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Implementation of Single-Walled Carbon Nanohorns

REVIEW
into Solar Cell Schemes
Fabian Lodermeyer, Rubén D. Costa,* and Dirk M. Guldi*

We would like to dedicate this paper to Prof. Dr. Nazario Martín on the occasion of
his 60th birthday.

spherical – i.e., fullerenes with alternating

Recent advances in dye-sensitized solar cells (DSSC), including the use of five- and six-membered rings
nanocarbons, resulted in breakthroughs relevant to both the academic and and different number of car-
industrial sectors. Their relevance encompasses, on one hand, the develop- bon atoms like C60, C70, etc.[1–3]
ment and integration of novel nanocarbon/dye hybrids for superior light-har- Hereby, the two earlier carbon nano-
vesting and improved charge injection properties and, on the other hand, the structures form surfaces of zero Gaussian
integration of nanocarbons into each part of DSSCs for enhancing the charge curvature, whereas the latter represents
collection efficiency as well as the dye and electrolyte regeneration processes. the class of carbon nanostructures with
In the context of the earlier, control over the electron injection and recombi- a positive Gaussian curvature.[4] Impor-
tantly, carbon allotropes, such as holey-
nation rates is realized on the molecular level. In the context of the latter,
balls and holey-tubes, exhibit a non-
i) the charge transport and charge collection efficiencies in the photoelectrode positive Gaussian curvature.[5] Linking a
are increased, ii) the charge recombination processes are reduced, when used graphene sheet, while removing wedges,
as a nanocarbon-based buffer layer, iii) the ion diffusion and catalytic effects will eventually transform into a conical
into (quasi) solid-state electrolytes are improved, and iv) devices using Pt-free shape, whose apex is defined by one or
counter electrodes with similar device efficiencies are realized. Leading exam- more declinations taking the form of
pentagons.[4,6] The resulting carbon nano-
ples of nanocarbons are graphene, carbon black, multi-walled carbon nano-
cones and nanohorns are defined like
tubes, and single-walled carbon nanotubes. In this review, the focus is on a carbon nanotubes and graphene by a zero
novel carbon allotrope, namely single-walled carbon nanohorns (SWCNH), Gaussian curvature. Single-walled carbon
which is discussed in depth and in comparison with other nanocarbons. nanohorns (SWCNH) are a class of such
conical carbon nanostructures, with an
apical angle of 20°, a reproducible, high-
1. SWCNHs: Definition, Properties, yield, catalyst-free synthesis route, and distinct aggregate struc-
tures.[7] Noteworthy, the synthesis of carbon nanohorns via arc
and Characterization
discharge also results in multi-walled carbon nanohorns as they
In the field of carbon nanostructures, the scientific community have been isolated as a side-product in the synthesis of fuller-
has defined: enes.[8] SWCNHs possess conical structures with diameters
ranging from 2 to 5 nm, a length from 30 to 50 nm, and angles
tubular – i.e., carbon nanotubes in the form of single-, double-,
of the conical tips of around 20° (Figure 1).[4,9] In solution,
and multi-walled derivatives,
they associate into round-shaped and loosely-bound aggregates
sheets – i.e., single- or a few-layer graphene with purely hexago-
reaching sizes of 100 nm. Depending on the inert gas mixtures
nal carbon rings or graphene oxide with defects like
based on He, Ar, and N2 and their pressures either “dahlia”-
carboxylic and epoxy groups,
shaped or “bud”-like aggregates are formed, when produced
via CO2 laser ablation of graphite (Figure 2).[7] Sometimes, even
opening angles wider than 20°, which correspond to fewer pen-
F. Lodermeyer, Dr. R. D. Costa, Prof. D. M. Guldi tagonal declinations at the apex, are found in single- and multi-
Department of Chemistry and Pharmacy walled nanohorns.
Interdisciplinary Center for Molecular In this review, we concentrate on the application of well-
Materials (ICMM) defined SWCNHs. Here, the presence of pentagonal defects
Friedrich-Alexander-University Erlangen-Nuremberg
Egerlandstr. 3, 91058 Erlangen, Germany
impacts the electronic structure at both the local and global
E-mail: ruben.costa@fau.de; dirk.guldi@fau.de levels. The variation in the local sheet orientation near to the
cone and the two-dimensional nature of the electronic states
DOI: 10.1002/aenm.201601883 imply that external fields can generate nonuniform effective

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Fabian Lodermeyer
received both his B.Sc.
(2010) and M.Sc. (2012)
at the Friedrich-Alexander-
University Erlangen-Nürnberg
(Germany). He is currently
a Ph.D. candidate at this
university as a graduate
school member of the excel-
lence cluster Engineering of
Advanced Materials (EAM).
His research encompasses
the characterization, implementation, and assembly of
Figure 1. Top left – Schematic representation of an individualized novel nanostructured materials for highly efficient and
SWCNH. Bottom left – Schematic representation of the dahlia-type struc- long-term stable Dye-Sensitized Solar Cells (DSSC).
ture of SWCNH aggregates. Right – Built-up of SWCNHs with the five-
membered rings at the tip and the six-membered rings at the tube. Blue
He primarily focusses on the understanding of charge-
and green markings depict the fullerene- and graphene-/nanotube-like transport and recombination mechanisms in novel
regions of SWCNHs, respectively. nanocarbon-based hybrid materials and the influence on
both the performance and long-term stability of DSSCs.
local fields for states located in the cone.[4] This is due to the
response to electric or magnetic fields resulting in new Landau Rubén D. Costa com-
levels associated with Lissajous orbits that circle the apex mul- pleted both his B.Sc/M.
tiple times. This three-body problem generates transport phe- Sc studies (2006) and PhD
nomena governed by highly inhomogeneous local fields similar (2010) in Chemistry at
to those of defects in graphene sheets upon applying electric the University of Valencia
or magnetic fields.[11] All of the aforementioned renders them (Spain). From 2011–2013,
interesting for energy conversion and energy storage applica- he was a Humboldt postdoc
tions due to their electrocatalytic reactivity and ballistic electron at the Friedrich-Alexander-
transport.[12,13] University Erlangen-
Owing to their large surface area and porosity, they are Nürnberg (Germany),
readily dispersible in organic solvents at high concentrations where he is a junior group
(1–5 mg mL−1).[14,15] Recently, the interest in SWCNHs has been leader since 2014. Costa’s
intensified given their metal-free synthesis, semiconducting research involves the development of sustainable
character, and ease of suspendibility in organic solvents. There- electroluminescent materials, nanocarbon-based hybrids,
fore, some of the major bottlenecks in large-scale application and bioinspired components for lighting, photovoltaic,
of carbon nanostructures, that is, bundling and insolubility, and diagnostic applications.
are circumvented.[9] SWCNHs are produced in large scales of
around 1 kg day−1 and are applicable without further purifica- Dirk M. Guldi completed both
tion.[16,17] Complementary methods like torch arc in open air,[18] his undergraduate studies
cavity arc jet in open air,[19] and pulsed arc discharge[20] are the (1988) and PhD (1990) at
basis for a number of morphological variations, which might the University of Cologne
even drive the process faster into industrial applications. (Germany). Following
Concerning their features, the Raman spectrum of pristine postdoctoral appointments
SWCNHs exhibits characteristics originating from graphite, at the National Institute of
glassy carbon, nano-soot, and diamond-like amorphous carbon Standards and Technology
(Figure 2).[9,21] Two prominent bands are observed at around (USA), the Hahn-Meitner
1333 and 1594 cm−1. Whereas the earlier is of A1g symmetry and Institute Berlin (1992), and
relates to defects or edges (D mode),[22] the latter corresponds to Syracuse University, he joined
the E2g mode at the Γ point (G mode). The G band arises from the faculty of the Notre Dame
in-plane stretching of C–C bonds in graphitic materials. As Radiation Laboratory in 1995. Since 2004, he has been Full
such, it is commonly found in all sp2-carbon systems. Localized Professor in the Friedrich-Alexander-University Erlangen-
vibrational modes or basal plane disorder due to impurities or Nürnberg (Germany).
functionalization can couple with the extended phonon modes
of SWCNHs, resulting in a broadening of the G band or even
splitting thereof into G and G′ modes. When turning to the D underlines the significance of defects in SWCNHs (Figure 2).
band, interesting is its high intensity at 1333 cm−1. As already Like any other sp2-carbon systems, SWCNHs feature a 2D band
shown in previous investigations, SWCNHs exhibit a high ID/IG around 2655 cm−1. It is a second-order two-phonon process that
ratio.[7,23] Hereby, the ID/IG ratio often exceeds a value of 1, which is frequency dependent in terms of excitation laser energy.

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Figure 2.  Top left – TEM image of dahlia-like SWCNH aggregates. Bottom left – TEM images of bud-like SWCNH aggregates. The inset shows a TEM
image at higher magnification. Middle – Raman spectra of SWCNHs with different ID/IG ratios depending on their level of oxidation. Right – Geometrical
model of inter- and intra-SWCNH pores of aggregated films. Images are reproduced with permission.[7] Copyright 2002, American Chemical Society
and reproduced with permission.[10] Copyright 2016, Elsevier.
The electronic properties of SWCNHs are likewise influ-
enced by their conical structure. For example, theoretical
calculations shed light onto stability, optimum geometry, and
electronic properties.[9,24,25] Simulated scanning tunneling
microscopy images of SWCNHs and similar structures prompt
to a net electron transfer towards the pentagon vertex sites.
Later on, this theoretical prediction was confirmed in scanning
tunneling microscopy.[24] In addition, the electronic structure of
SWCNHs was studied within the continuum field-theory gauge
model by considering a hyperboloid geometry and allowing the
descriptions of the electronic states near the Fermi energy.[25] It
was found that the local density of states (LDOS) increases rap-
idly in the tip region with a distinct non-zero minimum at the
Fermi energy. Studies regarding the conductivity revealed that
SWCNHs are of semiconducting character. The adsorption of
CO2 is the inception to a donation of electrons to n-type semi-
conductors, whereas O2 accepts an electron from p-type mate-
rials.[26,27] Upon CO2 adsorption, the conductivity of pristine
SWCNHs is enhanced, which would signify a n-type character.
However, a drop in the electrical conductivity at CO2 coverages
below 2% was observed. In stark contrast, the conductivity of
oxidized SWCNHs (ox-SWCNH) continuously increases upon
CO2 adsorption, which indicates p-type character. As far as
O2 adsorption experiments are concerned, pristine SWCNHs
exhibited a decline in conductivity, whereas the conductivity of
ox-SWCNHs remain unaffected. In short, ox-SWCNHs behave
like p-type semiconductors, whereas a claim is made that pris-
tine SWCNHs are n-type semiconductors, which needs to be
corroborated by further experiments. Furthermore, dramati-
cally different electrical conductivity responses of ox-SWCNHs
are ascribed to bond transformations at the pentagonal sites
upon annihilation.[26] The ox-SWCNHs are synthesized either
via simple heat treatment between 300 and 600 °C under O2
or via chemical treatment with a mixture of H2SO4/H2O2 or
HNO3.[7,28,29] Nitrogen-induced SWCNHs have been success-
fully prepared via heating SWCNHs at 800 °C with urea under
nitrogen.[30] Such functionalization procedures are known to be
associated with an increase in porosity and specific surface area
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REVIEW
by a factor of ≈5.[28,30] Oxidation of SWCNHs enabled their indi-
vidualization by using sucrose gradient solutions accompanied
by centrifugation.[31]
Regarding electromagnetic properties, electron spin reso-
nance (ESR) and static magnetic susceptibility measurements
revealed that individual SWCNHs possess at least one unpaired
electron spin. Notable is a contribution from diamagnetic
susceptibility, which exceeds that of fullerenes, but is below
MWCNTs and bulk graphite.[32] High-resolution 13C NMR
revealed two components for SWCNHs. Firstly, a fast relaxation
component with a chemical shift of 124 ppm is assigned to sur-
face nanohorns. A rapid spin diffusion towards localized para-
magnetic centers stemming from structural defects is the main
cause for this fast spin-lattice mechanism. Secondly, a slow
relaxation component with a chemical shift of 116 ppm cor-
responds to a graphite-like core structure. Overall, the atomic
ratio of the surface SWCNH part to the interior graphite-like
part is 1:2. Thereby, the density of the localized electron spins is
much higher for the surface component.[33]
Owing to their good dispersibility, SWCNH-based thin films
are easily prepared by solvent-based techniques (vide infra).
Hereby, SWCNH-based thin films exhibited good field emis-
sion characteristics and long-term stability.[34] X-ray diffraction
profiles of SWCNH aggregates corroborate a van der Waals
distance of 0.4 nm. This is slightly larger than that of ordi-
nary graphite with a value of 0.336 nm. An averaged spacing
of horn-wall to horn-wall distance was assumed due to the
lack of a crystallinity.[35] As a matter of fact, SWCNHs feature
micro- and mesopores due to their specific structure.[9] The
subtracting pore effect (SPE) rather than normal Brunauer-
Emmett-Teller (BET) method was used to determine the micro-
and mesopores of SWCNHs, since the micropore sizes are ≈1
nm. N2 adsorption isotherm assays at 77 K documented that,
for example, SWCNHs exhibit a micropore distribution around
1 nm. However, Dollimore-Heal (DH) analysis of the SWCNHs
revealed a mesopore size distribution up to 9 nm, which were
assigned to the aggregated structure of the SWCNHs.[10] Here,
DH analysis was applied, since multi-layers of adsorbed N2
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are likely to remain on the inner surface of the pores of the
REVIEW
SWCNH aggregates. The authors, therefore, related inter- and
intra-nanohorn pores to micro- and mesopores, respectively.
High-temperature treatment in O2 opens almost exclusively the
internal pores, which increases the total pore volume from 0.11
to 0.47 mL g−1, resulting in an increase in the total specific area
from 308 up to 1006 m2 g−1.[36]
Owing to the morphology and catalytic behavior of SWCNH-
based films, they were used for i) gas storage and detection
applications, ii) reinforcement nanocomposites, iii) biomedical
applications, and iv) fuel cell applications.[9,37,38] For example,
SWCNHs adsorb xenon,[39] NH3,[40] benzene and water,[41] and
an aqueous electrolyte.[42] Importantly, their morphology allows
the storage of gases in both the cylindrical micropores, as well
as the interstitial mesopores, e.g., storage of H2 and D2 as well
methane was successfully documented.[43,44] Their sensitivity
towards gases opens their application in gas sensors, such as
for NH3, NO3,[45] and for ozone in water,[46] as well as biosen-
sors for H2O2, uric acid, dopamine, and ascorbic acid.[47–49]
Their application as reinforcing nanocomposites was theo-
retically studied with a SWCNH/epoxy matrix hybrid[50] and
experimentally examined with the admixing of SWCNHs to
polyacrylonitrile.[51] Moreover, they were also applied as immu-
nosensors for detection of microcystin-LR, as amperometric
biosensors for chloramphenicol, and as efficient biocarrier
for gene therapy.[52–54] Also, they were successfully applied in
biomedical engineering as intracellular carriers[55] and for sev-
eral anti-tumor drug delivery and therapies. ox-SWCNHs, for
example, entrap the anticancer drug cisplatin.[56,57] Similarly,
ox-SWCNHs were used as an antibiotics drug delivery system
for vancomycin hydrochloride[58] and as carriers for cancer
chemotherapy.[59,60] Furthermore, the biodistribution and
ultrastructural localization of SWCNHs were tested.[61] Finally,
SWCNHs were used as a platinum replacement in fuel cells
or as catalyst support material.[62–64] Moreover, SWCNH-based
nanocomposites made from an electropolymerization of meth-
ylene blue served as a cell anode in biofuel cells. Higher cur-
rent and power densities relative to conventional fuel cells are
promising for microscale electronics applications.[65] Moreover,
biofuel cells have great potential as portable power sources.[66]
Importantly, deposition of SWCNHs onto any substrate is
realized by electrophoretic means.[67] For example, dispersions
of SWCNHs were used without any surfactants in combina-
tion with conductive and non-conductive substrates including
metals, insulators, and 3D templates.[68]
So far, SWCNHs have been exclusively applied in DSSCs.
MWCNTs, in contrast, have been used in n-type crystalline sil-
icon solar cells.[69] By depositing MWCNTs onto n-type silicon
substrates, the film thickness of the solar cells was reduced by
a factor of 6 without compromising the efficiency. From latter a
tremendous reduction in fabrication costs evolves.
This review concentrates on how to implement SWCNHs
into different solar energy applications, namely i) the design
of novel SWCNH/dye hybrids and their application in solar
cells, and ii) the integration of SWCNHs into different parts
of dye-sensitized solar cells (DSSC). To this end, this review is
divided into different sections. Firstly, we discuss the function-
alization of SWCNHs along with the preparation of SWCNH/
dye hybrids and their use in solar light harvesting schemes.
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Secondly, we discuss the implementation of SWCNHs into
each part of the DSSCs, namely i) into the photoelectrode net-
work, ii) as buffer layers between the conducting substrate and
the semiconductor, iii) as active components for counter elec-
trodes, and iv) as additives for solid-state and quasi solid-state
electrolytes into DSSCs. At the end of each section, we provide
a comparison with devices based on other nanocarbons, such
as MWCNTs and SWCNTs, carbon black, and graphene. The
best performing devices are listed in a table in the end of each
section.
2. SWCNH-Based Solar Energy Conversion
Schemes
2.1. Novel SWCNH/Dye Hybrids
2.1.1. Description and Characterization of SWCNH/Dye Hybrids
The first example of a SWCNH/dye conjugate was published
by Prato et al., in the form of a covalently attached free-base
porphyrin (SWCNH-H2P) (Figure 3a).[70] The functionalization
has been performed by using two different synthetic protocols,
namely i) a direct attack of a free amino group onto SWCNHs
and ii) an amidation reaction of the carboxylic functions in
ox-SWCNHs. The functionalized SWCNHs were subsequently
coupled to H2P. In cyclic voltammetry, the SWCNH-H2P conju-
gates exhibited a continuum of faradaic and pseudocapacitive
behavior. These are associated with multiple-electron trans-
fers to and from SWCNHs. Three reductions at -2.26, -2.57,
and -2.84 V and one oxidation at 1.12 V vs. standard calomel
electrode (SCE) were attributed to H2P. Furthermore, tran-
sient absorption spectroscopy assays demonstrated an efficient
electron-transfer process from the H2P singlet excited state to
SWCNHs. In detail, after exciting H2P at 420 nm, a broad fea-
ture between 550 and 800 nm with a peak maximum at 650 nm
appeared, which was assigned to the electron-transfer product.
These findings set the stage for a variety of electron donor-
acceptor conjugates. For example, Ito et al. synthesized a
copper(II)-2,2′:6′,2′′-terpyridine (CuIItpy) complex, which was
linked to ox-SWCNHs (ox-SWCNH-CuIItpy) (Figure 3b).[71]
SWCNHs were thermally treated under mildly oxidizing condi-
tions to remove the conical-shaped tip and to introduce func-
tional carboxylic units. The latter were coupled to CuIItpy in
a 0.1 M NaOH solution and ultrasonicated for 30 min. Ultra-
violet–visible spectroscopy (UV-Vis), infrared spectroscopy (IR),
Raman, and thermogravimetric analysis (TGA) analysis con-
firmed the formation of the photoactive conjugate. Steady-state
emission spectroscopy revealed the good degree of electronic
communication between the ox-SWCNHs and CuIItpy. Upon
exciting ox-SWCNH-CuIItpy at 315 nm, a strongly quenched
fluorescence was observed. Cyclic voltammetry and differ-
ential pulse voltammetry revealed the oxidation of CuIItpy at
+0.47 V and the reduction of ox-SWCNHs at -0.12 V vs Ag/
AgCl. Time-resolved nanosecond laser flash photolysis provided
solid evidence for the electron-transfer product. After exciting
ox-SWCNH-CuIItpy, a broad absorption transient in the near-
infrared (NIR) appeared, which was attributed to electrons that
are trapped within ox-SWCNHs. In line with these results, a
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Figure 3.  Schematic representation of SWCNH/dye conjugates, namely a) SWCNH-H2P, b) ox-SWCNH-CuIItpy, c) SWCNH-NH2-(H2TPP(CO2H)4),
d) ox-SWCNH-crown-C60, e) SWCNH-nTV, f) SWCNH-MeH2P, g) SWCNH-(MeH2P)2.

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broad absorption peak between 400 and 600 nm was assigned
REVIEW
to oxidized (CuIItpy)•+. Furthermore, after the addition of elec-
tron mediating hexyl-viologen dication (HV2+) and hole trap-
ping 1-benzyl-1,4-dihydronicotinamide (BNAH), all absorption
transient features were rapidly quenched.
Another example for a photoactive SWCNH/dye conjugate
was published by Ijima et al. They functionalized SWCNH-NH2
with a tetracarboxylic acid carrying free-base tetra-phenyl por-
phyrin (H2TPP(CO2H)4) to produce water-soluble nanohybrids
and to investigate light induced charge-separation processes
(SWCNH-NH2-(H2TPP(CO2H)4)) (Figure 3c).[72] A red-shift
accompanied with broadening of the absorption was observed
for the Soret band and the Q bands suggesting π-π stacking
interactions between the H2TPP(CO2H)4 and SWCNHs. This
was accompanied by a 60% fluorescence quenching, when com-
paring H2TPP(CO2H)4 with SWCNH-NH2-(H2TPP(CO2H)4).
Femtosecond laser transient flash photolysis revealed the gen-
eration of H2TPP(CO2H)4•+ and SWCNH-NH2•−, via the singlet
and triplet excited states of H2P(CO2H)4. To the best of our
knowledge, this is the first example of a water-soluble SWCNH/
dye conjugate, which could possibly lead to hydrogen evolution.
A reversed approach using two nanocarbon allotropes,
namely SWCNH and fullerene, as electron donor and acceptor
(ox-SWCNH-crown-C60), respectively, was proposed by Vizuete
et al. (Figure 3d).[73] Mixing a benzocrown ether appended
fullerene and a SWCNH featuring NH3+ groups enabled ammo-
nium–crown ether interactions (ox-SWCNH-crown-C60). Here,
UV-Vis titration assays revealed mutual electronic interactions.
In the resulting system, SWCNHs either form the triplet excited
state observed at 590 nm or the radical cation observed at
580 nm. The rate constant of electron transfer was determined
from the rise in absorbance at 1000 nm as 6.5 × 1010 s−1, while
the back electron transfer rate constant was 9.7 × 108 s−1, which
was determined from the decay of absorbance at 1000 nm. In
follow-up work, the same group documented the amphoteric
character of SWCNHs by functionalizing them with several
oligo(thienylenevinylenes) (SWCNH-nTV) (Figure 3e).[74] In
this context, the SWCNHs acted as electron acceptor leaving
the role of electron donor to the oligo(thienylenevinylenes)
upon light excitation. A likely rationale for the amphoteric prop-
erties of SWCNHs stems from the larger number of carbon
atoms, when compared with fullerene and, therefore, a more
efficient electron delocalization. Thus, their flexibility, pris-
tine, metal-free nature, and semiconducting character, render
SWCNHs an interesting alternative for nanocarbon, such as
SWCNTs, MWCNTs, and fullerenes for solar energy conversion
schemes.[3]
Readers interested in nanocarbon-based solar energy conver-
sion schemes are referred to excellent reviews concerning the
functionalization of fullerenes, MWCNTs and SWCNTs, and
graphene.[2,75–77] In the following, we will summarize the last
advances concerning SWCNH/dye hybrids.
2.1.2. The Use of SWCNH/Dye Hybrids for Solar Light
Harvesting Schemes
Several approaches to increase the charge injection processes
have been explored. Schottky junctions, for example, facilitate
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electron injection from a photoexcited state of the dye into the
conduction band (CB) via an electron-cascade flow. Given the
favorable energy level alignment in CBs of TiO2/photexcited
states of most dyes, nanocarbons have been shown to increase
the electron injection yields.[78,79] As a result, photocurrents and
fill factors (FF) are enhanced due to improved charge carrier
separation and contacts across the interfaces. Following the
aforementioned approaches, also SWCNHs have been applied
in DSSCs. In contrast to, for example, MWCNTs and SWCNTs,
SWCNHs lack metal impurities, which might reduce the photo-
current by up to 30% due to enhanced charge recombination.[80]
Furthermore, a Schottky barrier increases the effective electron
diffusion length (Ln).[79] Hereby, Ln reflects the competition
between electron transport and recombination (1).
L2n = Deff τ (1)
with Deff being the effective electron diffusion coefficient and
τ the electron lifetime calculated from electrochemical imped-
ance spectroscopy (EIS) under illumination. Alternatively, Deff
is calculated from EIS measurements according to (2).
Deff = ( Rk RW ) dkeff (2)
with Rk being the resistance towards recombination under dark
conditions, Rw the electron transport resistance under illumi-
nation conditions, d the electrode thickness, and keff the effec-
tive rate for recombination. Both, Rk and Rw are taken from the
semicircle at intermediate frequencies, whereas keff is estimated
from the maximum frequency of the semiconductor semicircle
under illumination.[14,81,82]
To the best of our knowledge, SWCNHs in the form of a
SWCNH/porphyrin conjugate were first reported in DSSCs
by Pagona et al. in 2008.[83] In particular, α-5-(2-aminophenyl)-
α -15-(2-nitrophenyl)-10,20-bis(2,4,6-trimethylphenyl)por-
phyrin was covalently attached to the tips of SWCNHs via
an amide bond (SWCNH-MeH2P) (Figure 3f). Sufficient
driving force for charge separation from the porphyrin moiety
towards SWCNHs was validated by steady-state fluorescence
quenching and nanosecond transient absorption spectroscopy.
Here, the SWCNHs serve as electron acceptors resulting in
the formation of the SWCNH•-/porphyrin•+ charge separated
state. In terms of DSSC fabrication, a mesoporous SnO2 layer
was deposited onto a transparent conductive oxide (TCO) sub-
strate, which was subsequently covered with the hybrid mate-
rial via electrophoresis forming Schottky junction type DSSCs.
Incident photon-to-current efficiencies (IPCE) of ≈2.7% at
440 nm were achieved. Overall, the photocurrent is rational-
ized by an effective charge separation between the dye and the
semiconductor. In the next step, a porphyrin dimer as a means
to improve the light harvesting of the photoanode, was grafted
to SWCNHs (SWCNH-(MeH2P)2) (Figure 3g).[84] Again, suc-
cessful electron injection from the porphyrin towards the
SWCNH was monitored. Here, the charge recombination rate
was calculated to be 1.4 × 107 s−1, realizing IPCEs enhanced
by a factor of 3.5 to 9.6%, which is attributed to a better light
harvesting.
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2.2. SWCNHs as Integrative Component for Dye-Sensitized development of photoelectrodes with high charge carrier injec-

Solar Cells
2.2.1. General Information
Following major breakthroughs in DSSCs by M. Grätzel and
B. O’Regan, current research focusses on the increase in the
efficiencies of both liquid- and solid-state devices, while main-
taining long-term stability with environmentally benign and
low-cost materials.[13,85]
In brief, the working principle in n-type DSSCs is described
as follows. Upon photoexcitation, the dye injects electrons into
the CB of the semiconductor (Figure 4). After performing work
through an external load, the electrons reduce the redox couple
or hole transport material (HTM) at the counter electrode (CE).
Subsequently, the electrolyte or HTM reduces the oxidized dye.
Hereby, key challenges for highly efficient solar cells are i) the
REVIEW
tion yields and charge collection efficiencies (i.e., a low series
resistance), ii) the application of environmentally friendly buffer
layers to reduce the recombination reaction of charge carriers
from the transparent conductive oxide (TCO) to the electrolyte
(i.e., a high shunt resistance), iii) the development of Pt-free
CEs with similar or superior electrolyte regeneration yields,
and iv) the application of (quasi) solid-state and iodine-free elec-
trolytes with good ionic diffusion and conductivity properties.
Over the years, attempts have been made to improve any of the
aforementioned DSSC parts with a multitude of materials, such
as transition metal complexes (TMC) as replacement for Pt of
CEs,[86,87] the use of solid-state HTMs rather than liquid-based
electrolytes,[88,89] and novel photoelectrode nanostructures for
better charge transport, enhanced light scattering,[90] etc.
Among the materials to improve DSSCs, nanocarbons stand
out due to their low-cost production and multifunctionality.[91–94]

Figure 4.  Top – Energy diagram of n-type DSSC. Bottom left – Energy diagram of n-type DSSC upon applying a buffer layer. Bottom right – Energy
diagram of n-type DSSC upon implementing nanocarbons (NC) inside the TiO2 network. Desirable processes are depicted with black solid lines:
(1) electron injection from the dye into the CB, (1*) electron injection from the dye into the NC network, (2) charge collection from the quasi Fermi
level to the TCO, (2*) charge collection from the NC-based buffer layer to the TCO, (2**) charge transfer trough the NC/TiO2 network and subsequent
charge collection at the TCO, and (3) dye regeneration. The undesired processes are depicted with gray dashed lines: (4) electron back recombination
with the electrolyte and (5) with the oxidized dye.

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In fact, nanocarbons, such as carbon nanodots, carbon nano- as the balance between electrons reaching the external circuit
REVIEW

tubes, graphene, etc., can be cost-efficiently synthesized in high
yields via green chemistry approaches from renewable energy
sources. However, some of the roadblocks in large-scale appli-
cation of pristine, non-functionalized nanocarbons are their
tendency to bundle in common solvents and their poor dispers-
ability.[15] In stark contrast, the straightforward preparation of
SWCNH suspensions is achieved by a mild ultrasonication pro-
cess. Additionally, the dispersions are stable for months without
the needs of stabilizers.[14,23]
2.2.2. Implementation of SWCNHs into the
Photoelectrode Network
In DSSCs, the charge carrier transport is based on a trap-con-
trolled diffusive process, where the injected charges get trapped
in intra-bandgap states due to nanoparticle boundaries.[81,95]
Avoiding charge carrier trapping in either deep trap states or
at grain boundaries is likely to increase the rate of charge car-
riers to reach the external circuit, namely the charge collec-
tion efficiency (ηcc). One way to improve the DSSC efficiency
is to incorporate nanocarbons into the semiconductor network.
Charge carrier transport in nanocarbons, such as graphene,
SWCNTs, MWCNTs, and SWCNHs is ballistic and, in turn, the
transport resistance in the semiconducting network is effec-
tively reduced.[12,13] In turn, this results in efficient charge sep-
aration from the oxidized dye and injected electrons into the
CB, which reduces recombination processes (Figure 4). Upon
doping with nanocarbons, Rws decrease, Rks increase, and ηccs,
and electrons recombining, increase (3).
ηcc = 1 − RW Rk (3)
Nanocarbon bundling imposes serious challenges, especially
in terms of directional charge carrier flow in the semiconducting
network. Given their dispersibility, semiconducting character,
porosity, and surface area, SWCNHs were implemented into
TiO2-based photoelectrodes (Figure 5).[82] SWCNH/TiO2 hybrid
pastes with weight percentages of 0.1, 0.2, 0.5, and 0.7 wt%
were prepared via drop-wise addition of SWCNH suspen-
sions to a TiO2-based paste followed by rigorous stirring. The
hybrid pastes were doctor bladed onto fluorine-doped tin oxide
(FTO) glass substrates and subsequently sintered at 400 °C for
30 min. In a comprehensive study, the SWCNH/TiO2 hybrid
pastes were compared to those featuring graphene, SWCNTs,
and their oxidized analogs. To avoid heat-induced degradation
of the oxidized nanocarbons during the sintering, temperatures
of less than 450 to 500 °C were employed. Despite the fact that
pristine nanocarbons exhibit heat stability up to 900 °C,[70] ther-
mogravimetric analyses (TGA) indicated significant mass losses
for the hybrid pastes. A likely rationale infers that the different
binders and stabilizers, which are present in the TiO2 pastes,
are responsible for the mass loses. Importantly, the nano-
carbons are still maintained inside the TiO2 network without
indications of decomposition upon sintering. Raman experi-
ments further corroborated these findings. Signals at 1275 and
1595 cm−1 were assigned to the defect-induced D band and gra-
phitic G band of the nanocarbons present in the TiO2 network,

Figure 5.  Top – Schematic representation of SWCNH/TiO2 hybrid films applied in DSSCs. Blue arrows highlight the electron flow. Bottom left – J−V
characteristics for DSSCs prepared with the different nanocarbons/TiO2 photoelectrodes. Bottom middle – Corresponding IPCE spectra of the dif-
ferent nanocarbons/TiO2 photoelectrodes. Bottom right – Corresponding Bode phase plots of the different nanocarbons/TiO2 photoelectrodes under
1 sun illumination at open-circuit conditions.[82] Color code: reference (black squares), 0.5 wt% SWCNH (black circles), 0.2 wt% ox-SWCNH (dark grey
triangles), 0.1 wt% graphene (light grey triangles), 0.5 wt% ox-graphene (light grey diamonds), 0.1 wt% SWCNT (light grey left triangles), and 0.1 wt%
ox-SWCNT (light grey right triangles).

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respectively. Furthermore, signals at 397, 517, and 639 cm−1
were ascribed to the B1g, A1g+B2g, and Eg modes in TiO2 anatase
nanoparticles, respectively.[96] Also in XRD measurements the
TiO2 pattern was not affected by the use of nanocarbons. From
scanning electron microscopy (SEM) measurements, desorp-
tion experiments, diffuse reflectance, and α-step profilometry
measurements insights into microstructure of the TiO2 films
were derived. For example, upon implementing the nanocar-
bons, the roughness and, in turn, the amount of adsorbed dye
and light-scattering events increase (4).[97]
R = Dad N A DA (4)
where R is the roughness parameter, Dad the amount of
adsorbed dye per unit area (mol nm−2), NA the Avogadro con-
stant, and DA the area per dye (1.6 nm2 dye−1 for N719).
In line with a surface area increase upon oxidation of
SWCNHs (vide supra), oxidized SWCNHs gave rise to
increased R values. This is a general notion in nanocarbon-
based DSSCs that encompasses both more adsorbed dye and
enhanced light-scattering features of the electrode. As a matter
of fact, they significantly contribute to the general increase in
generated photocurrents compared to that of the reference
device (vide infra).
Furthermore, the work functions of the films were measured
by using the Kelvin probe technique. Upon nanocarbon integra-
tion, the work functions increased compared to pristine TiO2
reference DSSCs.[98,99] Moreover, the resistance reduced from
≈800 to ≈100 MΩ for pristine TiO2 and 0.5 wt% containing
electrodes, respectively. For example, pristine graphene- and
SWCNH-containing films feature sheet resistances as low as
36.6 and 51.4 MΩ for 0.5 and 0.1 wt% nanocarbon amounts,
respectively. In contrast, SWCNT- and ox-SWCNT-containing
photoelectrodes exhibited resistances of 200 MΩ and higher.
Due to the similar performances, the authors concluded that
graphene- and SWCNH-containing DSSCs feature comparable
benefits. Depending on the type of nanocarbon, the resistances
rose due to aggregation after certain nanocarbon amounts in
the hybrid materials, which was independently confirmed by
means of diffuse reflectance measurements. For SWCNTs,
the aggregation already sets in at levels of 0.1 wt%. Transient
absorption measurements with TiO2 films were performed
to document the electron conducting properties. Hereby, the
bleaching recovery at 460 nm of the excited state of N719 was
monitored upon exciting at 387 nm. Typically, the lifetimes
reflect the charge recombination and, in turn, electron injection
into the nanocarbon. As a matter of fact, the longest lifetimes
of 208 ns were detected for 0.5 wt% SWCNH-containing TiO2
films, while 127 ns evolved for 0.5 wt% graphene-containing
TiO2. Overall, DSSC efficiencies are as high as 8.0% for 0.5 wt%
SWCNH, while reference devices show efficiencies of 4.5%
(Figure 6). Especially, short-circuit current densities (Jscs) and
FFs went from 10.9 to 16.1 mA cm−2 and 0.57 to 0.67, respec-
tively. Notably, for graphene-containing DSSCs efficiencies of
up 7.6% were found, which is inferior to SWCNH-containing
DSSCs, mainly due to inferior photocurrents. In summary, the
highest DSSC efficiencies are for 0.1 wt% graphene-, 0.5 wt%
ox-graphene-, 0.1 wt% SWCNT-, 0.1 wt% ox-SWCNT-, 0.5 wt%
SWCNH-, and 0.1 wt% ox-SWCNH-incorporated electrodes
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with efficiencies of 7.6%, 7.5%, 5.0%, 5.1%, 8.0%, and 7.8%,
REVIEW
respectively (Figure 5).
To the best of our knowledge, the highest efficiencies for
nanocarbon-containing photoelectrodes are SWCNT/TiO2
nanocrystal core-shell nanocomposites using a genetically
engineered M13 virus as template (Table 1).[100] By using these
nanocomposites, the bundling of SWCNT was elegantly cir-
cumvented and 0.1 wt% of SWCNTs lead to an increase in
efficiency from 8.3% to 10.6% for reference and nanocarbon-
implemented DSSCs, respectively. For TiO2-based DSSCs an
efficiency increase from 7% to 9% was noted in the presence
of 0.01 wt% MWCNTs.[101] In a similar manner, graphene
sheets were incorporated into photoelectrodes to fine-tune
electron transport properties and reduction of electron recom-
bination processes.[98] Graphene oxide (GO) was, for example,
mixed with TiO2 to take advantage of the mutual interactions
between the functional groups of GO and TiO2. Subsequently,
the GO/TiO2 hybrid was reduced with hydrazine vapor at
40 °C to afford reduced graphene oxide (r-GO)/TiO2. Opti-
mized photoelectrodes, that is, those featuring 0.6 wt% gra-
phene, resulted in efficiencies of 7.0%, which are 45% higher
compared to reference DSSCs with efficiencies of 5.0%. Similar
results were obtained, when TiO2 nanotubes were incorporated
with graphene sheets with efficiencies maximizing at 7.5%.[102]
When graphene was applied as a buffer layer between FTO and
TiO2, the values further increased to 8.7%. For a more detailed
overview about nanocarbons other than SWCNHs, we refer the
interested reader to excellent recent reviews.[103,104]
Importantly, the optimum use of nanocarbons in photo-
electrodes is on the order of less than 1 wt%. As a matter of
fact, higher amounts of, for example, SWCNTs and MWCNTs
decrease the solar cell efficiency due to lower Jscs. A possible
rationale implies lower amounts of adsorbed dyes and poorer
light-scattering, which are both connected to changes in the
electrode morphology.[105,106] Costa et al. have demonstrated that
a nanocarbon content of more than 0.7 wt% in the electrodes
results in a Jsc drop for pristine graphene, ox-graphene, pristine
SWCNTs, ox-SWCNTs, pristine SWCNHs, and ox-SWCNHs.
The change in layer morphology was corroborated by diffuse
reflectance measurements and SEM analysis of the nano-
carbon/TiO2 films.[82]
2.2.3. SWCNH-Based Buffer Layer
Additionally to charge carrier recombination evolving
between the semiconductor network and the electrolyte,
recombination processes between TCO and the electrolyte
dominate in the absence of a buffer layer (i.e., a low shunt
resistance).[107,108] To prevent the shunting of charge carriers
to the electrolyte, in TiO2-based DSSCs a thin film of TiO2
is deposited onto TCO via hydrolyzing aqueous solutions
of TiCl4.[80] When a buffer layer is present, on one hand, a
higher charge carrier concentration in the semiconducting
network and, on the other hand, a higher quasi-Fermi level
increases Vocs (5).[109,110]
Voc = (kB T e ) ln ( Iinj
kreg nCB [I3− ] ) (5)
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Figure 6.  Top – Schematic representation of a SWCNH-based buffer layer. Center left – J–V curves for 0 (light grey triangles), 15 (black squares), and
30 (dark grey circles) nm thick SWCNH-based and TiCl4-based (grey triangles) buffer layers. Center right – Corresponding measured (solid lines) and
calculated (squares) IPCE spectra. Bottom left – Corresponding Nyquist plots under illumination conditions. Bottom right – Corresponding Nyquist
plots under dark conditions.

Table 1.  Figures-of-merit of best performing DSSCs with nanocarbon/TiO2 hybrid photoelec- Here, kB is the Boltzmann constant, T is
trodes. Electrolytes based on a I−/I3− mixture in acetonitrile were used. The applied CE mate- the absolute temperature, e is the elementary
rial was Pt. charge, Iinj is the flux of injected electrons
from the sensitizer, kreg is the regeneration
Nanocarbon [wt%] Jsc Voc FF η Photoanode thickness Dye Reference rate constant for I3−, and [I3−] is the concen-
[mA cm−2] [V] [%] [µm]
tration of I3− in the bulk electrolyte (Figure 4).
SWCNT 0.1 19.4 0.78 0.70 10.6 13.0 N719 [100] Next to an intimate contact between TCO
MWCNT 0.01 16.0 0.76 0.74 9.0 16.4 N719 [101] and TiO2, smoothening of the rough TCO
rGO 0.6 16.3 0.69 0.62 7.0 7.0 N3 [98] surface the buffer layer assists in realizing
higher photovoltages.[78,111,112] The low sta-
graphene 1.0 18.3 0.56 0.74 7.5 15.0 indoline [102]
bility and the corrosiveness of TiCl4 solutions
SWCNH 0.5 16.1 0.67 0.74 8.0 14.0 N719 [82] impose limitations to the applicability of the

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TiCl4 treatment – not to underestimate production and recy-
cling costs. Nanocarbon-based buffer layers offer incentives
as a low-cost and eco-friendly alternative (Figure 6).[78,113,114]
Due to their good dispersibility, SWCNHs stand out, since
they can be easily spin coated onto TCO substrates.[14] For
example, Casillas et al. prepared SWCNH-based buffer layers
of thicknesses from 5 to 30 nm by varying the spin velocity
and/or the amount of SWCNH dispersions. SWCNH disper-
sions (3.6 mg mL−1) were spin-coated onto pre-cleaned FTO
substrates with spin velocities of 800 and 1200 rpm yielding
SWCNH-based buffer layers with transparencies above 94%.
Imaging by means of SEM confirmed a homogenous layer
with no bare FTO sites that might affect the recombination
dynamics. Upon increasing the thickness of the SWCNH-
based buffer layers, a mesoporous-like network was noted.
This facilitates connection with the TiO2 nanoparticles and,
in turn, perfects the contact across the TiO2|FTO interface.
In addition, SWCNH-thicknesses of 5 and 15 nm resulted in
sheet resistances of 15 and 22 kΩ, which are comparable to
18 kΩ for TiCl4-based buffer layers prepared on FTO. In other
words, SWCNH-buffer layers below 20 nm should reveal sim-
ilar device characteristics than TiCl4-treated reference DSSCs.
This was proven by similar light-harvesting efficiencies (LHE)
of electrodes that are built around SWCNH- and TiCl4-based
buffer layers. In the case of a 15 nm thick SWCNH-based
buffer layer, higher Jscs, Vocs, and FFs relative to non-treated
devices changed the efficiency from 4.3% to 8.2%.
Nevertheless, thicker buffer layers went hand-in-hand with
lower FFs and Jscs due to unfavorable resistances and reduced
light-harvesting. This trend was further confirmed by IPCE
measurements, where 15 nm thick buffer layers result in max-
imum IPCEs of 80%, whereas IPCEs drop to 50% for 30 nm
thick layers (Figure 6). Notably, IPCEs were related to LHEs and
yields of electron injection (ηinj), regeneration (ηreg), and collec-
tion (ηcc) according to (6).[115]
IPCE = LHE ηinj ηreg ηcc
(6)
For N719-based electrodes with a liquid I−/I3−-based electro-
lyte, ηinj and ηreg are close to unity and LHEs are not dramati-
cally impacted. From this correlation it was concluded that the
major changes stemming from SWCNH-based buffer layers
is the improvement of ηcc.[110,116] Hereby, ηcc correlates with
FF and accounts for electron loss processes and sheet resist-
ances. As a complement, EISs were performed under open-
circuit conditions in the dark and under illumination. The Rws
are influenced by the presence of a buffer layer. Given iden-
tical electrodes, namely TiO2, 7 µm, and N719, different Rws
Table 2.  Figures-of-merit of best performing DSSCs with nanocarbon-based buffer layers. Electrolytes based on a I−/I3− mixture in acetonitrile were
used. The applied CE material was Pt.
Nanocarbon Buffer layer thickness Jsc Voc
[nm] [mA cm−2] [V]
graphene ≈44 21.3 0.74
graphene 500–3000 19.5 0.75
SWCNH 15 16.4 0.78
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relate to changes across the FTO|SWCNH|TiO2 interfaces. For
REVIEW
example, Rws gradually decrease from 19.2 to 13 Ω for 0 and
5 nm thick buffer layers and increase from 14.5 to 34.1 Ω for
15 and 30 nm thick buffer layers. However, the highest Rks
of 75.3 Ω (i.e., the lowest recombination of electrons with the
electrolyte) for 15 nm SWCNH layers give rise to the highest
ηcc of 81% (3). In reference DSSCs, Rks of 36.3 Ω are linked
to moderate ηccs of only 47%. As a result, when a 15 nm thick
SWCNH-based buffer layer is applied, better performances
than non-treated DSSCs are observed.
In short, SWCNH-based buffer layers have emerged as a
viable and environmentally friendly alternative to the corro-
sive, costly, and non-recyclable TiCl4 procedure (Table 2). A gra-
phene-based buffer layer has similar effects with an efficiency
increase from 7.5% to 8.7%.[102] Similar results were reported
by Chen et al. with graphene in both in the photoelectrode and
as buffer layer. Efficiencies of 7.2% and 8.1% were derived for
0.02 wt% graphene-containing TiO2 without and with a gra-
phene buffer layer, respectively.[117]
2.2.4. SWCNH-Based Counter Electrodes
Highly efficient CE materials for DSSCs should feature high
catalytic activity towards the reduction of the electrolyte and
electrical conductivity.[118,119] Hereby, the former can be quanti-
fied via the exchange current density (J0) from Tafel polariza-
tion curve measurements and the charge transfer resistance
(Rct) deduced from EIS measurements at the high frequency
semicircle.[120,121] J0s represent the slope of the Tafel polariza-
tion curves and is indirectly proportional to Rct(7).
JO = RT nFRct (7)
with R being the Avogadro constant, n the number of electrons
transferred in the redox reaction, and F the Faraday constant.
Higher J0s relate therefore to lower Rcts and, in turn, to higher
catalytic activity of the CE material.[122,123] Platinum is widely
used as CE material given its low Rcts.[124,125] Nevertheless,
platinum is one of the scarcest elements and requires 400 °C
of sintering.[126–130] Aside to TMCs and conductive polymers,
nanocarbons have emerged as a potent replacement for plat-
inum as part of highly efficient CEs.[118,119] Criteria such as
high specific surface area, superior conductivity, good catalytic
activity towards the reduction of redox couple, and low produc-
tion costs (vide supra) are great assets of nanocarbons.[131] Rea-
sonable performances with nanocarbon-based CEs were only
realized when complicated and time-consuming deposition
FF η Photoanode thickness Dye Reference
[%] [µm]
0.55 8.7 10.0 indoline [102]
0.56 8.1 11.0 N719 [117]
0.64 8.2 7.0 N719 [14]
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Figure 7.  Top – Schematic representation of a SWCNH-based counter electrode. Center left – Tafel polarization curves of symmetric cells with SWCNH-
and Pt-based CEs. Center right – Corresponding Nyquist plots measured at 0 V. Bottom left – J–V curves of DSSCs with SWCNH- and Pt-based CEs
under 1 sun and AM 1.5 conditions. Bottom right – Corresponding Nyquist plots measured under Voc conditions. Color code: SWCNH-based CEs of
increasing layer thickness from thin (black squares) to thick layers (light grey diamonds) and Pt-based CEs (grey triangles).

techniques were employed. Here, poor dispersibility and/
or high temperature sintering under inert gas conditions are
the major obstacles.[132,118,119,133–135] In contrast, SWCNHs are
readily dispersible in high weight ratios and, therefore, could
be successfully applied as CE material via facile drop casting or
spray coating (Figure 7).[15–139]
In chronological order, firstly, Lodermeyer et al. reported on
the assembly of SWCNH-based CEs, which showed efficiencies
comparable to Pt-based CEs.[15] To this end, SWCNH-based CEs
of varying thickness were fabricated by drop casting different
volumes of SWCNH dispersions (3.6 mg mL−1) onto pre-cleaned
FTOs. 13.3 to 106.7 µL translated to film thicknesses from 1.5
to 8.9 µm, respectively. Simultaneously, the roughness of the
SWCNH layers increased from ≈500 to ≈6000 nm. Larger active
areas are important and assist in larger J0s and lower Rcts as
derived from Tafel polarization curves and EIS measurements
with symmetric FTO|SWCNHs|electrolyte|SWCNHs|FTO
cells (Figure 7). Taking a liquid I−/I3−-based electrolyte, J0s of
27.3 and 42.85 mA cm−2 were determined for layer thicknesses
of 1.5 and 8.9 µm, respectively. A higher catalytic activity as
found upon increasing the layer thickness is reflected in an
effective diffusion coefficient (Ddiff) of 9.1 × 10−10 m2 s−1. Ddiffs

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are directly related to the Warburg resistance in the bulk elec-
trolyte (Rdiff) deduced from the low frequency semicircle in EIS
measurements (8).
Ddiff = ( kBT ) (n2q2R [I3− ]Rdiff δ )
with δ being the electrolyte thickness. SEM images gave
additional proof for an increased active area. Here, thicker
electrodes exhibited larger nm-sized gaps in the overall homog-
enous layers. Notably, Rcts were well below those found in
Pt-based reference devices. This accounts for a higher catalytic
activity of SWCNHs towards I3− reduction relative to platinum.
Due to the mesoporous-like SWCNH network the I3− diffusion
is, however, hindered. This results in lower Ddiffs relative to
platinum. Finally, DSSCs with SWCNH-based CEs were tested
to validate the previous findings. From J-V measurements it
was concluded that the Jscs and FFs increased as a function
of CE thickness. Only Vocs failed to provide a clear trend due
to a high series resistance of the CEs with low SWCNH layer
thicknesses. However, the Jscs of CEs with SWCNH thick-
nesses above 8 µm decreased from 16.1 to 14.43 mA cm−2. The
authors rationalized this finding with trapping of I3− inside
the mesoporous-like SWCNH network as a means to suppress
the dye regeneration. This postulate is in sound agreement
with EIS measurements, where Ddiffs decrease for SWCNH
layer thicknesses above 8 µm. As a matter of fact, the most effi-
cient Pt-free CEs of 7.7% had thicknesses of ≈6 µm, which is
close to the efficiency of Pt-based reference devices with 7.9%.
Susmitha et al. used SWCNHs, which were prepared by
the arc discharge method, and subsequently oxidized them at
500 °C for 15 min in air.[137] The synthesized SWCNHs were
dispersed in a mixture of water and isopropanol with the help
of ethyl cellulose. The aqueous solutions were spray-coated onto
FTO substrates and heated to 150 °C for 30 min. Raman experi-
ments revealed a ID/IG ratio of 0.86 of SWCNHs prepared by
arc discharge compared to 1.09, when produced via CO2 laser
ablation.[23] The authors also compared the performance of
SWCNH-based with graphene nanoplatelets-based (GNP) CEs.
Optimized SWCNH-based CEs featured efficiencies of 4.1% for
CEs with a SWCNH loading of 3.0 mg, which are higher than
GNP-based CE devices showing efficiencies of 3.1% with 3.0 mg
GNP loading. The main reason for this finding is a higher sur-
face area and, in turn, a higher amount of catalytically active
sites for SWCNH-based CEs. Similar to previous findings,[15]
thicker SWCNH layers result in increased solar cell perfor-
mances.[23] In line with the aforementioned publication, the
efficiencies decreased from 4.1% to 3.7% for SWCNH loadings
of 3.0 and 4.0 mg, respectively. Here, the EIS measurements
did not reveal three semicircles for fitting the Rws and Rdiffs.
The results were validated by noting a decrease in the series
resistance from 26.4 to 17.5 Ω for SWCNH loadings of 0.5 and
3.0 mg, respectively. In contrast, CEs with SWCNH loadings
of 4.0 mg exhibit an increase to 26.3 Ω. Jscs reach a maximum
value of 14.5 and decrease to 13.2 mA cm−2 for SWCNH
loadings of 3.0 and 4.0 mg, respectively. Overall, the efficien-
cies are lower for spray-coated SWCNH-based CEs compared
to drop-casted ones.[15] This might be due to the lower ID/IG
ratio of the arc discharge synthesized SWCNHs, to a lower
thickness, or to a different morphology of the SWCNH layers.
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Finally, SWCNH-based CEs were tested with a Co(II)/
REVIEW
Co(III) redox couple. This was done, since the catalytic activity
of nanocarbon-based CEs is typically higher compared to Pt-
based CEs, when a cobalt-based electrolyte is applied.[119,140] As
(8) a matter of fact, DSSCs with Co-based electrolytes exhibit Vocs,
which are higher compared to those of device with I−/I3−-based
electrolytes.[141–143] Ox-SWCNHs were produced by acid HNO3
treatment of pristine SWCNHs for 8 h.[138] Hereby, a better
adhesion to FTO is achieved via the introduction of carboxylic
side groups. SWCNH dispersions in ethanol were spray-coated
under a N2 stream onto FTOs, which were heated at 120 °C.
Subsequently, the films were sintered at 400 °C for 15 mins to
achieve a better conductivity and adhesion properties. Impor-
tantly, TGA indicated that the number of carboxylic groups are
reduced to ≈1%. This finding was confirmed by Raman experi-
ments, where the ID/IG ratio increased from ≈0.9 to 1.22 for
pristine and ox-SWCNHs, respectively.[17] Symmetric FTO|(ox-)
SWCNHs|electrolyte|(ox-)SWCNHs|FTO cells were tested in
slow scan rate cyclic voltammetry (SSCV) and EIS analysis.
PEDOT- and Pt-based CEs were used as references. Similar
Jlims of ≈21.0 mA cm−2 were observed for SWCNH- and ox-
SWCNH-based CEs, while PEDOT- and Pt-based CEs exhib-
ited higher Jlims of 22.7 and 25.4 mA cm−2, respectively. The
adsorption of additives such as 4-tert-butyl pyridine could also
be responsible for slower charge transfer kinetics. Devices
with SWCNH-, ox-SWCNH-, and PEDOT-based CEs exhibit
Rcts of 0.21, 0.75, and 0.18 Ω, respectively, and efficiencies of
6.8%, 6.8%, and 6.7%, respectively. The efficiencies of devices
with Pt-based CEs of 5.7% are lower compared to the nano-
carbon-based CEs. After 10 days, the latter with SWCNH- and
ox-SWCNH-based CEs exhibit similar efficiencies, whereas
PEDOT-based CEs show a progressive decay of their electro-
chemical response.
When comparing graphene-based CEs with SWCNH-based
CEs, a lower catalytic activity in the reduction of the redox
couple was noted for the former. A likely rationale is a lack of
defects and functional groups, which assist in the regeneration
of the electrolyte.[144–146] However, graphene sheets modified
with nitrogen or phosphorous atoms provide higher catalytic
activities. For example, Kim et al. produced in a two-step pro-
cess N-graphene nanoplatelets (NGnPs) and deposited them
onto FTO via an electrostatic spray technique (Table 3). After
6 min of deposition, DSSCs with NGnP-based CEs featured
PCEs of 9.05%, which is higher than the efficiency of 8.4%
found for Pt-based CE reference DSSCs.[133] In another
approach to functionalize graphene, edge-fluorinated graphene
nanoplatelets (FGnPs) were synthesized and deposited via the
electrostatic spray technique.[132] Both the reduced grain size
and the introduction of defective sides by fluorine doping, leads
to an increased Raman intensity of the FGnPs with a ID/IG ratio
of 0.92. Compared to hydrogen-terminated graphene sheets,
FFs and, in turn, efficiencies increased from 0.46 to 0.72 and
6.0% to 10.0%, respectively.
Comparable efficiencies were achieved by directly growing
CNTs onto FTO by means of CVD.[134] Uniform MWCNT-based
layers with thicknesses up to 5 µm were created. Similar Jscs
and Vocs, but a rise in FFs from 0.68 to 0.73, when comparing
Pt- with MWCNT-based CEs, lead to efficiencies of 8.8% and
10.0% for Pt- and MWCNT-based CEs, respectively. Fast and
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Table 3.  Figures-of-merit of best performing DSSCs with nanocarbon-based CEs. The electrolytes were prepared in acetonitrile.
Nanocarbon CE thickness Jsc Voc FF
[µm] [mA cm−2] [V]
MWCNT 5.0 17.6 0.76 0.73
FGnPa) – 14.4 0.97 0.72
b)
NGnP – 13.8 0.88 0.74
SWCNH 6.3 16.1 0.79 0.61
a)edge-fluorinated graphene nanoplatelets; b)N-graphene nanoplatelets.
directional charge transfer as well as large surface area render
MWCNTs as promising material for Pt-free CEs.[147]
2.2.5. SWCNH-Based (quasi) Solid-State Electrolytes
Under device operation conditions, the electrolyte plays a key
role, since it closes the circuit between working electrodes and
CEs. For highly efficient DSSCs, electrolytes with high Ddiff are
necessary to guarantee good dye regeneration yields.[141,148] To
this date, the liquid-based I−/I3− electrolyte is most commonly
used. However, evaporation of the solvent, large overpotentials
(>0.6 V), strong absorptions in the visible region, corrosive
nature, and distinct charge recombination processes, hinder
its application in the market.[141] Therefore, one of the major
challenges in the area of long-term stable DSSCs is the devel-
opment of iodine-free, (quasi) solid-state electrolytes, which
feature good contact with the mesoporous electrode, good diffu-
sion, and high ionic mobility.[13] Recently, a plethora of different
approaches for preparing non-corrosive and solid-state electro-
lytes can be found in the literature. Among them are p-type
semiconducting CsSnI, CuI, CuSCN, etc.[149–151] and HTMs
like N2,N2,N2′,N2′,N7,N7,N7′,N7′-octakis(4-methoxyphenyl)-9,9′-
spirobi[9H-fluorene]-2,2′,7,7′-tetramine (Spiro-MeOTAD).[89,152]
Also nanocarbons, such as carbon black,[93,153] SWCNTs and
MWCNTs,[154,155] and various graphene derivatives[156] con-
stitute a potent alternative for highly efficient solid-state
DSSCs (ssDSSCs). Notable is i) an increased ionic diffusion
throughout the redox electrolyte, ii) a reduction of the internal
resistance of the bulk electrolyte by introduction of a quasi-zero
distance between oxidized dyes and the counter electrode, iii)
an increase in catalytic activity towards the reduction of the oxi-
dized form of the electrolyte, and iv) dye regeneration yield of
almost unity.[23,93,157]
In a first approach, SWCNHs were added at different
weight ratios to 1-ethyl-3-methylimidazolium iodide ([EMIM]I)
(Figure 8). In detail, [EMIM]I/SWCNHs mixtures of 10:1,
5:1, and 1:1 wt% were prepared by admixing [EMIM]I with
SWCNHs dispersions of varying volumes in acetonitrile.
Higher SWCNH weight ratios could not be realized due to
miscibility problems. Rigorous stirring at 80 °C evaporated the
solvent and the resulting SWCNH-based solid-state electrolytes
were investigated. For (quasi) solid-state electrolytes, the crystal
growth inhibitor 1-butyl-3-methylimidazolium tetrafuoroborate
([BMIM][BF4]), 4-tert-butyl pyridine, and guanidinium thiocy-
anate were added for a better electrolyte penetration into the
mesoporous TiO2 network. Inspection of SEM images, verified
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η Electrolyte Photo-anode thickness Dye Deposition method Ref.
[%] [µm]
10.0 I−/I3− – N719 CVD [134]
10.0 Co2+/Co3+ 8.0 JK-306/SGT-301 Electrostatic spray [132]
9.1 Co2+/Co 3+ 9.0 O-alkylated-JK-225 Electrostatic spray [133]
7.7 I−/I3− 7.0 N719 drop cast [15]
the good mixing properties between [EMIM]I and SWCNHs.
Differential scanning calorimetry (DSC) measurements
revealed a large hysteresis of ≈60 and ≈40 °C for solid-state
electrolytes composed of pristine [EMIM]I and SWCNH-based
[EMIM]I, respectively. Furthermore, the ionic diffusivity of the
solid-state electrolytes in symmetric devices of the configura-
tion FTO|Pt|electrolyte|Pt|FTO was measured by linear-sweep
voltammetry (LSV) assays to measure the cathodic and anodic
steady-state polarization diffusion current density (Jss).[154]
Upon increasing SWCNHs in the electrolyte, Jsss improved
gradually. Hereby, the lowest Jsss were observed for pure
[EMIM]I electrolytes, while maximum Jsss were observed for
1:1 wt% mixtures without showing a significant change in the
ionic diffusion in the bulk electrolyte. In contrast, EIS measure-
ments at 0 V bias revealed a tremendous decrease of the War-
burg resistance of the electrolyte when SWCNHs are present in
[EMIM]I. In detail, Rdiffs decreased from 2676.1 to 35.9 Ω for
pure [EMIM]I and the 1:1 wt% electrolyte, respectively. The use
of the above-mentioned additives in the latter further decreased
the Rdiff to 31.4 Ω. Rcts decreased from 190.5 to 7.4 Ω for pure
[EMIM]I and the 1:1 wt% electrolyte, respectively. In the final
device, a hysteresis comparable to the DSC experiments was
also observed in temperature-dependent J–V measurements,
where the efficiency increased upon heating due to a phase
transition of [EMIM]I from the crystalline to the liquid phase in
good agreement with DSC assays. Upon cooling to room tem-
perature, the efficiency of ssDSSCs remained at its peak value.
After 30 min at room temperature, crystallization of the elec-
trolyte is the inception to an efficiency decrease. After 24 h, the
efficiency decayed to about half of the initial value. As already
seen in the CEs, SWCNHs act as catalytic active material.
When applied inside the bulk electrolyte, a quasi-zero distance
between oxidized dyes and the CE is introduced.[93,157] As a
consequence, when SWCNH-containing electrolytes were used
in ssDSSCs, Jscs improved dramatically due to a higher ionic
conductivity and better regeneration of the oxidized dye. In par-
ticular, the Jscs increased from 1.3 to 8.3 and to 16.0 mA cm−2
for pure [EMIM]I, the 1:1 wt% electrolytes, and the 1:1 wt%
electrolytes in the presence of all additives, reaching efficiencies
of 0.4%, 2.1%, and 7.8%, respectively. Again, the positive effect
of SWCNHs on the devices was proven by EIS measurements
under Voc conditions and illumination. In good agreement with
the symmetric devices (vide supra), the corresponding Ddiffs
increased from 0.1 to 7.6 and to 26.4 × 10−10 m2 s−1. Simulta-
neously, the corresponding Rcts decreased from 190.5 to 7.6
and to 1.8 Ω. In time-dependent J–V and EIS measurements,
the SWCNH-containing electrolytes were seen to lower the
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Figure 8. Top – Schematic representation of a DSSC containing a SWCNH-based electrolyte. Bottom left – Figures-of-merit of time-dependent
J–V assays of quasi solid-state DSSCs containing electrolytes with (black squares) and without (grey circles) SWCNHs. Bottom right – EIS assays of
quasi solid-state DSSCs containing electrolytes with (black squares) and without (grey circles) SWCNHs.

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REVIEW

Table 4.  Figures-of-merit of best performing solid-state DSSCs with nanocarbon-based electrolytes. N719 was used throughout as a dye.

Nanocarbon Jsc Voc FF η Electrolyte Photoanode thickness Reference

[mA cm−2] [V] [%] [µm]
carbon black 14.9 0.76 0.63 7.1 poly(acrylonitrile)/LiI/activated carbon composite gel polymer 20.0 [157]
MWCNT 15.3 0.68 0.66 6.7 poly(vinylidene fluoride co hexafluoropropylene)/LiI gel – [158]
graphene 18.3 0.59 0.48 5.2 graphene/polyethylene oxide composite – [156]
SWCNH 16.0 0.76 0.64 7.8 1-ethyl-3-methylimidazolium iodide/SWCNH composite 7.0 [23]

efficiencies (Figure 8). While Jscs and Vocs remained constant,
FFs increased gradually. DSSCs containing electrolytes without
SWCNHs show a loss of ≈75% relative to the initial efficiencies.
Substitution of SCN− by I3− or polyiodides in close proximity
to the electrode surface lead to the decrease in photocurrents.
Time-dependent EIS measurements revealed that after 5 days
the Rws of DSSCs containing electrolytes without SWCNHs
increased ≈1.7-fold, whereas the Rws of DSSCs with SWCNH-
containing electrolytes remained constant. Noteworthy, devices
with SWCNH-containing electrolytes show a gradual reduction
of the Rdiffs during this period of time. This was ascribed to an
enhancement of the electrolyte regeneration yields assisted by
slow degradation of the SWCNHs, as indicated by an increase
in the ID/IG ratio of the SWCNHs present in the electrolyte
from 1.08 to 1.22. Such a finding is important to improve the
long-term stability of electrolytes containing nanocarbons.
However, the question, if the use of SWCNHs in terms of
degradation, is self-limiting or, in stark contrast, enhances the
device performance, remains still unsolved.
For comparison, carbon black was activated with
poly(acrylonitrile) and LiI to form a composite gel polymer elec-
trolyte (Table 4).[157] The gelation of the electrolyte guarantees a
good penetration into the mesopores of the TiO2 network, which
has been proven by SEM and energy-dispersive X-ray (EDX)
spectroscopy. Upon increasing the carbon content, the ionic
conductivity of the gel electrolytes increased. As a result, the
best poly(acrylonitrile)/carbon black ratio resulted in efficien-
cies of 7.1%. In a similar manner, MWCNTs were functional-
ized with poly(vinylidene fluoride-co-hexafluoropropylene) and
LiI for a good dispersion of the gel electrolyte.[158] Consequently,
upon MWCNT-doping, the Ddiffs increased and the efficien-
cies culminated at 6.9%. At the same time, Rcts did not change
upon increasing the amount of MWCNTs, which implies negli-
gible catalytic activity of the polymer/MWCNT hybrid systems.
Also graphene was employed to improve the performance of
ssDSSCs.[156] Here, graphene sheets were uniformly coated by
a polyethylene oxide (PEO) matrix through the help of ester car-
boxylate bonds leading to overall conversion efficiencies of 5.2%.
3. Conclusion and Outlook
In this review, all the recent achievements related to the use
of SWCNHs for solar energy harvesting schemes have been
described. Furthermore, a comparison with other nanocarbons,
such as graphene, carbon black, MWCNTs, and SWCNTs is
drawn at the end of each section. Owing to their good dispersi-
bility, SWCNHs are easily applied by spin-coating, drop-casting,
spray-coating, doctor-blading, etc. This also facilitates their
functionalization with electron donors or acceptors by using
typical wet-chemistry approaches. As an illustration, we have
discussed several examples of SWCNH/dye conjugates with
good electrochemical communication. They were successfully
incorporated into DSSCs, showing a promising performance in
terms of charge injection and recombination processes.
Additionally, we have described the benefits of implementing
SWCNHs into the different parts of a DSSC, namely i) as inte-
grative materials into the electrode as buffer layers and into the
photoelectrodes to improve the charge transport and collection
efficiencies, ii) as additives into (quasi) solid state electrolytes
to enhance the ionic diffusivity and catalytic regeneration of
the redox couple in a quasi-zero distance, and iii) as only active
components in counter electrodes to replace platinum.
In terms of applicability, it is important to point out that
DSSCs are considered as micro-scale devices. Thus, this raises
the question of the compatibility of SWCNHs for nano-scale
devices, such as organic photovoltaics (OPV),[159] thin-film tran-
sistors (TFT),[160] organic light-emitting diodes (OLED),[161,162]
light-emitting electrochemical cells (LEC),[163] etc. Future work
will hopefully provide the information about the feasibility of
their implementation into nanoscale technologies.
Concerning the field of SWCNH-based DSSCs, several
major challenges need to be tackled in the near future. Firstly,
the electron transfer dynamics of SWCNH/dye hybrids have
to be improved to achieve higher solar cell efficiencies. There-
fore, a fundamental understanding of the electron transfer
dynamics from an electron donor towards SWCNHs and vice
versa is highly necessary.[164–167] Secondly, the application of
SWCNHs as buffer layers is limited by electrical conductivity
and transparency. Therefore, tuning SWCNHs in terms of con-
ductivity by chemical functionalization could further improve
the device performances. Thirdly, their use as additives in
solid-state electrolytes is limited by miscibility with ionic liq-
uids. Therefore, similar to what has been realized in SWCNH/
dye hybrids, the direct functionalization of SWCNH with ionic
liquids could be beneficial. Additionally, whether the electro-
lyte is directly regenerated by the SWCNHs in the bulk of the
electrolyte before reaching the CE needs to be further investi-
gated in the future. To this end, a comprehensive study with a
focus on the impact of the type of defects or functionalization
in SWCNHs on the electrolyte regeneration might be realized.
This also affects the SWCNH-based counter electrode optimiza-
tion. A detailed study of the active area combined with a control
of the ID/IG ratios without compromising the electrical con-
ductivity of the SWCNHs films is necessary to understand the
underlying processes at the electrolyte|CE interface.
Finally, we should consider the need of up-scaling for indus-
trial applications, namely roll-to-roll, 3D printing, etc. As a

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matter of fact, DSSC fabrication processes are straightforward.
Owing to the multifunctionality of SWCNHs, it is expected
that printable SWCNH-based DSSCs should be realized. For
instance, graphene and SWCNH buffer layers emerged as viable
alternatives to the corrosive TiCl4-based treatment. Notably, all
of the aforementioned are not only applicable to DSSCs but
also to, e.g., H2-production and battery technologies.[168–171]
Taking all of the aforementioned into concert, the use of
SWCNHs in solar energy conversion schemes has evolved
into an active field, featuring breakthroughs comparable to
those achieved with other nanocarbons. However, a full-fledged
understanding on the mechanisms involved upon SWCNH-
implementation is necessary to build the basis for the applica-
tion on an industrial scale.
Acknowledgements
F.L., R.D.C., and D. M. G. acknowledge the EAM cluster in the frame of
the DFG excellence programs for their support. D.M.G. acknowledges
the DFG, ICMM, and the ZMP for financial and intellectual support.
Received: August 26, 2016
Revised: October 17, 2016
Published online:
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