DOI: 10.1002/cey2.

11

REVIEW

Carbon‐based perovskite solar cells: From single‐junction

to modules
Rui He1 | Xiaozhou Huang1 | Mason Chee1 | Feng Hao2 | Pei Dong1

1
Department of Mechanical Engineering,
George Mason University, Fairfax, VA
2
School of Materials and Energy,
University of Electronic Science and
Technology of China, Chengdu, China
Correspondence
Pei Dong, Department of Mechanical
Engineering, George Mason University,
Fairfax, VA 22030.
Email: pdong3@gmu.edu
Funding information
George Mason University Startup Fund;
National Natural Science Foundation of
China, Grant/Award Number: 51702038
Abstract
Perovskite solar cells (PSCs) have attracted more and more attention in the
scientific community due to their high performance and simple fabrication process.
In the past few years, emerging technologies have made manufacturing large‐scale
PSC modules possible. However, stability and fabrication issues still limit the
modularization and commercialization of PSCs. Carbon materials have been
widely used in PSCs to overcome these challenges due to their excellent optical,
electrical, and mechanical properties. In addition, the hydrophobic properties of
certain carbon materials are highly effective at protecting the perovskite film from
moisture and improving the stability of PSCs. All these superior properties have
made carbon one of the most promising materials to fabricate future high‐
performance PSC modules with long service lifetimes. In this review, recent
developments of carbon‐based materials in different layers of single‐junction PSCs
will first be discussed, with an emphasis on functionalities related to PSCs’ stability
and modularization. Then, current improvements and future discussions in the
manufacturing of monolithic PSC modules will be reviewed in detail.

KEYWORDS
carbon, modules, perovskite solar cells, stability

1 | INTRODUCTION (3D) structures. In each of these formats, these carbon

Carbon is a marvelous element with diverse bond
structures and a variety of allotropes. For example,
fullerene (C60) contains 60 atoms arranged in a spherical
structure and can be considered a zero‐dimensional (0D)
nanoparticle. Carbon nanotubes (CNTs) are linearly
structured one‐dimensional tubes, and graphene is a
two‐dimensional (2D) material consisting of a one‐layer
thick sheet of carbon atoms. Graphite, carbon black, and
activated carbon have unique spatial three‐dimensional
Rui He and Xiaozhou Huang contributed equally to this work.
materials show extraordinary optical, electrical, physical,
and chemical properties.1-5 In addition, carbon’s envir-
onmental friendliness and low‐cost fabrication process
make it very appealing for solar cell applications.6
Compared with other kinds of energy resources, solar
energy is renewable, sustainable, and environment‐friendly.
Typically, solar cells can be categorized into three genera-
tions: first‐generation crystalline silicon solar cells, second‐
generation thin‐film solar cells, and a diverse third genera-
tion of solar cells. In first‐generation crystalline silicon solar
cells, amorphous carbon operates as an antireflective coating
due to its high bandgap.7 In second‐generation thin‐film

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© 2019 The Authors. Carbon Energy published by John Wiley & Sons Australia, Ltd on behalf of Wenzhou University.

Carbon Energy. 2019;1–15. wileyonlinelibrary.com/journal/cey2 | 1

2 | HE ET AL.

solar cells, carbon serves as the electrode material.8
Combining the advantages of the first‐ and second‐genera-
tion solar cells, the economical and highly efficient third‐
generation solar cells, including dye‐sensitized solar cell
(DSSC), organic solar cell (OSC), perovskite solar cell (PSC),
and others,9 have become a popular research area in recent
years. For example, in DSSCs, graphene is utilized as a
transparent conductive material,10,11 while CNTs, graphene,
and their hybrid materials have been widely used as counter
electrodes12-16 due to their high surface area and excellent
conductivity. C60 and CNTs are used in the photoactive layer
in OSCs due to their excellent carrier transport abilities.17-19
As shown in Figure 1, carbon materials such as fullerene,
graphene, graphite, CNTs, hybrid carbon materials, and
porous 3D carbon materials also show superior performance
in PSCs.
PSCs, as a new type of third‐generation solar cell, have
been developed significantly during the last decade. Because
of their high power conversion efficiency (PCE) and facile
processing, PSCs have the potential to be mass‐produced and
subsequently contribute significantly to solar energy produc-
tion in the future.23,24 The ABX3 inorganic‐organic hybrid
halide perovskite layer (Figure 1B) is the most important
part. Atom A usually represents the methyl ammonium
(MA) organic cation, atom B represents a divalent metal
cation, and atom X represents Cl−, I−, or Br−. A combination
of long carrier diffusion length (>100 nm), high charge
carrier mobility (~10 cm2 V−1 S−1), and excellent absorption
efficiency (internal quantum efficiency nearly 100%) result in
an outstanding solar cell performance.25-28 Typical PSCs have
a n‐i‐p structure (Figure 1C), while p‐i‐n inverted PSCs also
exist with corresponding transport layer materials. After
absorbing the photons, electron‐hole pairs are generated in
the perovskite layer, charges separate, and transportation
occurs. The holes move to the hole transport layer (HTL)
and are collected by electrode while electrons flow towards
the electron transport layer (ETL) and are collected by the
transparent conducting oxide (TCO) layer.29,30 Finally, the
electrode and TCO are connected to an external circuit to
form a loop. To improve existing PSC properties, a variety of
modifications have been implemented on different layers of
PSCs, such as increasing the conductivity of the electrode,
improving the extraction efficiency of the HTL and ETL,
and forming the monolithic structure in the perovskite layer
for a smoother carrier transportation.31-34 These modifica-
tions have increased the record‐certified PCE of PSCs up to
25.2% over the last several years.35,36 Due to carbon’s
superior electrical, mechanical, and hydrophobic properties
various carbon materials as shown in Figure 1A have been
widely used in various functional layers in advanced PSCs.
Nowadays, advanced technologies have prompted the
creation of new designs and manufacturing methods of
large‐area PSC modules (Figure 1D), which will be
discussed in detail in Section 3.3. This review will first
summarize the applications of carbon materials in each
layer of single‐junction PSCs, emphasizing the device
stability and manufacturing methods, and then discuss
the carbon‐based monolithic PSC modules.

FIGURE 1 Carbon materials in PSCs. A, Carbon allotropes including fullerene, graphene, graphite, CNTs, and 3D structures, which
have been used or could be used in PSC. Reproduced with permission: Copyright 2014, the Royal Society of Chemistry12; Copyright 2018, the
Royal Society of Chemistry20; Copyright 2018, the Elsevier.21 B, Perovskite ABX3 structure, where blue, green, and red dots represent A, B,
and X atom, respectively. C, Structure of the typical n‐i‐p‐type PSC with moisture resistance property. D, The large‐area PSC module.
Reproduced with permission: Copyright 2017, John Wiley and Sons.22 3D, three‐dimensional; CNT, carbon nanotube; ETL, electron
transport layer; HTL, hole transport layer; PSC, perovskite solar cell; TCO, transparent conducting oxide
HE ET AL.
2 | C A R BO N M A T E RI A L S I N
S I N G L E‐J U N C T I O N P S C s
Various morphologies of carbon materials are great
candidates for applications in PSCs due to their low cost,
hydrophobicity, high transparency, high conductivity,
flexibility, and other superior properties. Many carbon
materials have already been used in PSCs, including carbon
black, graphite, fullerene, CNTs, graphene, and others. In
this section, we will discuss some recent achievements
made with carbon materials in the electrode, charge
transport, and perovskite layers. Due to the tremendous
amount of research available, this discussion will focus on
the work related to PSC module applications.
2.1 | Carbon‐based electrodes
Carbon has been widely used as an alternative electrode
material to replace metal cathodes in PSCs for several
reasons. First, carbon materials’ abundant allotropes and
excellent properties could greatly improve the perfor-
mance of PSCs. Second, hydrophobic and flexible carbon‐
based films are among the most effective protective layers
used in PSCs to enhance the stability. Third, carbon’s low
cost and environmental friendliness make it one of the
most suitable choices for the use in PSCs.
2.1.1 | Performance improvement
Certain morphologies of carbon materials such as surface
roughness, thickness, and pore size can be optimized to
improve interfacial contact between the carbon electrode
and underlying layer. A self‐adhesive microporous
carbon film developed by Zhang et al37 was prepared by
a solvent‐exchange low‐temperature process that sup-
pressed the curing of the carbon powder. The weakened
curing, in turn, suppressed the formation of carbon
blocks and bulges, which was believed to be one of the
main issues causing roughness. The PCE of their PSC
reached as high as 19.2% and retained over 94% of its
initial efficiency after 80 hours. In comparison, the PCE
of a cell made by a conventional process requiring high
annealing temperature38 was only 15.2%. In addition,
Ryu et al39 used multiwalled carbon nanotubes
(MWCNTs) as bridges to connect the perovskite film
and carbon electrode by a new solvent dripping method.
The pathways created by the bridges could largely
increase the hole transfer efficiency between two layers.
The average efficiency of MWCNT modified cells was
11.5%, and the champion device achieved a PCE of
13.57% without hysteresis.
Though carbon materials are less conductive than Au,
a lot of research efforts have focused on lowering the
| 3
resistance by tuning the morphology, crystallinity, or
doping. For example, graphite‐based film has a relatively
high conductivity compared to that of with single‐wall
carbon nanotubes (SWCNTs) and graphene‐based film.
The conductivity of graphite film could be improved by
using larger and more uniformly sized graphite. To
improve the conductivity of the carbon electrode, Jiang
et al40 developed a highly conductive carbon paste film
with a sheet resistance of 4 Ω/sq by using suitably sized
graphite and adjusting the ratio of carbon black
and graphite. In their studies, the larger and more
uniform graphite particles lead to better graphite‐
graphite particle contact and less interparticle voids,
which resulted in higher conductivity. Similarly, Zhang
et al31 also discovered that the conductivity of graphite
film was correlated to the size of graphite. The sheet
resistance of carbon film can also be greatly decreased by
p‐type doping. Chu et al41 used p‐type NiO nanoparticle‐
doped carbon electrodes to decrease the charge transfer
resistance. The PCE of the doped cell was 13.26%.
2.1.2 | Stability improvement
In the early stages of PSC development, the cell only
lasted about 10 minutes (80% degradation).42 Even now,
stability is still one of the biggest concerns for future PSC
development. Carbon materials could help dramatically
extend a PSC’s service lifetime due to their hydrophobi-
city for functional stability and flexibility for mechanical
stability. Carbon materials’ hydrophobic properties make
them ideal to prevent moisture‐related degradation and
improve stability in PSCs.43 Siram et al44 explored the
stability of PSCs with organic nanocrystal modified
MWCNTs and conventional Au electrodes under four
different situations. In a stability test (25°C, 25‐35%
relative humidity [RH]), the PCE of unencapsulated PSCs
with Au dramatically decreased after around 45 days,
while the PCE of cells with MWCNTs were very stable
even after 60 days of testing. During photostability testing
in ambient conditions, MWCNT‐based PSCs were more
stable as well. In addition, Raminafshar et al45 also
confirmed the moisture‐resistant properties of the carbon
electrode. The PCE of all their PSC cells were around 10%
within 4 months without encapsulation under ambient
temperature (~25°C) and humidity (20‐30%). The hydro-
phobic carbon layer effectively protected the PSC from
humidity penetration, which was an important factor to
increase the stability of PSC.
Furthermore, the mechanical stability of flexible PSCs
was also attributed to the pliability of carbon‐based films.
Yoon et al46 developed a super‐flexible PSC using a
graphene electrode. In a 1.77 mm2 device, PCE was 16.8%
without hysteresis. The flexible device maintained 90%
4 | HE ET AL.

efficiency after 1000 2‐mm‐radius bending cycles, but the
PCE of the cells fabricated on conventional indium‐tin
oxide (ITO)/polyethylene naphthalate (PEN) substrates
decreased to 40% after 1000 4‐mm‐radius bending cycles.
Jang et al47 further developed another flexible PSC with a
modified graphene electrode and Ag reflectors at both
sides of the cell, achieving a forward and reverse PCE of
10.96% and 11.16%, respectively. The PCE maintained
more than 70% of its original value even after 1000 8‐mm‐
radius bending cycles. More information about the
mechanical properties of the TCO layer in carbon‐based
PSCs will be discussed later in Section 2.3.
2.1.3 | Economic benefits
Carbon‐based electrodes also have advantages because of
their low cost and simple fabrication process. Meng
et al48 fabricated an economical and stable coal‐based
PSC that attained a PCE of 10.87% (0.3 cm2) and 8.72%
(1 cm2) by a simple hot‐press method. Wei et al49
converted the greenhouse gas CO2 into a 3D honey-
comb‐like structured graphene through a reaction
between potassium and CO2. The graphene‐based film
acted as an electrode in an HTL‐free PSC that achieved a
PCE of 10.06%. This will contribute significantly to
further facile PSC module manufacturing, which will be
discussed in Section 3.3.
2.2 | Carbon materials in charge
transporting layers
Although carbon‐based PSCs are reliable and efficient,
their performance is still restricted by a variety of factors
shown in Figure 2A, such as moisture, thermal degrada-
tion, and recombination loss. Carbon materials are also
great candidates to solve the challenges that occur in the
charge transporting layers.
Doping is a promising strategy to enhance the
performance of the PSCs, but it also leads to some
defects and decreases the stability of the PSCs. However,
the inherent p‐type nature of CNTs makes it viable as an
alternative material to be used in charge‐transporting
layers as a p‐type contact in PSCs. This eliminates the
need to dope without sacrificing the existing performance
and improves the stability of the PSCs. In 2014,
Habisreutinger et al50 fabricated a CNTs/polymer

FIGURE 2 Carbon materials in charge transporting layers. A, Challenges in each layer of a carbon‐based PSC. B, CNTs/polymer
composite HTL layer with high performance. Reproduced with permission: Copyright 2014, American Chemical Society.50 C, Electrical
performance of HTL with PEDOT:PSS, CNT, and hybrid material. Reproduced with permission: Copyright 2019, Elsevier.51 D, PCE of PSCs
by using graphene quantum dots modified SnO2 ETL layer. Reproduced with permission: Copyright 2014, American Chemical Society.52
E, Current density of graphene‐modified SnO2 as ETL. Reproduced with permission: Copyright 2018, American Chemical Society.53 CNT,
carbon nanotube; ETL, electron transport layer; FTO, fluorine‐tin oxide; HTL, hole transport layer; PCE, power conversion efficiency;
PEDOT:PSS, poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate; PMMA, poly (methyl methacrylate); PSC, perovskite solar cell
HE ET AL. | 5

composite HTL layer to mitigate thermal degradation.
The CNTs/polymer composite serves as an insulating
layer to improve the thermal stability of the PSCs. As a
result, the PCE reached 15.3%, and its average efficiency
was 10% ± 2% (Figure 2B). Moreover, rather than solely
using CNTs as an HTL alone, Yoon et al51 used a hybrid
HTL layer consisting of CNTs and poly(3,4‐ethylene
dioxythiophene) polystyrene sulfonate (PEDOT:PSS) to
decrease hole vacancies. The highest performing (Figure
2C) composition showed effective surface and photo-
luminescence quenching properties, with a PCE of 16.0%
and a negligible hysteresis. The average PCE of metallic
CNT was 15.6%; while the PCE of the control group was
13.2%. In addition, CNTs could also be used in the ETL
layer. Batmunkh et al54 used SWCNTs‐incorporated TiO2
nanofibers to accelerate electron transportation. It not
only created a pathway for electron transportation but
also suppressed the charge recombination in the PSC.
The hysteresis effect, recombination losses, and carrier
extraction efficiency are challenges that are influenced by
many factors, such as the interfacial interaction between
layers, the grain size, and the energy level of each layer.
To solve such problems, Xie et al52 added a small amount
of graphene quantum dots (GQDs) to SnO2 film to
improve its conductivity. The electrons generated by the
GQDs filled the trap states in SnO2 created by the
solution process, and as a result, the PCE reached up to
20.23% (Figure 2D) with little hysteresis. Zhu et al53 used
graphene to modify SnO2 in the ETL to increase electron
mobility and attenuate recombination loss. The forward/
reverse PCE (Figure 2E) of the cells was improved from
15.45%/17.01% to 17.36%/18.11% compared with the cell
with SnO2 ETL only. Inserting an interlayer between the
perovskite layer and the carbon layer is another strategy
to potentially boost the PCE. Bashir et al55 added a thin
layer of Cu‐doped NiOx nanoparticles into the PSC for the
purpose of increasing the extraction efficiency of the
holes. They further made it into monolithic PSC modules,
and the efficiency of the champion device reached 12.1%.
Zhang et al56 used CuPc nanorods to enhance hole
transportation and suppress recombination losses, attain-
ing a PCE of up to 16.1%, which is higher than that of
devices with an HTL‐free structure (9%) or with
conventional HTL materials (10.4%).
Energy level mismatching between layers in PSCs is
another challenge that must be overcome. As shown in
Figure 3, when light is absorbed by perovskite, hole‐
electron pairs are created. Electrons are transported
through the ETL, and holes are transported through the
HTL. Taking electron transition as an example, if
the lowest unoccupied molecular orbital level (LUMO)
of the perovskite layer is much higher than the LUMO
level of the ETL, it will lead to excessive energy loss
(Figure 3A). However, if the LUMO level of perovskite
layer is lower than LUMO level of the ETL, the electrons
are difficult to transfer to the ETL because of large energy
barrier62 (Figure 3B). Thus, decreasing energy level
mismatching is very important to help save energy and
improve the efficiency of PSCs. C60 is often used to
improve the electron extraction of the ETL. Tian et al57
used a C60‐modified TiO2 layer to decrease energy
mismatching between the ETL and perovskite layer.
From Figure 3, it is noticeable that the C60 shifted the
LUMO level of TiO2 up from −4.2 to −4.11 eV, which is
closer to the LUMO level of perovskite. As a result, the
PCE of the device increased from 13.7% to 15.4% owing to

FIGURE 3 Energy level of each layer in PSCs.51,55,57-61 A, Energy loss exists when LUMO level of perovskite is much larger than
that of ETL. B, Energy barrier exists when LUMO level of perovskite is smaller than that of ETL. CNT, carbon nanotube; ETL, electron
transport layer; FTO, fluorine‐tin oxide; GO, graphene oxide; LUMO, lowest unoccupied molecular orbital level; PCBM, XXX; PSC,
perovskite solar cell; PEDOT:PSS, poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate
6 |
modification of C60, and it also decreased the hysteresis
effect of the device. Similarly, Wojciechowski et al62 used
a C60 self‐assembled monolayer (SAM) as an interlayer
between TiO2 and perovskite. The inserted C60‐SAM
layer removed the electronic barrier across the interface,
leading to a favorable upwards shift in the LUMO level of
perovskite.
In summary, various carbon materials are utilized in
different layers of the PSC cell based on their unique band
structural features. For example, CNTs are used in the
electrode and charge‐transporting layers. Due to the
electronic heterogeneity of CNTs, the electrical properties
of CNTs can be changed with their chirality. For the one‐
third CNTs chiralities,63 the valence band and conduction
band overlap and give CNTs metallic properties. In this
case, the metallic CNTs are suitable in the electrode layer,
which requires high conductivity as well as advanced
mechanical properties. Similarly, graphene could also be
used in the electrode layer because of its metallic proper-
ties.63 For the other two‐third CNTs chiralities, since the
valance band and conduction band do not overlap, there
exists a bandgap in the band structure, which gives the
CNTs semiconducting properties. In this case, the semi-
conducting CNTs are more suitable to be used in the charge
transporting layers, which requires a longer carrier
transporting lifetime. Moreover, C60 is suitable in the
electron transportation layer because it is an n‐type
semiconductor.62 The high electron affinity, mobility, and
long carrier transport lifetimes make C60 an ideal electron
transport material in PSCs.
2.3 | Carbon materials in perovskite
layer
Carbon materials in perovskite layers can enhance the
electrical property of the device. It is reported that
graphene with a scaffold structure can improve the
short‐circuit current density (Jsc) and fill factor of PSCs
while reducing the hysteresis effects, since the perovskite
material is surrounded by a 3D porous‐reduced graphene
scaffold with high surface area and lower resistance.60
More importantly, the 3D‐reduced graphene scaffold has
higher transmittance than the typical 2D graphene
because of its light trapping property, which further
reduced reflection. The PCE of the 3D graphene device is
17.2%, compared with 13.5% of the TiO2‐based PSC, and
the average Jsc showed a nearly 20% increase with 3D
graphene. As for CNTs, reduced‐graphene oxide (RGO)
and carbon nanoparticles assist with the perovskite
crystallization process, which results in a larger perovskite
grain size, decreases the grain boundaries, and benefits the
transportation of holes and electrons. The recorded PCEs
were 19.5%, 18.8%, and 18.3%, respectively.64-66
HE ET AL.
Carbon materials can also improve the stability of
the device by forming heterojunction structures with
perovskite, due to the hydrophobic properties of the
carbon materials. Han’s group have been conducting
research in developing mesoscopic PSCs (m‐PSCs): in
2014, Mei et al67 developed a fully printable HTL‐free
carbon‐based m‐PSC. The PCE of their device was
12.8% and kept stable over 1000 hours in ambient air
under sunlight. Very recently from Han’s group, Tian
et al57 achieved a PCE of 15.4% with high stability by
using a C60‐modified TiO2 layer in the m‐PSCs. For
planar PSCs (p‐PSCs), Fu et al68 used C60‐PEG to
fabricate the perovskite films. As a result, the PCE of
their device reached 17.71%, and the PCE of the device
held at 86% of its original value after 40 days of ambient
conditions testing.
2.4 | Carbon materials in the TCO layer
Carbon allotropes with high transmittance, excellent
conductivity, and bending properties are attractive
alternatives to replace the brittle and expensive conven-
tional TCOs such as ITO or fluorine‐tin oxide. Acting as
the transparent conducting electrodes in both single‐
junction and PSC modules, carbon materials could offer
the great potential to boost PSC module development and
flexible PSC development in the wearable electronics
area.69-72
2.4.1 | High transmittance and
conductivity performance
Graphene and CNTs are the most common allotropes
utilized in the TCO layer. Solution‐processed graphene
was first utilized as a transparent electrode in 2016.69 The
solution processing method is able to form a large‐area
film, which gives it the potential to be used in PSC
module production. However, finding the fine balance
between film transparency and sheet resistance has
proven difficult. The resistance can be reduced by using
a thicker film, but this, in turn, has a negative influence
on the optical properties of the film (Figure 4A and 4B).
As a result, the highest PCE of the Au/spiro‐OMeTAD/
perovskite/TiO2‐graphene/RGO structure PSC is less
than 1%. This low efficiency was improved by using
technologies such as chemical vapor deposition (CVD)
for the growth of graphene and vacuum thermal
evaporation methods for the preparation of MoO3.10 It
is reported that perovskite grains grow larger on the
smooth graphene/PEDOT:PSS surface, resulting in less
defects at the grain boundary, improved photovoltaic
properties, and an offset of the low conductivity of the
graphene electrode, producing a PCE up to 17% of an
HE ET AL. | 7

inverted p‐i‐n structure PSC. Furthermore, the usage of
graphene also has a positive effect on the optical
properties of the device; the transmittance of the device
is as high as 97% compared to a PSC using conventional
ITO materials (89%).
In addition, doping Ag nanowire into graphene can
further enhance the conductivity.71 Besides shifting the
Fermi level of graphene and changing it into an n‐type to
make it more appropriate in the TCO layer, doping with
Ag nanowire also decreased the resistance of the
transparent conducting electrode (from 560 to 52 Ω/sq).
The highest PCE achieved was 15.8% on a glass substrate,
nearly 6% higher than the one without dopant. All of
PSCs have over 80% transmittance.
2.4.2 | Mechanical improvement
Besides excellent electrical properties, graphene and
CNTs also increased the stability of devices subjected to
bending behavior. The PCE of PSCs based on graphene or
CNTs will not dramatically decrease even after thousands
of bending cycles. Compared with the ITO/PEN
substrate, whose normalized PCE dropped below 60%
after 1000 bending cycles, both graphene and CNT
transparent conducting layers showed minimal degrada-
tion in their PCE (Figure 4C).73 The PCE of graphene‐
based PSCs (13.3%) is better than that of CNTs‐based
PSCs (11%) because the average roughness value of
graphene film (3.5 nm) is smaller than that of SWCNT
film (15.1 nm). This results in a larger contact area
between the electrode layer and the perovskite layer
could improve hole transportation efficiency. However,
due to defects on the grain boundary, the sheet resistance
of graphene electrodes also increased after bending.
Despite the tiny decrease in efficiency, graphene electro-
des should still be recognized as an excellent TCO layer,
maintaining a PCE above 80% even after 500 cycles of a
harsh bending test as shown in Figure 4E (R = 1.3 mm).
In addition, 1.75, 3.65, and 6.7 mm glass tubes are also
used for mechanical properties characterization, the J‐V
curves of PSCs are shown in Figure 4C.73,74 Moreover, the
usage of ultrathin flexible substrates makes devices more
portable when compared with glass substrate planar solar
cell modules.

FIGURE 4 PSCs with a flexible and transparent substrate using carbon as the TCO layer. A, Structure of high transparency PSC.
Reproduced with permission: Copyright 2019, Elsevier.47 B, Resistance and transmittance of graphene transparent electrodes with different
thickness. Reproduced with permission: Copyright 2016, the Royal Society of Chemistry.69 C, Degradation curve of PSCs using ITO/PEN,
graphene/PEN, and SWCNT/PEN as TCO layer, insert shows the PSC structure. Reproduced with permission: Copyright 2017, American
Chemical Society.73 D, Structure of p‐i‐n flexible PSC. E, Bending behavior of the PSC on glass tube with a radius of 1.3 mm (Bending on
R = 6.7mm , R = 3.65mm , R = 1.75 mm tubes are also tested). F, J‐V curve of PSC after bending on glass tubes with different radius.
Reproduced with permission: Copyright 2016, Elsevier.74 ITO, indium‐tin oxide; PCBM, XXX; PCE, power conversion efficiency; PEN,
polyethylene naphthalate; PSC, perovskite solar cell; RGO, reduced graphene oxide; SWCNT, single‐wall carbon nanotube; TCO, transparent
conducting oxide
8 |
3 | C A R BO N M A T E RI A L S I N
MONOLITHIC P SC MODULES
On the basis of the superior performance of single‐junction
PSCs, more research works have utilized carbon electrodes
for large‐area monolithic PSC module production.
3.1 | Carbon electrode in PSC modules
As a promising electrode material in PSC modules,
carbon has been widely used in PSC modules with a
monolithic structure for two reasons: first, by forming a
mesoscopic structure, carbon materials can greatly
improve the stability of the modules, which is a key
factor for the module function. Second, most carbon‐
based electrodes are compatible with the continuous
(screen‐printing) and low‐cost (solution process) manu-
facturing processes, which is another important con-
sideration for the module’s future applications. Table 1
has summarized recent represented works focusing on
carbon‐based PSC (related to PSC module) and mono-
lithic PSC modules’ testing results.
3.2 | Stability
Methylammonium organic cation is the most popular
type of perovskite layer in organic‐inorganic PSCs.
However, the water‐soluble MA iodide causes degrada-
tion of the perovskite crystal structure in high‐moisture
environments (Figure 5A), resulting in a lower PCE after
outdoor exposure.43 Thus, the hydrophobicity of the
device plays a critical role for devices’ long‐term use.
Varieties of research have shown that hydrophobic
carbon materials used in each layer of the PSC can also
improve stability in high RH and high‐temperature
environments.37,44,50,75
3.2.1 | Stability improvement in
different layers of carbon‐based
single‐junction PSCs
Superior water resistance is one of the main reasons that
carbon electrode PSCs have excellent stability in high‐
moisture environments.43,91,92 Besides conventional car-
bon, CNT membranes, graphene oxide (GO), and GQDs
could also prevent water penetration into the perovskite
layer.37,44,63,93-95 When directly used as a hole transport
material (HTM), CNTs have a very high water vapor
transmission rate (3400 g/m2d).96 However, after mixture
with polymers (eg, poly(3‐hexylthiophene) [P3HT], poly
(triarylamine)), the dense hybrid polymer composite
formed prevented the water vapor from going through
into the perovskite layer, and the water vapor
HE ET AL.
transmission rate decreased to only 150 g/m2d with a
P3HT matrix.97 Furthermore, other modifications can be
made to improve the hydrophobicity of carbon‐based
PSCs, such as the encapsulation of the hydrophobic
materials,75 or the addition of Cs, Rb, Br ions into the
perovskite layer.83
In addition, SWCNTs can enhance the stability of the
device at high temperature.79 Compared with Au
electrode PSCs, whose PCE decrease 20% after only
8 hours in a 60°C environment, the device using SWCNTs
(initial PCE = 14.3%) shows a 0.04% PCE drop with the
sloop −0.005% h−1, illustrating its heat resistance
property. Some polymers such as poly (methyl metha-
crylate) (PMMA) also have a stable structure even at high
temperatures (80°C). The combination of CNTs main-
tains the high‐temperature stability (Figure 5B) while
also increasing conductivity. The device with CNTs‐
P3HT‐PMMA HTM shows no significant degradation and
had a final PCE around 14.6%.49
Fullerene and graphene applied in the ETL can also
improve the stability of PSCs. Fullerene could reduce the
charge trapping that occurs at the interface between the
ETL and perovskite layers, leading to a more stable PCE.
This is because of its lower conduction bandgap when
compared with conventional electron‐transporting mate-
rials such as TiO2 (Figure 3), while graphene acts as an
isolation layer that prevents the reaction between ZnO
and perovskite triggered by light.81,83,96
3.2.2 | Stability improvement in PSC
modules
Though stability was a significant problem in the early
years, the PSCs produced nowadays always have an
excellent long‐term stable PCE, even when scaled to
large‐area PSC modules. One of the reasons for the
good stability of module PSCs is the usage of hydro-
phobic carbons,22,86,87,98 which prevents the diffusion
of water into the perovskite. The PCE of the film only
decreased slightly after exposure to outdoor environ-
ments (Figure 5D and 5F). Besides utilizing the
inherent properties of carbon, doping it with water‐
resistant particles such as Co3O4 can also enhance the
stability of the whole solar cell.88
Most of the large‐area PSC modules using hydro-
phobic carbon electrodes are HTL‐free. Nevertheless,
the insertion of an HTL could enhance the stability of
the PSC.55 Compared with HTL‐free PSCs, which
showed 10% degradation, PSCs using carbon electrodes
with additional Cu‐doped NiOx HTM showed no
change in PCE even after 6000 hours of exposure to
ambient environment conditions (Figure 5C). In
addition, for large‐area PSCs with HTLs, the usage of
HE ET AL. | 9

T A B L E 1 Recent works on carbon‐based PSCs (related to PSC modules) and PSC modules, with an emphasis on stability

PCE drop
Perovskite structure PCE (%) Test condition rate Ref
Single‐junction PSCs
Electrode Ca/CH3NH3PbI3/TiO2/FTO 8.61 EC,a 3000 h 0% Liu et al75
C/spiro‐OMeTAD/P/TiO2/FTO 19.2 1000 h 5% Zhang et al37
C/poly(ethylene oxide)/P/TiO2/FTO 10.1 85°C/85% RH,a 192 h 9% Wu et al43
C/ZrO2/mesoporous TiO2/P/TiO2/FTO 6.7 35°C, 1046 h 0% Hashmi et al76
Organic nanocrystal‐MWCNT/CsPbBr3/ 5.44 60°C air, 24 h 0% Siram et al44
mesoporous TiO2/TiO2/FTO Outdoor, 1000 h 20%
HTL Ag/PMMA‐P3HT‐SWCNTs/P‐Al2O3/TiO2/ 14.6 80°C air, 96 h 0% Habisreutinger et al50
FTO
Ag/PCBM/P/PEDOT:PSS‐GO/ITO 15.3 15% RH, 940 h 17% Luo et al77
Au/PMMA‐GO‐SWCNTs/P/mesoporous 10.5 70‐80% RH, 240 h 0.50% Wang et al78
TiO2/TiO2/FTO
SWCNTs/spiro‐OMeTAD/P/mesoporous 14.3 20°C first 14 h then 60°C, 0.70% Aitola et al79
TiO2/TiO2/FTO 141 h
C/P3HT‐Ga/P/SnO2‐TiO2/FTO 17.2 50% RH, 1680 h 3% Chu et al80
16.3 EC, 600 h 11%
ETL Au/spiro‐OMeTAD/P/monolayer G‐ZnO/FTO 21 300 h 7% Tavakoli et al81
Au/spiro‐OMeTAD/CH3NH3PbI3/PCBM‐ 17.6 45% RH, 300 h <20% Yang et al82
GQDs/FTO
C/MAPbI3/C60/FTO 15.4 40‐60% RH, 480 h 5% Meng et al83
P a
Ag/BCP‐PCBM/CH3NH3PbI3‐C nanodots/ 18 40% RH, 504 h 0% Hsu et al84
NiOx/ITO
Ag/BCP‐PCBM/perovskite‐C60‐polyethylene 17.7 60% RH, N2, 960 h 7% Fu et al68
glycol/NiOx/ITO
PSC modules
C/ZrO2/perovskite/TiO2/FTO (100 cm2) 10.4 54% RH, 1000 h 0% Hu et al22
EC, outdoor, 720 h 0%
C/mesoporous ZrO2/P/mesoporous TiO2/TiO2/FTO 10.1 55°C, >10 000 h 0% Grancini et al85
(100 cm2)
C/perovskite/ZnO/TCO (25 cm2) 10.6 EC, outdoor, 3360 h 0% Cai et al86
C/ZrO2/perovskite/mesoporous TiO2/TiO2/FTO 10.7 65‐70% RH, 2016 h <5% Priyadarshi et al87
(70 cm2)
C/Co3O4‐ZrO2‐P/mesoporous TiO2/FTO (70 cm2) 11.4 70% RH, 2500 h 0% Bashir et al88
C/ZrO2‐Cu:NiOx/P/mesoporous TiO2/TiO2/FTO 12.1 65% RH, 6000 h 0% Bashir et al55
(70 cm2)
Au/P/GO‐Li/mesoporous TiO2‐G/TiO2/FTO (50.6 cm2) 12.6 EC, <30% RH, 1630 h 9% Agresti et al89
Abbreviations: BCP, bathocuproine; C, carbon; EC, encapsulated; ETL, electron transport layer; FTO, fluorine‐tin oxide; G, graphene; GO, graphene oxide,
GQD, graphene quantum dot; ITO, indium‐tin oxide; MWCNT; multiwalled carbon nanotube; P, perovskites; P3HT, poly(3‐hexylthiophene); PCBM, phenyl
C61 butyric acid methyl ester; PEDOT:PSS, poly(3,4‐ethylenedioxythiophene) polystyrene sulfonate; PCE, power conversion efficiency; PMMA, poly (methyl
methacrylate); PSC, perovskite solar cell; RH, relative humidity; SWCNT, single‐wall carbon nanotube; TCO, transparent conducting oxide.
a
Unless specified, all measurement was conducted with unencapsulated samples 1 Sun, AM 1.5 G at room temperature.

SWCNTs/GO/PMMA HTLs can result in improved 3.3 | Processing and manufacturing

stability when compared to that of traditional HTL
The scalability of each component in PSCs is a big
materials (Figure 5E). Thus, these carbon materials
concern for the modularization of PSCs. Although
with different structures have the potential to be
manufacturing lines for different carbon materials have
incorporated into different types of PSC modules to
already been developed, simple fabrication and contin-
provide extra stability.
uous preparation process of carbon‐based PSCs is still
10 | HE ET AL.

FIGURE 5 The stability of PSCs. A, Broken down of perovskite in moisture environment. Reproduced with permission: Copyright 2016,
the Royal Society of Chemistry.90 B, Degradation behavior of CH3NH3PbI3‐xClx perovskite layer with different cover materials at 80°C.
Reproduced with permission: Copyright 2014, American Chemical Society.50 C, PCE degradation curve for carbon‐based PSC with and
without HTL at 25°C with 65% RH. Reproduced with permission: Copyright 2019, Elsevier.55 D, The structure of a large‐area (100 cm2) PSC.
Reproduced with permission: Copyright 2017, John Wiley and Sons.22 E, Stability characterization of PSC with traditional spiro‐OMeTAD
HTL and SWCNT/GO‐based HTL under 70% to 80% RH condition. Reproduced with permission: Copyright 2016, the Royal Society of
Chemistry.78 F, The stability performance at the outdoor environment for 30 days (units: V for Voc, mA/cm2 for Jsc, % for PCE). Reproduced
with permission: Copyright 2017, John Wiley and Sons.22 FTO, fluorine‐tin oxide; GO, graphene oxide, HTM, hole transport material; HTL,
hole transport layer; PCE, power conversion efficiency; PMMA, poly (methyl methacrylate); PSC, perovskite solar cell; PTTA, poly‐
triarylamine; RH, relative humidity; SWCNT, single‐wall carbon nanotube

waiting to be fully developed and optimized. Some
methods such as CVD, though it can be used for the
growth of graphene or CNTs with excellent electrical
properties,71,73,99,100 are still not mature for large‐area
module preparations. As such, solution processing is one
of the most suitable methods for module manufactur-
ing.29,101 After dispersing carbon materials into an
organic solvent, large‐area carbon film can be coated
onto the substrate. Therefore, the solution processing
carbon ink is applicable for several printing methods.
Inkjet printing technology is a low cost, scalable
fabrication method. The first instance of inkjet printing
as applied to the carbon‐based PSCs fabrication was by
Wei et al.102 They designed the carbon/CH3NH3I ink for
the instant construction of a better interface between the
perovskite layer and the carbon electrode, which not only
provided a major step towards the large‐scale carbon‐
based PSC fabrication but also maintained the high
performance of the PSCs (Figure 6A). The solution
process is an important step during mass‐producible
fabrication of carbon paste electrode PSCs, m‐PSCs, and
many other carbon‐based PSCs. Inkjet printing and any
other solution process methods need a suitable solvent
that must meet at least three requirements to avoid any
damage on perovskite materials.38 This solvent must be
nonpolar, cannot dissolve or react with perovskite
HE ET AL. | 11

materials or the underlying layer, and have a low boiling
point.
Screen‐printing (Figure 6B) and the subsequent
annealing process is an effective method to mass‐produce
PSCs modules. Mishra et al105 explored how the
annealing temperature would affect the electrical, and
structural properties of the carbon electrode. It is believed
that there was a temperature point to achieve the best
performance, but negative effects would occur if tem-
perature surpassed this point. Figure 6C shows the
proposed production line of perovskite solar modules
with triple mesoporous layers as a scaffold.22 Three layers
with mesoporous TiO2, ZrO2, and carbon are printed on
the compact TiO2, respectively. Then perovskite solution
is dropped into the triple layers. Each 1 m2 panel consists
of 96 perovskite solar modules that contain different
numbers of subcells. Figure 6D shows the structure of the
monolithic PSC module.104 P1, P2, and P3 represent the
laser processes, which are used to separate different
layers and form subcells.
After around 10 years of PSC technology develop-
ment, the availability of materials, easy fabrication
processes, and improved performance have allowed
researchers to turn their focus to the modularization
and commercialization of PSCs. According to a
techno‐economic analysis of PSC module fabrication
from Song et al, 104 the average direct cost is $31.7 per
m2 , and the minimum sustainable price is $0.41 per
peak DC watts. The proposed manufacturing technol-
ogy is a low‐temperature deposition method. As
shown in Figure 6E, the flow diagram shows all
processes, including PSC manufacturing, module
integration, encapsulation, and testing. PSC modules
have benefits on its manufacturing cost compared
with the crystalline silicon solar cells, which have an
average market price of approximately $0.4 to 0.5 per
watt. 104 In addition, PSC modules capable of a 12‐
month service lifetime without degradation have been
developed.22 Though the solar cell life is still far below
than that of Si solar cell, 106 the degradation preven-
tion technologies have been developed rapidly recent
years. The lower cost and high efficiency make PSC
modules a strong contender for future applications in
the grid. Combined with carbon’s tremendous advan-
tages in PSC modules, the current proposed and future
manufacturing methods will further boost the
PSC module development and commercialization
processes.

FIGURE 6 Carbon‐based PSCs fabrication process and manufacture line. A, Fabrication process of an instant inkjet fabrication by
using carbon ink. Reproduced with permission: Copyright 2014, John Wiley and Sons.102 B, Fabrication of paintable carbon‐based
PSCs process. Reproduced with permission: Copyright 2016, the Royal Society of Chemistry.103 C, Proposed fabrication process of
carbon‐based mesoscopic PSC modules. Reproduced with permission: Copyright 2017, John Wiley and Sons.22 D, Monolithic integrated
PSC modules and (E) PSC modules manufacturing line. Reproduced with permission: Copyright 2017, the Royal Society of Chemistry.104
PSC, perovskite solar cell; ITO, indium‐tin oxide
12 | HE
4 | C ON C LU S I O N
Due to the PSC’s high‐performance nature and the
tremendous research efforts recently, PSCs have moved
into the module era, which requires both high efficiency
and stability. First, to obtain the high‐performance PSC,
carbon materials have come into prominence for their
beneficial optical, electrical, and mechanical properties
when applied in multiple different layers of the solar
cells. Second, to maintain the stable performance of
PSCs, hydrophobic 0D to 3D carbon materials can also be
used to protect the perovskite layer from moisture and
temperature‐related degradation. Moreover, the flexibil-
ity of the carbon materials also improves the PSC’s
lifetime due to its enhanced mechanical property. Other
than pursuing both high PCE and stability in single‐
junction PSCs, researchers have also begun the explora-
tion into carbon‐enabled PSC modules. Finally, although
the PCE of carbon‐based PSC modules at the current time
is still around 10%, many of the latest technologies used
in small‐scale carbon‐based PSCs have yet to be applied
to large‐scale modules. With the rapid development of
manufacturing technologies coming out every day, the
mass production of carbon‐based PSC modules can now
be realized. Integrating more and more breakthroughs
from existing single‐junction PSCs into large‐scale PSC
modules will certainly further push the current pace in
the PSC module area and push the PSC towards the field
testing, potentially as a part of the electrical grid. Given
the recent advances in PSC technology, carbon materials
will surely play a key role in paving the way towards
affordable solar energy with a long service lifetime to
meet global societal needs.
ACKNOWLEDGMEN TS
PD acknowledges George Mason University for startup
support. FH acknowledges the support by the National
Natural Science Foundation of China NSFC (51702038).
ORCID
Pei Dong http://orcid.org/0000-0002-9408-4764
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HE ET AL. | 15

92. Oo TT, Debnath S. Application of carbon nanotubes in AUTHOR BIOGRAPHIES

perovskite solar cells: a review. AIP Conf Proc. 2017;1902:
020015. Rui He obtained his master in the
93. Wang Y, Zhao H, Mei Y, Liu H, Wang S, Li X. Carbon
Department of Material Science
nanotube bridging method for hole transport layer‐free
and NanoEngineering from Rice
paintable carbon‐based perovskite solar cells. ACS Appl Mater
Interfaces. 2019;11(1):916‐923. University in 2018 and is currently
94. Ouyang J. Applications of carbon nanotubes and graphene for a PhD student at George Mason
third‐generation solar cells and fuel cells. Nano Mater Sci. University. He is currently work-
2019;1(2):77‐90. ing on carbon nanomaterials and
95. Bouclé J, Herlin‐Boime N. The benefits of graphene for hybrid polymer materials.
perovskite solar cells. Synth Met. 2016;222:3‐16.
96. Ahn N, Jeon I, Yoon J, et al. Carbon‐sandwiched perovskite
solar cell. J Mater Chem A. 2018;6(4):1382‐1389.
Xiaozhou Huang received his
97. Lee HW, Yoon Y, Park S, et al. Selective dispersion of high purity
semiconducting single‐walled carbon nanotubes with regioregu- master in Material Science and
lar poly(3‐alkylthiophene)s. Nat Commun. 2011;2:541. NanoEngineering at Rice Univer-
98. Rong Y, Hu Y, Mei A, et al. Challenges for commercializing sity. He is currently a PhD student
perovskite solar cells. Science. 2018;361(6408):eaat8235. at George Mason University. His
99. Shin DH, Kim JM, Shin SH, Choi S‐H. Highly‐flexible research focuses on energy and
graphene transparent conductive electrode/perovskite solar water treatment.
cells with graphene quantum dots‐doped PCBM electron
transport layer. Dyes Pigm. 2019;170:107630.
100. Kim TH, Lee T, El‐Said W, Choi JW. Graphene‐based
materials for stem cell applications. Materials. 2015;8(12):
8674‐8690. Pei Dong is an Assistant Professor
101. Huang F, Li M, Siffalovic P, Cao G, Tian J. From scalable in the Department of Mechanical
solution fabrication of perovskite films towards commer- Engineering. She obtained her BS
cialization of solar cells. Energy Environ Sci. 2019;12(2): in Microelectronics from Nankai
518‐549. University and her PhD in Me-
102. Wei Z, Chen H, Yan K, Yang S. Inkjet printing and instant
chanical Engineering from Rice
chemical transformation of a CH3NH3PbI3/nanocarbon elec-
University. She then did her post-
trode and interface for planar perovskite solar cells. Angew
Chemie ‐ Int Ed. 2014;53(48):13239‐13243. doctoral research in the Depart-
103. Liu Z, Shi T, Tang Z, Sun B, Liao G. Using a low‐temperature ment of Materials Science and
carbon electrode for preparing hole‐conductor‐free perovskite NanoEngineering at Rice University before joining
heterojunction solar cells under high relative humidity. George Mason University. She was awarded the Franz
Nanoscale. 2016;8(13):7017‐7023. and Frances Brotzen Fellowship. Her current research
104. Song Z, McElvany CL, Phillips AB, et al. A technoeconomic interests include design, synthesis, and applications of
analysis of perovskite solar module manufacturing with low‐
advanced materials in energy and water areas.
cost materials and techniques. Energy Environ Sci.
2017;10(6):1297‐1305.
105. Mishra A, Ahmad Z, Zimmermann I, et al. Effect of
annealing temperature on the performance of printable
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2019;65:375‐380.
106. Meng L, You J, Yang Y. Addressing the stability issue of
From single‐junction to modules. Carbon Energy.
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