See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/334663007

Carbon-Based Electrode Engineering Boosts the Efficiency of All Low-

Temperature-Processed Perovskite Solar Cells

Article  in  ACS Energy Letters · July 2019

DOI: 10.1021/acsenergylett.9b01294

CITATIONS READS

8 285

8 authors, including:

Sisi He Longbin Qiu

Fudan University Southern University of Science and Technology
43 PUBLICATIONS   1,471 CITATIONS    91 PUBLICATIONS   5,139 CITATIONS   

SEE PROFILE SEE PROFILE

dae yong Son Zonghao Liu

Samsung Advanced Institute of Technology Huazhong University of Science and Technology
28 PUBLICATIONS   3,180 CITATIONS    51 PUBLICATIONS   2,068 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

catalysis View project

large area perovskite solar cells View project

All content following this page was uploaded by Sisi He on 20 August 2019.

The user has requested enhancement of the downloaded file.

 Letter
Cite This: ACS Energy Lett. 2019, 4, 2032−2039 http://pubs.acs.org/journal/aelccp

Carbon-Based Electrode Engineering Boosts

the Efficiency of All Low-Temperature-
Processed Perovskite Solar Cells
Sisi He, Longbin Qiu, Dae-Yong Son, Zonghao Liu, Emilio J. Juarez-Perez,⊥ Luis K. Ono,
Collin Stecker, and Yabing Qi*
Energy Materials and Surface Sciences Unit (EMSSU), Okinawa Institute of Science and Technology Graduate University (OIST),
Downloaded via OKINAWA INST SCI TECHLGY GRAD UNIV on August 1, 2019 at 22:18:42 (UTC).
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.

1919-1 Tancha, Kunigami-gun, Onna-son, Okinawa 904-0495, Japan

*
S Supporting Information

ABSTRACT: Carbon electrode-based perovskite solar cells (PSCs)

with low-cost and long-term stability have been recognized as a
competitive candidate toward future practical applications. However,
energy level mismatch and ineffective hole extraction at the carbon
electrode/perovskite interface limit device performance. Herein, we
develop a low-cost carbon-based electrode that utilizes a cheap
small-molecule semiconductor copper phthalocyanine (CuPc) as
both the interface modifier and dopant. The resultant planar PSC
yields a power conversion efficiency of 14.8%, ∼30% higher than that
based on the bare carbon electrode. This is due to higher work
function and better hole extraction properties of the CuPc-modified
carbon electrodes. The simple modification process of the carbon
electrode has potential applications for large-scale fabrication. We
further applied such electrodes in large-area solar modules and
flexible solar cells, demonstrating their capability of upscaling and flexibility.

L ead halide perovskite solar cells (PSCs) have garnered

much attention due to the high power conversion
efficiency (PCE) and low-cost of production compared
with other thin film photovoltaic technologies.1−4 However,
the fabrication cost and instability still remain major barriers
standing in the way for commercialization.5 A typical PSC
structure consists of a transparent electrode, electron transport
layer (ETL), perovskite active layer, hole transport layer
(HTL), and back contact electrode.6 Among them, the most
common HTL is 2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-
amine)-9-9′-spirobifluorene (spiro-MeOTAD), which is ex-
pensive and requires dopants for high performance.7−9
Moreover, it exhibits severe issues such as heat-induced
degradation,10,11 crystallization,12 and phase segregation of
dopants.13 The use of gold or silver as top electrodes requires
thermal evaporation under high-vacuum conditions, which not
only increases the cost and energy consumption but also has
detrimental effects on the device stability due to the metal
diffusion during the operation of devices.14,15 An alternative
structure is to use carbon to function as both a HTL and back
contact electrode, which can significantly lower the cost,
improve the device stability, and expand applications to flexible
substrates.16−20
Much effort regarding the carbon-based PSCs has been
devoted to improving the performance.21−26 To date, many
PSCs employ a conventional mesoporous structure with a
metal oxide mesoporous scaffold (such as TiO2 or TiO2/ZrO2)
deposited on top of the TiO2 compact layer.20,27−31 Employing
this structure in PSCs can efficiently assist charge carrier
collection.32 The printing process of carbon is beneficial for
upscalable fabrication in solar modules. On the basis of this
mesoporous structure and carbon electrode, solar modules
have been successfully fabricated with the largest area of 623.7
cm2 (an active area of 198 cm2) and a corresponding efficiency
of 3.2% using carbon electrode.30,31,33 However, the high-
temperature fabrication process for depositing the metal oxide
scaffold increases the energy payback time and also makes it
incompatible with flexible substrates.27 The PSCs with a planar
structure without the mesoporous scaffold can be fabricated at
low temperatures and at a reduced cost.34−36 Low-temper-
ature-deposited ETL has been developed, which is useful for
low-temperature-processed carbon electrode-based devices.
For planar structure devices, SnO2 can be deposited by a
number of methods, e.g., a low-temperature solution-based
chemical bath process,37 a vacuum-based sputtering process,38
Received: June 17, 2019
Accepted: July 24, 2019
Published: July 24, 2019

© XXXX American Chemical Society 2032 DOI: 10.1021/acsenergylett.9b01294

ACS Energy Lett. 2019, 4, 2032−2039
ACS Energy Letters
and an atomic layer deposition process,39 which all exhibited
PCEs over 20% using spiro-MeOTAD and Au as the bottom
electrode. Furthermore, for a carbon electrode-based PSC
TiO2/SnO2 bilayer, the Zn-doped SnO2 layer and evaporated
CdS layer have been studied and show promising perform-
ance.40−42 In this case, the carbon electrode/perovskite
interface, which is the only effective hole extraction interface
in this device, is also expected to have a significant impact on
the device performance.43 Many strategies have been
developed to facilitate hole transport to improve the
performance of PSCs, such as inserting a low-cost HTL layer
between the perovskite film and the electrode to facilitate hole
transport such as a copper phthalocyanine (CuPc) layer by
thermal evaporation in vacuum.27,40−42 The reported device
structure with CuPc is based on a layered structure of inserting
a thin layer of CuPc with different morphology before
deposition of a carbon electrode. The best PCE is 16.1% by
using CuPc nanorods as the HTL and carbon as the counter
electrode based on the mesoporous structure.27 On the other
hand, to lower the fabrication temperature and obtain high
performance, further optimization of the ETL with a planar
structure was applied, such as using a TiO2/SnO2 bilayer,
evaporated CdS, and Zn-doped SnO2 as the ETL.40−42
However, insertion of a monolayer of CuPc in vacuum can
complicate the fabrication process. Moreover, the open-circuit
voltage (Voc) of carbon-based PSCs is lower than that of
conventional PSCs and needs to be further enhanced. One of
the reasons responsible for the lower Voc in carbon electrode-
based devices is the energy level mismatch between the carbon
electrode (e.g., graphite, carbon black) and the perovskite film
(e.g., CH3NH3PbI3 (MAPbI3), CH(NH2)2PbI3,
CH3NH3PbBr3).26,43,44 Therefore, a carbon electrode with a
suitable work function (WF) is also vital for attaining high
performance of PSCs.
In this work, we develop an elaborate process to engineer
carbon paste to optimize the properties of carbon electrodes
and the perovskite/carbon interface at the same time to
fabricate all low-temperature-processed carbon electrode-based
PSCs. CuPc was used as an additive to modify the carbon
electrode due to its low cost, high thermal and chemical
stability, small bandgap, and relatively high hole mobility.45,46
The CuPc-modified carbon electrode exhibits better interface
interaction with perovskite and an upshift of the WF favoring
Voc, charge transport, and extraction. The PCE of the PSCs
with a simple structure (FTO/compact TiO2/MAPbI3/carbon
film, where FTO is fluorine-doped tin oxide) was improved
from ∼11% (without CuPc) to ∼15% (with CuPc). The
efficiency of the PSCs with a CuPc-modified carbon electrode
was also higher than that with the evaporated CuPc interlayer
between the bare carbon electrode without modification and
the perovskite, showing better performance with a simple and
scalable process. In addition, the low-temperature coating
process is fully compatible with large-scale and continuous
fabrication. As a demonstration, carbon electrode-based solar
modules with a 22.4 cm2 designated area on a substrate with an
area of 5 cm × 5 cm have been fabricated with an efficiency
over 7%. Moreover, carbon electrode-based flexible solar cells
can be also fabricated on flexible conductive substrates thanks
to the low-temperature process and their compatibility with
printing processes.
We first studied the effect of the CuPc additive on hole
transport at the perovskite/electrode interface. The planar
structure PSCs of FTO/compact TiO2/MAPbI3/carbon were
2033
Letter
fabricated. Figure 1a−c shows the schematic illustration and
the scanning electron microscopy (SEM) images of the device
Figure 1. (a) Schematic drawing showing our carbon electrode-
based PSC structure. (b) Cross-sectional SEM image of the carbon
electrode-based PSC. (c) Enlarged image of (b).
structure. First, a compact TiO2 layer was prepared by sputter
deposition on FTO/glass substrate in vacuum. The MAPbI3
film was prepared by spin-coating the precursor solution with
diethyl ether dripping during the spinning process, followed by
annealing at 100 °C for 20 min.47 The as-prepared perovskite
film showed a full coverage and high crystallinity with large
grains densely packed on the surface (Figure S1). Finally, a
carbon electrode with CuPc additive was coated on the
perovskite layer by the doctor-blade method, followed by
annealing at 100 °C for 40 min. The thickness of the carbon
electrode was about 30 μm (Figure S2), and the carbon
electrode uniformly covered the perovskite layer. The carbon
electrode was mainly made by mixing carbon black and
graphite with the CuPc dispersed in the carbon source, which
can all be purchased at low cost. The morphologies of the
resultant carbon electrode with and without CuPc were almost
the same (Figure S3). Here, the planar structure PSCs were
fabricated with all of the steps with temperatures below 100
°C.
We further confirm the interaction between CuPc and
perovskite via high-resolution X-ray photoelectron spectrosco-
py (XPS) analysis. To be able to detect the signal at the
interface between perovskite and carbon, we removed the
majority of the top carbon electrode by using scotch tape. With
this removal process, some carbon remained on top of the
perovskite layer. As shown in Figure S4a, on the perovskite
surface that has a little carbon electrode remaining, i.e., at the
interface between carbon and perovskite, a clear main peak
with a satellite peak at higher binding energies ranging from
930 to 950 eV can be seen, which can be assigned to the Cu
2p3/2 species. The main feature at a binding energy of 934.75
eV corresponds to Cu2+.48 It is difficult to deconvolute the XPS
signals corresponding to Cu2+ and Cu+ accurately due to the
close proximity of these two peaks and the signal-to-noise ratio,
which is a result of the small amount of copper present. Two
other features in the range of 135−150 eV and 624−639 eV
correspond to Pb 4f and I 3d3/2, respectively (Figure S4b,c).
DOI: 10.1021/acsenergylett.9b01294
ACS Energy Lett. 2019, 4, 2032−2039
ACS Energy Letters Letter

Figure 2. Performance of PSCs using the CuPc-modified carbon electrode with the bare carbon electrode as a reference. (a) J−V curves of
the best PSCs with forward and reverse scans. (b) IPCE spectra of the best PSCs. (c) TRPL of the perovskite (PVSK) with CuPc-modified
carbon and perovskite with/without bare carbon as a reference. (d) UPS spectra of the carbon electrode, revealing WF differences (CuPc-
modified carbon: WF = 4.22 eV; bare carbon: WF = 4.03 eV). The inset shows the schematic energy level diagram of perovskite and carbon.
(Evac = vacuum level; EF = Fermi energy.)

Table 1. Photovoltaic Parameters for PSCs Using CuPc-Modified Carbon as the Electrode, Bare Carbon without Modification
as the Electrode, the CuPc Interlayer/Bare Carbon Electrode Structure, and the Spiro-MeOTAD/Au Electrode Structurea
device type Voc [V] Jsc [mA/cm2] FF [%] PCE [%]
CuPc-modified carbon 1.02 21.4 68 14.8
1.00 ± 0.03 20.7 ± 0.5 67 ± 1 13.9 ± 0.9
bare carbon 0.98 20.7 56 11.4
0.96 ± 0.03 20.6 ± 0.7 55 ± 6 11 ± 1
CuPc interlayer/bare carbon 0.95 20.7 65 12.8
0.96 ± 0.04 20.7 ± 0.4 59.2 ± 0.2 12 ± 1
spiro-MeOTAD/Au 1.02 22.0 75 16.8
1.06 ± 0.04 21.3 ± 0.7 71 ± 4 15.9 ± 0.9
a
The values in the upper line are the characteristics for the highest efficiencies, and the values with deviations are the average characteristics.

The two features at 138.4 and 143.4 eV detected on the bare
perovskite film were assigned to Pb2+.3 The peak at 630.9 eV
was assigned to I−.3 In this case, we compared the spectra of
the CuPc/perovskite interface and the bare CuPc film with a
thickness of 10 nm. The main peak of 934.75 eV associated
with the Cu 2p3/2 species showed a slight shift to the lower
binding energy after introduction of the CuPc additive (Figure
S4a). On the other hand, the position of Pb2+ showed a shift
toward a higher binding energy, indicating chemical doping
(Figure S4b).49 The enhanced interfacial coupling from the
interaction may endow the CuPc-modified carbon electrode
with better hole extraction ability,50 i.e., the photogenerated
2034
hole can be effectively transferred to the CuPc-modified
carbon electrode by this hole-transfer pathway.
We evaluate the photovoltaic properties of the PSCs with
carbon electrodes containing different CuPc contents under
AM 1.5 G 100 mW/cm2 illumination (Figure S5 and Table
S1). As expected, the PSC using the CuPc-modified carbon
electrode showed better performance compared with that of
the bare carbon electrode without modification. The best
performance was obtained in the case of the 1.0 wt % CuPc-
modified carbon electrode. Therefore, we chose the carbon
electrode with 1.0 wt % CuPc as the typical modified electrode
below, unless specified otherwise. Figure 2a shows the current
density−voltage (J−V) characteristics of the best PSCs with
DOI: 10.1021/acsenergylett.9b01294
ACS Energy Lett. 2019, 4, 2032−2039
ACS Energy Letters Letter

Figure 3. (a) Schematic drawing showing the two different device structures by applying CuPc as the additives in the carbon electrode and
the interface layer between the perovskite and carbon electrode. (b) J−V curves of the best PSCs based on these two different structures with
the forward and reverse scans. (c) UPS spectra of the CuPc-modified carbon including the photoemission secondary electron cutoff (left)
and the occupied states (right) as a function of CuPc content with the bare carbon as a comparison. (d) Experimentally determined energy
level diagrams of the CuPc-modified carbon as a function of CuPc content. (e) UPS spectra of the CuPc interlayer on the surface of the
carbon electrode including the photoemission secondary electron cutoff (left) and the occupied states (right) as a function of CuPc
thickness with the bare carbon electrode as a comparison. (f) Experimentally determined energy level diagrams of the CuPc interlayer on the
surface of the carbon electrode as a function of the CuPc film thickness.

the CuPc-modified carbon electrode with the bare carbon
electrode as comparison, measuring with both reverse and
forward scans. It is clear that introduction of the CuPc additive
to the carbon electrode led to an improvement of the device
performance in all of the photovoltaic parameters. As shown in
2035
Table 1, the champion PSCs with 1.0 wt % CuPc-modified
carbon electrode showed an impressive PCE of 14.8% under
reverse scan with a short-circuit current density (Jsc) of 21.4
mA/cm2, a Voc of 1.02 V, and a fill factor (FF) of 68%, which is
slightly lower than those of the PSCs with a spiro-MeOTAD/
DOI: 10.1021/acsenergylett.9b01294
ACS Energy Lett. 2019, 4, 2032−2039
ACS Energy Letters
Au electrode. The current density increased from 20.7 to 21.4
mA/cm2, which agrees well with the incident photon-to-
current conversion efficiency (IPCE) spectrum (Figure 2b).
However, the devices with the bare carbon electrodes showed a
lower IPCE in the wavelength range between 600 and 750 nm.
To reveal this phenomenon, we measured the absorption of
the perovskite and the reflection of the carbon electrode
(Figures S6 and S7). It is important to note that the black
carbon electrode barely reflects any light, while the absorption
of the perovskite layer is relatively weak in the wavelength
range between 600 and 750 nm. This is the reason why the
performance with the carbon electrode is slightly lower than
that of the PSCs with the spiro-MeOTAD/Au electrode.
We also investigated charge transport and extraction
dynamics in our PSCs by steady-state and time-resolved
photoluminescence (PL and TRPL) measurements (Figures 2c
and S8). With the carbon electrode employed, the PL intensity
decreased and the CuPc-modified carbon electrode exhibited
the lowest PL intensity, indicating more efficient charge
extraction capability from the perovskite film to the carbon
electrode after introducing the CuPc additive. The TRPL data
were fitted to a biexponential decay model, i.e., τ = A1τ1 + A2τ2,
where A1 and τ1 correspond to the shorter decay amplitude
and lifetime, respectively, associated with the processes of
charge transfer from the perovskite film to the electrode. A2
and τ2 are the longer decay amplitude and lifetime,
respectively, for the process of nonradiative decay in the
bulk perovskite film (Table S2).51 τ1 is shorter after
introducing CuPc additive, showing faster charge extraction
from MAPbI3 to the carbon electrode. On the basis of the
device performance data, J SC and FF increased after
introducing the CuPc additive, which is in good agreement
with the PL and TRPL data.
Besides the improved JSC and FF, Voc was also enhanced
after introducing the CuPc additive. To further elucidate the
underlying mechanism, we traced the WF changes of the
carbon electrode after introducing the CuPc additives by
employing ultraviolet photoemission spectroscopy (UPS), as
shown in Figure 2d (marked by the dashed line). Introduction
of CuPc leads to an increase of the WF from 4.03 to 4.22 eV.
Combined with the energy level diagrams (inset in Figure 2d),
we can estimate the relationship between the performance of
PSCs and the WF. Voc is mainly determined by the difference
between the hole quasi-Fermi level (Efp) and electron quasi-
Fermi level (Efn), in which Efp is determined by the interaction
of perovskite with a carbon electrode.52 As the WF is the
energy difference between the vacuum level (Evac) and Fermi
level (EF), when the WF of the carbon electrode increases, it
indicates a shift of the vacuum level away from the Fermi level,
i.e., a lower EF of the carbon electrode, resulting in a lower Efp
position and a higher Voc. In this case, after introduction of
CuPc into the bulk of the carbon electrode, the WF exhibited
an increase of about 0.2 eV, in agreement with the enhanced
Voc. The PSC with the CuPc-modified carbon electrode
exhibited stable behavior under a high temperature of 85 °C
and a low humidity of 5% over 200 h (Figure S9). On the
other hand, under high humidity, the performance decreased
to below 60% of the initial performance within 20 h, indicating
the necessity for suitable encapsulation.
To find out whether the additive effect is mainly related to
the interface or also has any influence on the bulk film, we did
control experiments in which a CuPc interlayer was evaporated
between the perovskite film and the carbon electrode. A
2036
Letter
schematic drawing showing the structure of the PSC with the
CuPc interlayer, i.e., FTO/compact TiO2/perovskite/CuPc
interlayer/carbon, is shown in Figure 3a. We first investigated
the influence of the CuPc film thickness on the performance of
PSCs (Figure S10). With the increasing thickness of the CuPc
interlayer, the performance first increased as the thickness of
the CuPc interlayer increased to 10 nm and then decreased as
the thickness of the CuPc interlayer further increased to 20
nm. As the thickness of the CuPc interlayer increased, hole
transport was improved, contributing to a higher FF. However,
due to the intrinsic low conductivity of CuPc, the series
resistance of the device also rose with the increasing thickness
of the undoped CuPc interlayer. We selected the best
performance of PSCs with the 10 nm thick CuPc interlayer
for comparison (Figure 3b). The J−V characteristics of the
best PSCs with two configurations of CuPc-modified carbon
electrode and a CuPc interlayer are summarized in Table 1.
The best device with the CuPc interlayer showed a lower value
for all photovoltaic parameters including a PCE of 12.8%, a Voc
of 0.95 V, a Jsc of 20.7 mA/cm2, and a FF of 65%, compared
with the best device with the CuPc-modified carbon electrode
(PCE of 14.8%, Voc of 1.02 V, Jsc of 21.4 mA/cm2, and FF of
68%). Also the hysteresis was larger with the CuPc interlayer.
This is possibly due to the low conductivity of pristine CuPc
that reduces charge transfer, while mixing of CuPc with carbon
could enhance the charge transport and reduce hysteresis. The
fact that the device with the CuPc-modified carbon electrode
shows better performance than that with the CuPc interlayer
between carbon and perovskite suggests that the additive CuPc
not only improves the charge transport in the interface
between the carbon electrode and perovskite as the role of
CuPc interlayer but also has an influence on the bulk
properties of the carbon electrode.
To further investigate the influence of CuPc additive on the
bulk property of the carbon electrode, we studied the
influences on the energy level position of the carbon electrode
using the two methods to introduce CuPc. We analyzed the
energy level alignment via UPS (Figure 3c) and the specific
variations of Cu species via XPS (Figures S11 and 12). The left
panel of UPS (Figure 3c) exhibits the photoemission
secondary electron cutoff from which one can extract the
WF, and the right panel corresponds to the occupied states
near the Fermi level from which one can extract the highest
occupied molecular orbital (HOMO) or valence band
maximum. For the bulk modified carbon, the WF increased
from 4.03 to 4.22 eV when the CuPc content increased to 1.0
wt % (Figure 3c). The corresponding EF shifted downward
away from EVAC. To evaluate energy level alignment, the
optical bandgap of CuPc was used to calculate the lowest
unoccupied molecular orbital (LUMO) value (Figure S13),
and here, we used the vacuum level alignment. Then we
obtained band diagrams with a CuPc bandgap value of 1.6 eV
(Figure 3d). When the CuPc content increased to 1.0 wt %,
the hole transport level (EHOMO) obviously increased to the
deepest with the highest WF (4.22 eV). To fully understand
the CuPc influence on energy level, we carried out in situ
evaporation of the CuPc interlayer on the surface of carbon
and UPS measurement in the same ultrahigh vacuum
environment. We tuned the thickness of the CuPc interlayer
in the range of 0−30 nm (Figure 3e,f). With the increasing
thickness, the HOMO shifted to higher binding energies with
an amount of about 1 eV in the range of 0−6 nm thickness.
However, the corresponding EF slightly shifted toward Evac
DOI: 10.1021/acsenergylett.9b01294
ACS Energy Lett. 2019, 4, 2032−2039
ACS Energy Letters
Figure 4. Scalable fabrication of the carbon-based PSC modules. (a,b) Schematic figure of the module structure. The corresponding optical
microscopic photo and detailed description about P1, P2, and P3 can be found in Figure S14. (c) J−V curve of the as-prepared PSC module
on a 5 cm × 5 cm FTO substrate with 22.4 cm2 designated area (Inset, photograph of solar module with the carbon electrode). (d)
Dependence of the PCE change of the PSC on a flexible substrate on the increasing bending cycle number (Inset, photograph of a solar
module in bending conditions).
(around 3.90 eV). Note that this behavior of EF changing is
different with the CuPc-modified carbon electrode where EF
shifts downward away from Evac (4.22 eV). The higher EF will
form an enhanced built-in electric field for holes. Moreover,
the HOMO edge of the CuPc-modified carbon electrode is
located closer to EF than the CuPc interlayer, reducing the
energy loss for extraction of holes. Therefore, the strategy of
applying CuPc into the carbon electrode is more effective than
an interlayer between the perovskite and electrode, resulting in
enhanced device performance.
With the full low-temperature process and low-cost carbon
electrode, the solar cell can be easily scaled up and even
fabricated on a flexible substrate to achieve the flexibility
(Figure 4a−d). We applied carbon paste in the fabrication of a
solar cell module using a 5 cm × 5 cm substrate. The
schematic illustration of the architecture is shown in Figure
4a,b. By carefully patterning the compact TiO2 layer, the
perovskite, and carbon the electrode in narrow stripes and
slightly shifting them with respect to one another (Figure S14),
a high geometric FF of 89.6% with a designated area of 22.4
cm2 was achieved (Figure 4c). The resulting uniform device
exhibited a PCE of 7.2% with a Voc of 6.4 V, Jsc of 2.37 mA/
cm2, and FF of 47.5% on a 5 cm × 5 cm FTO substrate.
Furthermore, with replacement of FTO glass with a flexible
conductive substrate, we demonstrate a flexible solar cell with a
carbon electrode generating a PCE of around 6%, which is on a
similar level as the efficiency of other reported flexible PCSs
based on evaporated CdS as the ETL and carbon as the
electrode (9.56%).39 The resultant solar cell can be bent
(Figures 4d and S15).
We show a method to engineer an efficient carbon-based
electrode by employing a low-cost small-molecule semi-
conductor of CuPc. Our planar PSCs with CuPc-modified
carbon as the counter electrode generated the highest PCE of
2037
Letter
14.8%, corresponding to ∼30% improvement in PCE when
compared to the bare carbon. Fundamental studies showed
that the improvement results from CuPc additive as both an
interface modifier and dopant, where the hole is transferred
with a better hole extraction ability from the perovskite to
electrode due to an enhanced built-in electrical field at the
perovskite/modified carbon interface. Our strategy offers a
new way to improve the performance of the PSC employing
carbon as the counter electrode. Furthermore, we fabricated
carbon electrode-based solar modules on glass and flexible
substrates, which demonstrated the capability of upscaling and
flexibility. This work paves the way for the development of
low-cost, stable, large-area, printable, and flexible PSCs.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsenergy-
lett.9b01294.
Experimental section, including methods and character-
ization (PDF)
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: Yabing.Qi@OIST.jp.
ORCID
Zonghao Liu: 0000-0003-4743-6971
Yabing Qi: 0000-0002-4876-8049
Present Address
⊥
E.J.J.-P.: ARAID, Government of Aragon, Institute of
Nanoscience of Aragon (INA), University of Zaragoza 50018
Zaragoza, Spain.
DOI: 10.1021/acsenergylett.9b01294
ACS Energy Lett. 2019, 4, 2032−2039
ACS Energy Letters
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
This work was supported by funding from the Energy
Materials and Surface Sciences Unit of the Okinawa Institute
of Science and Technology Graduate University, the OIST
Proof of Concept (POC) Program, the OIST R&D Cluster
Research Program, and JSPS KAKENHI Grant Number
JP18K05266 and Number 17K14551. We would like to
thank the OIST Mech. Eng. & Microfabrication Support
Section for maintenance of the cleanroom and sputtering
equipment.
■ REFERENCES
(1) Lee, M. M.; Teuscher, J.; Miyasaka, T.; Murakami, T. N.; Snaith,
H. J. Efficient hybrid solar cells based on meso-superstructured
organometal halide perovskites. Science 2012, 338, 643−647.
(2) Im, J.-H.; Jang, I.-H.; Pellet, N.; Grätzel, M.; Park, N.-G. Growth
of CH3NH3PbI3 cuboids with controlled size for high-efficiency
perovskite solar cells. Nat. Nanotechnol. 2014, 9, 927.
(3) Zhou, Y.; Zhu, K. Perovskite solar cells shine in the “valley of the
sun. ACS Energy Lett. 2016, 1, 64−67.
(4) Yang, M.; Zhou, Y.; Zeng, Y.; Jiang, C.-S.; Padture, N. P.; Zhu,
K. Square-centimeter solution-processed planar CH3NH3PbI3 perov-
skite solar cells with efficiency exceeding 15%. Adv. Mater. 2015, 27,
6363−6370.
(5) McGehee, M. D. Fast-track solar cells. Nature 2013, 501, 323−
325.
(6) Correa-Baena, J.-P.; Saliba, M.; Buonassisi, T.; Grätzel, M.;
Abate, A.; Tress, W.; Hagfeldt, A. Promises and challenges of
perovskite solar cells. Science 2017, 358, 739−744.
(7) Calabrò, E.; Matteocci, F.; Palma, A. L.; Vesce, L.; Taheri, B.;
Carlini, L.; Pis, I.; Nappini, S.; Dagar, J.; Battocchio, C.; Brown, T. M.;
Di Carlo, A. Low temperature, solution-processed perovskite solar
cells and modules with an aperture area efficiency of 11%. Sol. Energy
Mater. Sol. Cells 2018, 185, 136−144.
(8) You, J.; Meng, L.; Song, T.-B.; Guo, T.-F.; Yang, Y.; Chang, W.-
H.; Hong, Z.; Chen, H.; Zhou, H.; Chen, Q.; Liu, Y.; De Marco, N.;
Yang, Y. Improved air stability of perovskite solar cells via solution-
processed metal oxide transport layers. Nat. Nanotechnol. 2016, 11,
75−81.
(9) Zhou, H.; Chen, Q.; Li, G.; Luo, S.; Song, T.-b.; Duan, H.-S.;
Hong, Z.; You, J.; Liu, Y.; Yang, Y. Interface engineering of highly
efficient perovskite solar cells. Science 2014, 345, 542−546.
(10) Divitini, G.; Cacovich, S.; Matteocci, F.; Cinà, L.; Di Carlo, A.;
Ducati, C. In situ observation of heat-induced degradation of
perovskite solar cells. Nat. Energy 2016, 1, 15012.
(11) Kato, Y.; Ono, L. K.; Lee, M. V.; Wang, S.; Raga, S. R.; Qi, Y. B.
Silver iodide formation in methyl ammonium lead iodide perovskite
solar cells with silver top electrodes. Adv. Mater. Interfaces 2015, 2,
1500195.
(12) Malinauskas, T.; Tomkute-Luksiene, D.; Sens, R.; Daskeviciene,
M.; Send, R.; Wonneberger, H.; Jankauskas, V.; Bruder, I.; Getautis,
V. Enhancing thermal stability and lifetime of solid-state dye-
sensitized solar cells via molecular engineering of the hole-trans-
porting material spiro-OMeTAD. ACS Appl. Mater. Interfaces 2015, 7,
11107−11116.
(13) Juárez-Pérez, E. J.; Leyden, M. R.; Wang, S.; Ono, L. K.;
Hawash, Z.; Qi, Y. B. Role of the dopants on the morphological and
transport properties of spiro-meotad hole transport layer. Chem.
Mater. 2016, 28, 5702−5709.
(14) Domanski, K.; Correa-Baena, J.-P.; Mine, N.; Nazeeruddin, M.
K.; Abate, A.; Saliba, M.; Tress, W.; Hagfeldt, A.; Grätzel, M. Not All
That Glitters Is Gold: Metal-migration-induced degradation in
perovskite solar cells. ACS Nano 2016, 10, 6306−6314.
2038
Letter
(15) Guarnera, S.; Abate, A.; Zhang, W.; Foster, J. M.; Richardson,
G.; Petrozza, A.; Snaith, H. J. Improving the long-term stability of
perovskite solar cells with a porous Al2O3 buffer layer. J. Phys. Chem.
Lett. 2015, 6, 432−437.
(16) Chen, H.; Wei, Z.; He, H.; Zheng, X.; Wong, K. S.; Yang, S.
Solvent engineering boosts the efficiency of paintable carbon-based
perovskite solar cells to beyond 14%. Adv. Energy Mater. 2016, 6,
1502087.
(17) Mei, A.; Li, X.; Liu, L.; Ku, Z.; Liu, T.; Rong, Y.; Xu, M.; Hu,
M.; Chen, J.; Yang, Y.; Grätzel, M.; Han, H. A hole-conductor−free,
fully printable mesoscopic perovskite solar cell with high stability.
Science 2014, 345, 295−298.
(18) Xiang, S.; Fu, Z.; Li, W.; Wei, Y.; Liu, J.; Liu, H.; Zhu, L.;
Zhang, R.; Chen, H. Highly Air-stable carbon-based α-CsPbI3
perovskite solar cells with a broadened optical spectrum. ACS Energy
Lett. 2018, 3, 1824−1831.
(19) Luo, Q.; Ma, H.; Hou, Q.; Li, Y.; Ren, J.; Dai, X.; Yao, Z.;
Zhou, Y.; Xiang, L.; Du, H.; He, H.; Wang, N.; Jiang, K.; Lin, H.;
Zhang, H.; Guo, Z. All-carbon-electrode-based endurable flexible
perovskite solar cells. Adv. Funct. Mater. 2018, 28, 1706777.
(20) Tsai, C.-M.; Wu, H.-P.; Chang, S.-T.; Huang, C.-F.; Wang, C.-
H.; Narra, S.; Yang, Y.-W.; Wang, C.-L.; Hung, C.-H.; Diau, E. W.-G.
Role of tin chloride in tin-rich mixed-halide perovskites applied as
mesoscopic solar cells with a carbon counter electrode. ACS Energy
Lett. 2016, 1, 1086−1093.
(21) Zhou, H.; Shi, Y.; Dong, Q.; Zhang, H.; Xing, Y.; Wang, K.; Du,
Y.; Ma, T. Hole-conductor-free, metal-electrode-free TiO 2 /
CH3NH3PbI3 heterojunction solar cells based on a low-temperature
carbon electrode. J. Phys. Chem. Lett. 2014, 5, 3241−3246.
(22) Liu, Z.; Zhang, M.; Xu, X.; Bu, L.; Zhang, W.; Li, W.; Zhao, Z.;
Wang, M.; Cheng, Y.-B.; He, H. p-type mesoscopic NiO as an active
interfacial layer for carbon counter electrode based perovskite solar
cells. Dalton Transactions 2015, 44, 3967−3973.
(23) Cao, K.; Zuo, Z.; Cui, J.; Shen, Y.; Moehl, T.; Zakeeruddin, S.
M.; Grätzel, M.; Wang, M. Efficient screen printed perovskite solar
cells based on mesoscopic TiO2/Al2O3/NiO/carbon architecture.
Nano Energy 2015, 17, 171−179.
(24) Liu, L.; Mei, A.; Liu, T.; Jiang, P.; Sheng, Y.; Zhang, L.; Han, H.
Fully Printable mesoscopic perovskite solar cells with organic silane
self-assembled monolayer. J. Am. Chem. Soc. 2015, 137, 1790−1793.
(25) Liu, T.; Liu, L.; Hu, M.; Yang, Y.; Zhang, L.; Mei, A.; Han, H.
Critical parameters in TiO2/ZrO2/Carbon-based mesoscopic perov-
skite solar cell. J. Power Sources 2015, 293, 533−538.
(26) Yan, K.; Wei, Z.; Li, J.; Chen, H.; Yi, Y.; Zheng, X.; Long, X.;
Wang, Z.; Wang, J.; Xu, J.; Yang, S. High-performance graphene-based
hole conductor-free perovskite solar cells: schottky junction enhanced
hole extraction and electron blocking. Small 2015, 11, 2269−2274.
(27) Zhang, F.; Yang, X.; Cheng, M.; Wang, W.; Sun, L. Boosting
the efficiency and the stability of low cost perovskite solar cells by
using CuPc nanorods as hole transport material and carbon as counter
electrode. Nano Energy 2016, 20, 108−116.
(28) Zheng, X.; Chen, H.; Li, Q.; Yang, Y.; Wei, Z.; Bai, Y.; Qiu, Y.;
Zhou, D.; Wong, K. S.; Yang, S. Boron doping of multiwalled carbon
nanotubes significantly enhances hole extraction in carbon-based
perovskite solar cells. Nano Lett. 2017, 17, 2496−2505.
(29) Rong, Y.; Hou, X.; Hu, Y.; Mei, A.; Liu, L.; Wang, P.; Han, H.
Synergy of ammonium chloride and moisture on perovskite
crystallization for efficient printable mesoscopic solar cells. Nat.
Commun. 2017, 8, 14555.
(30) Priyadarshi, A.; Haur, L. J.; Murray, P.; Fu, D.; Kulkarni, S.;
Xing, G.; Sum, T. C.; Mathews, N.; Mhaisalkar, S. G. A large area (70
cm2) monolithic perovskite solar module with a high efficiency and
stability. Energy Environ. Sci. 2016, 9, 3687−3692.
(31) Grancini, G.; Roldán-Carmona, C.; Zimmermann, I.; Mosconi,
E.; Lee, X.; Martineau, D.; Narbey, S.; Oswald, F.; De Angelis, F.;
Graetzel, M.; Nazeeruddin, M. K. One-Year stable perovskite solar
cells by 2D/3D interface engineering. Nat. Commun. 2017, 8, 15684.
DOI: 10.1021/acsenergylett.9b01294
ACS Energy Lett. 2019, 4, 2032−2039
 ACS Energy Letters Letter

(32) Park, N.-G.; Grätzel, M.; Miyasaka, T.; Zhu, K.; Emery, K. (48) Biesinger, M. C.; Lau, L. W. M.; Gerson, A. R.; Smart, R. S. C.
Towards stable and commercially available perovskite solar cells. Resolving surface chemical states in XPS analysis of first row
Nature Energy 2016, 1, 16152. transition metals, oxides and hydroxides: Sc, Ti, V, Cu and Zn. Appl.
(33) De Rossi, F.; Baker, J. A.; Beynon, D.; Hooper, K. E. A.; Surf. Sci. 2010, 257, 887−898.
Meroni, S. M. P.; Williams, D.; Wei, Z.; Yasin, A.; Charbonneau, C.; (49) Ge, Q.-Q.; Shao, J.-Y.; Ding, J.; Deng, L.-Y.; Zhou, W.-K.;
Jewell, E. H.; Watson, T. M. All Printable Perovskite Solar Modules Chen, Y.-X.; Ma, J.-Y.; Wan, L.-J.; Yao, J.; Hu, J.-S.; Zhong, Y.-W. A
with 198 cm2 Active Area and Over 6% Efficiency. Adv. Mater. Two-dimensional hole-transporting material for high-performance
Technol. 2018, 3, 1800156. perovskite solar cells with 20% average efficiency. Angew. Chem., Int.
(34) Zhang, F.; Yang, X.; Wang, H.; Cheng, M.; Zhao, J.; Sun, L. Ed. 2018, 57, 10959−10965.
Structure engineering of hole−conductor free perovskite-based solar (50) Chen, S.; Goh, T. W.; Sabba, D.; Chua, J.; Mathews, N.; Huan,
cells with low-temperature-processed commercial carbon paste as C. H. A.; Sum, T. C. Energy level alignment at the methylammonium
cathode. ACS Appl. Mater. Interfaces 2014, 6, 16140−16146. lead iodide/copper phthalocyanine interface. APL Mater. 2014, 2,
(35) Zhou, H.; Shi, Y.; Wang, K.; Dong, Q.; Bai, X.; Xing, Y.; Du, Y.; 081512.
Ma, T. Low-temperature processed and carbon-based ZnO/ (51) Yu, H.; Yeom, H.-I.; Lee, J. W.; Lee, K.; Hwang, D.; Yun, J.;
CH3NH3PbI3/C planar heterojunction perovskite solar cells. J. Phys. Ryu, J.; Lee, J.; Bae, S.; Kim, S. K.; Jang, J. Superfast room-
Chem. C 2015, 119, 4600−4605. temperature activation of SnO2 thin films via atmospheric plasma
(36) Wei, Z.; Chen, H.; Yan, K.; Yang, S. Inkjet printing and instant oxidation and their spplication in planar perovskite photovoltaics. Adv.
chemical transformation of a CH3NH3PbI3/nanocarbon electrode and Mater. 2018, 30, 1704825.
interface for planar perovskite solar cells. Angew. Chem., Int. Ed. 2014, (52) Caprioglio, P.; Zu, F.; Wolff, C. M.; Márquez Prieto, J. A.;
Stolterfoht, M.; Becker, P.; Koch, N.; Unold, T.; Rech, B.; Albrecht,
53, 13239−13243.
S.; Neher, D. High open circuit voltages in pin-type perovskite solar
(37) Anaraki, E. H.; Kermanpur, A.; Steier, L.; Domanski, K.;
cells through strontium addition. Sustain. Energy Fuels 2019, 3, 550−
Matsui, T.; Tress, W.; Saliba, M.; Abate, A.; Grätzel, M.; Hagfeldt, A.;
563.
Correa-Baena, J.-P. Highly efficient and stable planar perovskite solar
cells by solution-processed tin oxide. Energy Environ. Sci. 2016, 9,
3128−3134.
(38) Qiu, L.; Liu, Z.; Ono, L. K.; Jiang, Y.; Son, D.-Y.; Hawash, Z.;
He, S.; Qi, Y. B. Scalable Fabrication of Stable High Efficiency
Perovskite Solar Cells and Modules Utilizing Room Temperature
Sputtered SnO2 Electron Transport Layer. Adv. Funct. Mater. 2018,
29, 1806779.
(39) Lee, Y.; Lee, S.; Seo, G.; Paek, S.; Cho, K. T.; Huckaba, A. J.;
Calizzi, M.; Choi, D.; Park, J.-S.; Lee, D.; Lee, H. J.; Asiri, A. M.;
Nazeeruddin, M. K. Efficient Planar Perovskite Solar Cells Using
Passivated Tin Oxide as an Electron Transport Layer. Adv. Sci. 2018,
5, 1800130.
(40) Liu, Z.; Liu, X.; Sun, B.; Tan, X.; Ye, H.; Tu, Y.; Tu, Y.; Shi, T.;
Tang, Z.; Liao, G. Fully low-temperature processed carbon-based
perovskite solar cells using thermally evaporated cadmium sulfide as
efficient electron transport layer. Org. Electron. 2019, 74, 152−160.
(41) Ye, H.; Liu, Z.; Liu, X.; Sun, B.; Tan, X.; Tu, Y.; Shi, T.; Tang,
Z.; Liao, G. 17.78% efficient low-temperature carbon-based planar
perovskite solar cells using Zn-doped SnO2 electron transport layer.
Appl. Surf. Sci. 2019, 478, 417−425.
(42) Liu, Z.; Sun, B.; Liu, X.; Han, J.; Ye, H.; Tu, Y.; Chen, C.; Shi,
T.; Tang, Z.; Liao, G. 15% efficient carbon based planar-
heterojunction perovskite solar cells using a TiO2/SnO2 bilayer as
the electron transport layer. J. Mater. Chem. A 2018, 6, 7409−7419.
(43) Chen, H.; Yang, S. Carbon-based perovskite solar cells without
hole transport materials: the front runner to the market? Adv. Mater.
2017, 29, 1603994.
(44) Jiang, P.; Xiong, Y.; Xu, M.; Mei, A.; Sheng, Y.; Hong, L.; Jones,
T. W.; Wilson, G. J.; Xiong, S.; Li, D.; Hu, Y.; Rong, Y.; Han, H. The
influence of the work function of hybrid carbon electrodes on
printable mesoscopic perovskite solar cells. J. Phys. Chem. C 2018,
122, 16481−16487.
(45) Seo, J.; Jeon, N. J.; Yang, W. S.; Shin, H.-W.; Ahn, T. K.; Lee, J.;
Noh, J. H.; Seok, S. I. Effective electron blocking of CuPc-doped
spiro-OMeTAD for highly efficient inorganic−organic hybrid perov-
skite solar cells. Adv. Energy Mater. 2015, 5, 1501320.
(46) Yang, G.; Wang, Y.-L.; Xu, J.-J.; Lei, H.-W.; Chen, C.; Shan, H.-
Q.; Liu, X.-Y.; Xu, Z.-X.; Fang, G.-J. A facile molecularly engineered
copper (II) phthalocyanine as hole transport material for planar
perovskite solar cells with enhanced performance and stability. Nano
Energy 2017, 31, 322−330.
(47) Son, D.-Y.; Kim, S.-G.; Seo, J.-Y.; Lee, S.-H.; Shin, H.; Lee, D.;
Park, N.-G. Universal Approach toward Hysteresis-free perovskite
solar cell via defect engineering. J. Am. Chem. Soc. 2018, 140, 1358−
1364.

2039 DOI: 10.1021/acsenergylett.9b01294

ACS Energy Lett. 2019, 4, 2032−2039

View publication stats