum achievable current density
for qssDSCs are lower than the reported values for liquid DSCs.
The presence of metal oxide nano particles or the organic
polymers in the electrolyte affects the pore filling and viscosity
of the electrolyte and the diffusion of redox mediators which
lowers the efficiency. Thus the thinner sealants and smaller redox
couples are more preferable. The mass transport is a more
prominent issue377,398,399 and the corresponding ionic trans-
port in the electrolyte is evaluated by impedance spectroscopy
(Section 6.1), light intensity dependence of current density
(Section 4.1.2) or CV (3.9.1).195,196,327,377,391,392,398 Furthermore,
the presence of the polymer/nanoparticles in the electrolyte
results in new interactions with the TiO2/dye interface and/or
ionic species in the electrolyte and thus affects the device
efficiency.228,327 Absorption, rheological and thermal (TG)
analyses are particularly employed to further characterize the
gel electrolytes. The main efforts have been devoted to achiev-
ing better ionic conductivities, less mass transport limita-
tions and also reaching better pore filling of the polymer
electrolyte in the pores of the photoanode. We refer the reader
to a recently published review about the characterization techni-
ques for quasi solid state polymer electrolyte DSCs for further
information.196
8. Concluding remarks
As DSC research continues going forward, the need of more
fundamental research becomes more clear and essential for
developing a low cost, large area, highly stable and efficient
solar cell. For stability tests, comprehensive characterization of
different light/temperature induced chemical changes and the
corresponding impacts on the device efficiency are vital. Under
thermal stress DSCs can change from the situation of Rrec c Rtr
to Rrec { Rtr and alter the impedance behaviour of the cell
changes respectively.320 Relative positions of the redox Fermi
level and the CB position, the diffusion coefficient of the redox
mediator and the electron lifetime of the TiO2 electrons are
dependent on the temperature of the device40,342,400 and can be
further altered by temperature induced changes in the long
Section(s)
5.1.2
5.2, 5.1.3, 6.2 and 6.1
5.1.3 and 3.3
6.1, 6.2 and 5.1.3
6.1 and 6.2
5.2, 5.3 and 5.1.3
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Table 2 Characterization techniques for the energy levels of DSC components

Component energy level Measurement method Section(s)

Dye HUMO level CV, XPS 3.9.1 and 3.6
Dye LUMO level Emission/UV_Vis and CV 3.7 and 3.9.1
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TiO2 CB edge Light perturbation, Mott Shottky, spectroelectrochemistry 6.2, 6.3, 6.1 and 3.9.2
Fermi level at short circuit Large light perturbation 6.3.2
TiO2 valence band edge XPS(UPS), spectroelectrochemistry 3.6 and 3.9.2
Surface density of states STM 3.3
Intra-band gap density of states CV, EIS, spectroelectrochemistry 3.9.1, 6.1 and 3.9.2
Redox mediator Fermi level CV 3.9.1
Hole conductor energy level CV, XPS 3.9.1 and 3.6
Counter electrode Fermi level Over-potential estimation from CV and simulations 3.9.1

Table 3 Techniques for measurement of other important parameters of DSCs

Parameter Technique for measurement Section(s)

Thickness of working/counter electrode SEM, profilometry 3.1
Porosity of working/counter electrode SEM, BET, UV/Vis & SEM, reflectometry 3.1, 3.2, 3.7
Diffusion length of electrons EIS, small light perturbation, IMPS/IMVS, IPCE 6.1, 6.2, 4.2
Diffusion coefficient of redox mediator CV, EIS, limited current 3.9.1, 6.1, 4.1
Diffusion coefficient of electrons EIS, small light perturbation, IMPS/IMVS 6.1 and 6.2
Hole transporter pore filling PIA, XPS, reflectometry, laser spectroscopy, UV-Vis, SEM 5.2.1, 3.6, 5.1, 3.7, 3.1
Hole transporter conductivity Four point probe, TOF, terahertz spectroscopy, PICC 3.8
Conductivity of working/counter electrode Four point probe, TOF, terahertz spectroscopy, PICC 3.8
Light harvesting efficiency UV-Vis, IPCE 3.7 and 4.2
Electro catalytic efficiency of counter electrode EIS, CV 6.1 and 3.9.1
Dye coverage UV-Vis, dye deloading, photocurrent transient, 3.7 and 3.6
quartz crystal microbalance, NICIS, XPS
Interface electric field PIA, EA 5.2 and 5.3
Dye regeneration efficiency Laser spectroscopy 5.1.3
Electron injection efficiency Laser spectroscopy, IPCE, PIA 5.1.1, 4.2, 5.2
Charge collection efficiency EIS, small light perturbation, IMPS/IMVS 6.1, 6.2
Dye adsorption mode STM, XPS 3.3 and 3.6
Electron density of states Charge extraction, EIS, CV, XPS 6.3, 6.1, 3.9.1 and 3.6
Recombination rate/charge transfer resistance EIS, CV 6.1 and 3.9.1
Stored charge in WE Charge extraction, EIS, CV 6.3, 6.1 and 3.9.1
Redox Concentration changes in stability tests Mass spectroscopy, small and large light perturbations, EIS 8, 6.2 and 6.3
Limiting current Dark current 4.1.2
Dye coloration efficiency Spectroelectrochemistry 3.9.2
WE crystallite size TEM, XRD 3.1 and 3.5
Dye dipole moment changes EA/PIA 5.2 and 5.3
Blocking layer charge transfer resistance CV, EIS 3.9.2 and 6.1
TiO2 flat band potential Mott–Schottky 6.1

term stability tests. A 20 year lifetime for DSCs is predicted401
and studying high viscous electrolytes such as MPN is currently
pursued specially for stability tests.169,402 Besides, in a very
recent study, Jiang et al. have reported the 2000 hour stability of
cobalt electrolyte based DSCs with acetonitrile.403 Mass spectro-
scopy can be an interesting method for studying the chemical
reaction in stability tests.404
Regarding the presented examples, voltage, current and fill
factor losses in the liquid/solid state devices can be classified
into topics related to the energy levels, reaction rates and
charge transport characteristic lengths. Last but not the least,
Tables 1–3 show a summary of different investigated techni-
ques for different processes, components and important para-
meters of liquid and solid state DSCs.
Acknowledgements
We gratefully acknowledge the Swedish Energy Agency, the
Swedish Research Council (VR), and the ST and UP for
Energy program for financial support. We thank Dr Roghayeh
Imani for her help in the preparation of the table of content
graphic (TOC).
Notes and references
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