Article

Cite This: ACS Appl. Energy Mater. 2019, 2, 6195−6199 www.acsaem.org

Perovskite Solar Cells: 18% Efficiency Using Zn(II) and Cu(II)

Octakis(diarylamine)phthalocyanines as Hole-Transporting
Materials
Kyung Taek Cho,† Marco Cavazzini,‡ Kasparas Rakstys,† Simonetta Orlandi,‡ Sanghyun Paek,†
Marius Franckevičius,§ Hiroyuki Kanda,† Rokas Gegevičius,§ Queloz Valentin Emmanuel,†
Gianluca Pozzi,*,‡ and Mohammad Khaja Nazeeruddin*,†
†
Group for Molecular Engineering of Functional Materials, Institute of Chemical Sciences and Engineering, É cole Polytechnique
Fédérale de Lausanne, Valais Wallis, Rue de l’Industrie 17, 1950 Sion, Switzerland
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‡
Institute of Molecular Science and Technologies (ISTM-CNR), Via Golgi 19, 20133 Milano, Italy
§
Center for Physical Sciences and Technology, Savanorių Aveniu 231, LT-02300 Vilnius, Lithuania
Downloaded via UNIV OF NEW ENGLAND on October 22, 2019 at 21:30:49 (UTC).

*
S Supporting Information

ABSTRACT: Metallophthalocyanines (MPcs) are currently

emerging as alternative hole-transporting materials (HTMs) in
perovskite solar cells (PSCs). However, the lack of systematic
structure/photovoltaic properties investigations still hampers the
rational design of MPcs that might act as efficient HTMs for PSCs.
We designed and tested a series of symmetric MPcs (M = Zn(II)
or Cu(II)) bearing eight diarylamino substituents of diverse type
connected at the peripheral positions of the ligand through N−C
bonds. The new MPcs were used as HTMs in solution-processed
PSCs. The nature of the diarylamino substituents was found to play
a major role in determining the photovoltaic parameters of the
device. Comparison of devices fabricated using ZnPcs and their Cu
analogs evidenced that the nature of the core metal cation has a
more elusive influence. The highest power conversion efficiency of
18.10% was obtained using a ZnPcs bearing eight bis(p-butoxyphenyl)amino substituents.
KEYWORDS: metallophthalocyanines, hole-transporting materials, perovskite solar cells,
ZnPcs bearing eight bis(p-butoxyphenyl)amino substituents, octakis(diarylamine)phthalocyanines

he photovoltaic field is dominated at present by silicon-

T based solar cells. However, extensive research efforts are
directed toward development of cheaper, more easily
implemented technologies among which perovskite solar cells
(PSCs) hold much promise.1−4 Impressive progress has been
made in terms of perovskite composition, device architecture,
optical management, and manufacturing processes since the
first report of PSCs appeared less than 10 years ago.5 At the
same time, the design and optimization of hole-transporting
materials (HTMs), which were early identified as key
components of PSCs,6,7 remain crucial for the development
of highly efficient and stable devices.8−10 Despite all efforts,
spiro-OMeTAD (2,2′,7,7′-tetrakis(N,N-di-p-methoxyphenyl-
amine)-9,9′-spirobifluorene) is still the benchmark HTM in
PSCs studies, despite some well-known drawbacks (high cost,
low intrinsic hole mobility and conductivity, and lack of
stability) that clearly limit its potential in large scale
applications.8−10 Transition metal complexes of metalloph-
thalocyanines (MPcs) are currently emerging as viable HTMs
that could avoid the shortcomings of spiro-OMeTAD, thanks
to their superior thermal and chemical stability, ready synthetic
access, and outstanding semiconducting behavior in the solid
state.11−26 Moreover, the optoelectronic and solubility proper-
ties of MPcs can be tuned by introducing suitable substituents
in the peripheral (or nonperipheral) positions of the
phthalocyanine ligand, which can host a variety of metal
cations. These structural modifications allow one to improve
the processability of MPcs and have a great influence on the
final device performance. For instance, PSCs containing a layer
of Cu(II) complex of unsubstituted phthalocyanine (Pc) as
HTM were fabricated by vacuum thermal evaporation of the
complex, affording PCEs ranging from 5.0 to 15.4%.12,13
Because thermal procedures can be tricky and can destroy the
underlying perovskite layer, more soluble CuPcs bearing
lipophilic substituents that can be deposited as films via spin-
coating on top of the perovskite material have been
developed.14−18 Best results were obtained in the case of
Received: March 26, 2019
Accepted: August 14, 2019
Published: August 14, 2019

© 2019 American Chemical Society 6195 DOI: 10.1021/acsaem.9b00637

ACS Appl. Energy Mater. 2019, 2, 6195−6199
ACS Applied Energy Materials
solution-processed PSCs based on the Cu(II) complex of a Pc
bearing one peripheral tert-butyl group on each of the four
isoindole subunits which displayed an average PCE of 17.5%,
with a high PCE of 18.8% by a reverse J−V scan.17 The nature
of the core metal cation is known to affect the optoelectronic
properties of MPcs.11 Transition metal derivatives of Pcs other
than Cu(II) complexes have been thus investigated as HTM in
PSCs in the attempt to improve device performance.18−26
Promising results have been obtained in the case of solution-
processable Zn(II) derivatives of Pcs functionalized with
electron donating substituents.21−25 Unfortunately, these
studies are usually focused on a single compound, with no
direct comparison among different candidates. This compli-
cates the assessment of the real impact of the modifications
introduced in the MPc structure. In one of the few exceptions
to this trend, we have recently shown that the introduction of
proper aromatic secondary amines at four peripheral positions
of the Pc ring can have positive effects on the efficiency of
PSCs based on ZnPcs.23 This prompted us to study the
behavior of the corresponding octasubstituted derivatives
(Figure 1) and to extend the investigation to their Cu(II)
analogs.
Figure 1. Molecular structures of diarylamino octasubstituted MPcs.
Figure 2. (a) Cross-sectional SEM image of perovskite solar cell (BL50 as HTM). (b) J−V curves of perovskite solar cells using the new MPcs as
HTMs. The curves were recorded by scanning at 5 mV/s from backward scan.
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Despite the huge amount of Pc derivatives reported in the
literature, octasubstituted MPcs with eight secondary aromatic
amines bound to the peripheral positions of the macrocycle by
C−N bonds remain virtually unknown, with the exception of
two recently reported zinc octa(carbazolyl) derivatives.27 We
found that ZnPcs BL25, BL38, BL40, and BL51 (Figure 1) can
be readily obtained in yields ranging from 22% (BL38) to 62%
(BL50) by metal-templated cyclotetramerization of the
appropriate 4,5-disubstituted phthalonitrile precursor (see the
Supporting Information). The phthalonitrile precursors of
ZnPcs BL51 and BL40 were also used to prepare the
corresponding CuPcs BL50 and BL52 (Figure 1), which
were obtained in 62 and 52% yields, respectively. This allowed
the comparison of PSCs based on Zn(II) and Cu(II)
complexes of the same Pc ligand in order to reveal the effects
of the central metal cation.
The new complexes exhibit the distinctive UV−vis
absorption spectra of MPcs (Figure S1, Supporting Informa-
tion), featuring an intense band in the near UV region (B
band) and an even more intense band in the vis region (Q
band) assigned to the π → π* transition (a1u → eg*) from
HOMO to LUMO of the Pc ring.27 The energy required for
this transition is lower with respect to other peripherally
substituted Cu- and ZnPc tested so far as solution-processable
HTMs in PSCs,14−18,22−26 as shown by comparison of the
wavelengths of absorption maxima. In addition, broad bands of
low intensity are observed in the 400−600 nm region which
are lacking in the above-mentioned examples. These bands are
characteristic of MPcs with aromatic secondary amine
substituents and were first observed in tetra- and trisubstituted
ZnPcs,23,28 after having been predicted by computational
models.29 They have been recently assigned to low-energy
amine to phthalocyanine charge-transfer transitions.27 Bath-
ochromic effects in the order of >+20 nm are observed for the
Q band of the octasubstituted ZnPcs in comparison with their
tetrasubstituted analogs. As an example, in THF solution the
absorption maximum of BL25 is centered at 725 nm, whereas
the corresponding tetrasubstituted complex absorbs at 693
nm.23 The presence of electron donating p-alkoxy groups in
the structure of diarylamine substituents also influences the
energy of the π → π* transition responsible for the Q band, as
shown by the red-shifted absorptions of BL51 (756 nm) and
BL40 (758 nm) with respect to BL38 (743 nm). A non-
negligible red shift of the absorption maxima is also triggered
by changing the coordinated metal cation from Zn(II) to
DOI: 10.1021/acsaem.9b00637
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ACS Applied Energy Materials
Cu(II). Thus, CuPcs BL52 and BL50 show absorption maxima
at 763 and 766 nm, respectively.
To compare the energy levels of new HTMs, we performed
cyclic voltammetry (CV) measurements in DCM solution in
the presence of 0.1 M n-Bu4NPF6 (Figure S2). The
experimental HOMO energy levels were thus derived from
the ground-state oxidation potentials ES+/S. Dimethoxycarba-
zole-substituted ZnPc BL25 has a significantly more stabilized
HOMO level of −5.23 eV vs vacuum compared with that of
stronger diphenylamine donor-substituted BL38 (−5.05 eV)
and bis(p-methoxyphenyl)amino-substituted BL51 (−4.92
eV), respectively. Comparing the latter with BL40 having p-
butoxy groups in diphenylamine donors, an almost identical
value (−4.90 eV) was obtained showing that the length of the
alkoxy chains do not considerably influence the electro-
chemical properties. The same holds true for CuPcs BL50 and
BL52. However, compared to their ZnPCs analogs BL40 and
BL51, Cu complexes BL50 and BL52 have around 200 mV
deeper HOMO levels leading to the very suitable values of
−5.09 and −5.10 eV, respectively. All MPcs show enough
potential gaps for leading to efficient charge extraction from
the triple cation perovskite Cs0.1FA0.74MA0.13PbI2.48Br0.39
(Figure S3).
To test whether the synthesized MPcs could actually act as
HTMs in PSCs, we fabricated devices of the configuration
FTO/TiO2/Cs0.1FA0.74MA0.13PbI2.48Br0.39/HTM/Au, as exem-
plified in Figure 2a. For the electron tranporting layer, a TiO2-
blocking layer was coated on FTO and the SnCl4 was treated
on the TiO2 layer additionally. The perovskite thin film was
deposited by dropping chlorobenzene during spin-coating the
perovskite procedure on TiO2. This process was uniformly
applied across devices featuring the various HTMs tested.
Finally, the different MPcs were spin-coated on the top of
perovskite film to give ≈200 nm thick HTM layers. As shown
in the Supporting Information (Figure S5), all devices looked
similar, each single layer having the same morphology and
thickness. Moreover, the top view scanning electron micros-
copy (SEM) images of the perovskite films revealed stark
differences between before and after HTMs coating (Figure
S13a−g). The pristine perovskite film deposited on top of the
ETL layer showed a compact, pinhole free, and large grains
having distinct grain boundaries like a rock wall in Figure
S13a). Among all devices, the perovskite layer was uniformly
covered by a different layer of amorphous HTM except for
BL25 and BL38. We expected the devices using BL25 and
BL38 to have low efficiency due to low solubility or higher
crystallinity.
The best photovoltaics performances of these solar cells
recorded under standard AM1.5G illumination are displayed in
current density−voltage (J−V) curves (Figure 2b), while the
detailed parameters are summarized in Table 1. Cells
fabricated using spiro-OMeTAD were used as the reference.
Statistical analysis of devices (Figure S6) demonstrated the
reproducibility of the photovoltaics performances.
The octasubsituted MPcs afforded short-circuit current
densities (JSC) comparable to that of spiro-OMeTAD.
However, BL25 and BL38 exhibited low open-circuit voltages
(VOC) and fill factors, leading to worst performances with
respect to the other MPcs. This can be attributed to a lower
conductivity for the hole-transporting layer, leading to a higher
recombination at the interface perovskite/HTM (see below).
On the other hand, PSCs fabricated with BL40, BL50, BL51,
and BL52 showed fair fill factors and high VOC, above 1.05 eV.
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Table 1. Summary of the Highest Photovoltaic
Characteristics Extracted from J−V Curves of Perovskite
Solar Cells Employing Diarylamino Octasubstituted MPCs
as HTMs
HTM Voc (V) Jsc (mA cm−2) FF (%) PCE (%)
BL25 0.69 20.07 0.357 4.93
BL38 0.89 21.46 0.568 10.89
BL40 1.07 22.92 0.735 18.10
BL50 1.06 22.52 0.742 17.81
BL51 1.04 22.58 0.694 16.25
BL52 1.04 22.54 0.703 16.46
spiro-OMeTAD 1.10 23.1 0.755 19.25
As a consequence, the observed PCEs were beyond 16% and
the best efficiency, obtained using BL 40 as HTM, attained
18.10%. Interestingly, BL40, BL50, BL51, and BL52 share a
bis[(p-alkoxyphenyl)amino] octasubstitution pattern. In addi-
tion, ZnPc BL 40 (PCE = 18.10%) showed slightly better
performance than its CuPc analog BL 50 (PCE = 17.81%),
while the opposite holds for the ZnPc BL51 (PCE = 16.25%)
and the corresponding CuPc BL52 (PCE = 16.46%). On the
basis of previous literature reports, one would have expected a
well-defined efficiency improvement for the cells fabricated
with CuPcs with respect to those featuring the corresponding
ZnPcs derivatives.17,18 The present PV data thus underline the
subtle influence of chemical modifications of the Pc ligand on
the final optoelectronic properties of MPcs when applied in
PSCs. Indeed, in this series of octasubstituted MPcs the overall
performances strongly vary with the nature of the diarylamino
substituents, rather than with the nature of the core cation.
The external quantum efficiencies (EQEs) of the devices on
J−V curves were also measured (Figure S7). As clearly
observed, the EQEs for devices based on BL40, BL50, BL51,
and BL52 are fully comparable, in agreement with the
similarity of JSC measured in J−V curves. At high-energy
wavelengths, these EQEs are close to the EQE (∼90%)
obtained with a device fabricated with spiro-OMeTAD, while
they decrease at wavelengths longer than 600 nm. This
behavior can be associated with the strong light absorption of
MPcs in the range from 650 to 850 nm, as shown by UV−vis
absorption spectra (Figure S1). In addition, these MPcs exhibit
reduced hysteresis in J−V curves between forward and reverse
scan at the same rate of 0.05 V·s−1 (Figure S8).
To get further insight into the interfacial hole-transfer
processes promoted by the new MPcs in PSCs, we first
measured photoluminescence decay kinetics of the perovskite
films deposited on glass with the 470 nm excitation light from
the interface at perovskite and HTM layers (Figure S10). The
PL decay kinetics of the perovskite films with HTMs were fit to
multiexponential functions with the fitting parameters listed in
Table S1, whereas the decay of perovskite without HTM was
approximated with a double exponential function. The pristine
perovskite showed the initial fast ∼30 ns and slow 600 ns PL
decay components accounting for the trap filling and low
Shockley−Read−Hall recombination rate, respectively.30 The
obtained long-lived PL decay of pure perovskite films implies a
high material quality with a low defects concentration and long
charge carrier diffusion lengths. Apparent photoluminescence
quenching and acceleration of the PL relaxation were observed
when the perovskite films were covered with a hole-
transporting materials. The possible mechanism leading to
such acceleration of the PL kinetics traces can be associated
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ACS Applied Energy Materials
with an efficient hole transfer from the perovskite to HTM
with τ1 lasting for several nanoseconds. Among all HTMs, the
PL quenching (see Figure S9) was found to be high for all
HTMs, except the BL25 and BL38 being in good agreement
with PCE of the devices. It is worth noting that the additional
very fast process, which occurs in the sub-nanosecond time
scale (comparable with the temporal resolution of our
instrument), was also observed in perovskite films containing
BL25 and BL38 HTMs (Figure S10). The amplitude of this
component is 10-fold larger than the other undergoing
processes. Considering that the fast PL decay component
could be assigned to hole extraction as well as possible charge
carrier recombination at the interface, it should be assumed
that the initial fast relaxation observed in devices holding
HTMs is associated with large nonradiative surface recombi-
nation, rather than with efficient carrier extraction from
perovskite. This also well-correlates with low performance of
the devices (with BL25 and BL38) (see Table 1), especially
low open-circuit voltage and fill factor, being caused by
nonradiative recombination and series resistance problems also
causing inefficient hole transfer at the interface.
To gain additional more in-depth insight about the hole
extraction properties in complete perovskite solar cells
employing different HTMs we performed electric field
dependent time-resolved photoluminescence experiments.
Taking into the account that the contact between perovskite
and TiO2 is identical in all solar cells, the dependence of the
PL relaxation on the electric field will be mainly determined by
the interface quality between perovskite and HTMs. Panels a−
g of Figure S11 show the PL relaxation kinetics of the
perovskite solar cells covered with different HTM materials
measured using time correlated single photon counting
(TCSPC) under the applied reverse bias voltages ranging
from 0 to 2.5 V. The PL relaxation kinetics as a function of the
applied electric field showed a slight difference between
devices. From voltage dependent PL decay kinetics we
observed that the solar cell devices with inserted BL40,
BL50, BL51, BL52, and spiro-OMeTAD showed very small or
even no field dependence, whereas the most field-sensitive
devices were those containing BL25 and BL38 HTMs. The
built-in electric field present in perovskite solar cells is the
main driving force affecting the charge carrier transport and
their extraction at the interfaces. Thus, for the successful
extraction of photogenerated holes, when the charge-selective
materials have good contact with perovskite, the application of
an external electric field is not required. This case is well-
reflected for the devices with HTMs that showed decent
performances, whereas BL25 and BL38 HTMs exhibited very
poor current−voltage characteristics, especially low open-
circuit voltage suggesting strong carrier recombination.
We have also investigated photocurrent kinetics upon
photoexcitation of the device with short nanosecond laser
pulses. Figure S12 shows transient photocurrent for working
perovskite solar cells with the different hole-transporting layers
measured under pulsed laser illumination. Photocurrent
kinetics shows two major components: fast, several nano-
second long increase and slow, microsecond scale extraction
component. As already demonstrated from photolumines-
cence, the faster the hole extraction is into the hole-
transporting layer, the more pronounced the fast rising
component also appears in photocurrent kinetics. The solar
cell with classical spiro-OMeTAD hole-transporting layer
shows a fast, several nanoseconds long growing component.
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From our perspective, this is the time required for holes to be
completely injected into the transporting layer, and after that,
there is a steady extraction of charge carriers which lasts several
microseconds. Other devices with comparable PCE such as
spiro-OMeTAD show similar behavior. BL40, BL50, and BL51
all have a fast, several nanoseconds long rising component,
which means that holes are effectively injected into the hole-
transporting layer without any losses. On the other hand
photocurrent kinetics of BL25 and BL38 devices with much
lower PCE shows different behavior. The rising component is
now on a microsecond time scale and with lower amplitude,
meaning that holes have an injection barrier in the transporting
material as this is clearly seen from device performance
parameters results.
In conclusion, the nature of the diarylamino substituents
plays a major role in determining the photovoltaic parameters
of devices based on diarylamino octasubstituted MPcs as
HTMs. Thus, MPcs bearing bis(p-alkoxyphenyl)amino sub-
stituents outperform their 9H-carbazol-9-yl and diphenylamino
analogs, and excellent PCEs up to 18.10% have been observed
in the case of a ZnPc bearing eight bis(p-butoxyphenyl)amino
substituents. The clear influence of the nature of the bound
metal cation on the optoelectronic characteristics of the new
diarylamino octasubstituted MPcs has been also highlighted. In
particular, in the present set of compounds the HOMO energy
levels of CuPcs are better matched with the work function of
the triple cation perovskite Cs0.1FA0.74MA0.13PbI2.48Br0.39 than
those of ZnPcs. However, this does not entail better
photovoltaic performances, as evidenced by direct comparison
of devices fabricated using octasubstituted CuPcs and their Zn
analogs. The trends shown in this work suggest that further
developments of MPcs as HTMs in PSCs can only be achieved
by systematic investigations involving different substitution
patterns.
■
*
ASSOCIATED CONTENT
S Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acsaem.9b00637.
Experimental details (synthesis of MPcs and devices
fabrication), UV−vis spectra, cyclic voltammograms,
cross-sectional SEM images, cells statistics, EQE spectra,
forward and reverse scan current−voltage curves, and PL
spectra (PDF)
■
AUTHOR INFORMATION
Corresponding Authors
*(G.P) E-mail: gianluca.pozzi@istm.cnr.it.
*(M.K.N.) E-mail: mdkhaja.nazeeruddin@epfl.ch.
ORCID
Simonetta Orlandi: 0000-0001-6783-4243
Sanghyun Paek: 0000-0002-2671-2909
Marius Franckevičius: 0000-0001-8020-7201
Mohammad Khaja Nazeeruddin: 0000-0001-5955-4786
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
M.C., S.O., and G.P. thank the CNR/Regione Lombardia
project “Integrated Zero Emission Buildings” for financial
support. We acknowledge the SNSF NRP 70 project, no.
DOI: 10.1021/acsaem.9b00637
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ACS Applied Energy Materials
407040_154056, and CTI 25590.1 PFNM-NM, Solaronix,
Aubonne, Switzerland. We thank Borun New Material
Technology for providing high quality spiro-OMeTAD
■
REFERENCES
(1) Seok, S. I.; Grätzel, M.; Park, N.-G. Methodologies toward
Highly Efficient Perovskite Solar Cells. Small 2018, 14, 1704177.
(2) Saliba, M.; Correa-Baena, J.-P.; Grätzel, M.; Hagfeldt, A.; Abate,
A. Perovskite Solar Cells: from the Atomic Level to Film Quality and
Device Performance. Angew. Chem., Int. Ed. 2018, 57, 2554−2569.
(3) Berry, J. J.; van de Lagemaat, J.; Al-Jassim, M. M.; Kurtz, S.; Yan,
Y.; Zhu, K. Perovskite Photovoltaics: the Path to a Printable Terawatt-
Scale Technology. ACS Energy Lett. 2017, 2, 2540−2544.
(4) Gao, P.; Grätzel, M.; Nazeeruddin, M. K. Organohalide Lead
Perovskites for Photovoltaic Applications. Energy Environ. Sci. 2014, 7,
2448−2463.
(5) Kojima, A.; Teshima, K.; Shirai, Y.; Miyasaka, T. Organometal
Halide Perovskites as Visible-Light Sensitizers for Photovoltaic Cells.
J. Am. Chem. Soc. 2009, 131, 6050−6051.
(6) Kim, H.-S.; Lee, C.-R.; Im, J.-H.; Lee, K.-B.; Moehl, T.;
Marchioro, A.; Moon, S.-J.; Humphry-Baker, R.; Yum, J.-H.; Moser, J.
E.; Grätzel, M.; Park, N.-G. Lead Iodide Perovskite Sensitized All-
Solid-State Submicron Thin Film Mesoscopic Solar Cell with
Efficiency Exceeding 9%. Sci. Rep. 2012, 2, 591.
(7) 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.
(8) Krishna, A.; Grimsdale, A. C. Hole Transporting Materials for
Mesoscopic Perovskite Solar Cells − Towards A Rational Design? J.
Mater. Chem. A 2017, 5, 16446−16466.
(9) Rodríguez-Seco, C.; Cabau, L.; Vidal-Ferran, A.; Palomares, E.
Advances in the Synthesis of Small Molecules as Hole Transport
Materials for Lead Halide Perovskite Solar Cells. Acc. Chem. Res.
2018, 51, 869−880.
(10) Urieta-Mora, J.; García-Benito, I.; Molina-Ontoria, A.; Martín,
N. Hole Transporting Materials for Perovskite Solar Cells: a Chemical
Approach. Chem. Soc. Rev. 2018, 47, 8541−8571.
(11) Claessens, C. G.; Hahn, U.; Torres, T. Phthalocyanines: from
Outstanding Electronic Properties to Emerging Applications. Chem.
Rec. 2008, 8, 75−97.
(12) Kumar, C. V.; Sfyri, G.; Raptis, D.; Stathatos, E.; Lianos, P.
Perovskite Solar Cell with Low Cost Cu-Phthalocyanine as Hole
Transporting Material. RSC Adv. 2015, 5, 3786−3791.
(13) Ke, W.; Zhao, D.; Grice, C. R.; Cimaroli, A. J.; Fang, G.; Yan, Y.
Efficient Fully-Vacuum-Processed Perovskite Solar Cells Using
Copper Phthalocyanine as Hole Selective Layers. J. Mater. Chem. A
2015, 3, 23888−23894.
(14) Sfyri, G.; Chen, Q.; Lin, Y.-W.; Wang, Y.-L.; Nouri, E.; Xu, Z.-
X.; Lianos, P. Soluble Butyl Substituted Copper Phthalocyanine as
Alternative Hole-Transporting Material for Solution Processed
Perovskite Solar Cells. Electrochim. Acta 2016, 212, 929−933.
(15) Jiang, X.; Yu, Z.; Li, H.-B.; Zhao, Y.; Qu, J.; Lai, J.; Ma, W.;
Wang, D.; Yang, X.; Sun, L. A Solution-Processable Copper(II)
Phthalocyanine Derivative as a Dopant-Free Hole-Transporting
Material for Efficient and Stable Carbon Counter Electrode-Based
Perovskite Solar Cells. J. Mater. Chem. A 2017, 5, 17862−17866.
(16) Jiang, X.; Yu, Z.; Lai, J.; Zhang, Y.; Hu, M.; Lei, N.; Wang, D.;
Yang, X.; Sun, L. Interfacial Engineering of Perovskite Solar Cells by
Employing a Hydrophobic Copper Phthalocyanine Derivative as
Hole-Transporting Material with Improved Performance and
Stability. ChemSusChem 2017, 10, 1838−1845.
(17) Kim, Y. C.; Yang, T.-Y.; Jeon, N. J.; Im, J.; Jang, S.; Shin, T. J.;
Shin, H.-W.; Kim, S.; Lee, E.; Kim, S.; Noh, J. H.; Seok, S. I.; Seo, J.
Engineering Interface Structures between Lead Halide Perovskite and
Copper Phthalocyanine for Efficient and Stable Perovskite Solar Cells.
Energy Environ. Sci. 2017, 10, 2109−2116.
(18) Calió, L.; Follana-Berná, J.; Kazim, S.; Madsen, M.; Rubahn,
H.-G.; Sastre-Santos, A.; Ahmad, S. Cu(II) and Zn(II) Based
6199
Article
Phthalocyanines as Hole Selective Layers for Perovskite Solar Cells.
Sustainable Energy Fuels 2017, 1, 2071−2077.
(19) Wang, Y.; Zheng, X.; Liu, X.; Feng, Y.; Shan, H.; Dong, L.;
Fang, G.; Xu, Z.-X. A Study of Different Central Metals in
Octamethyl-Substituted Phthalocyanines as Dopant-Free Hole-Trans-
port Layers for Planar Perovskite Solar Cells. Org. Electron. 2018, 56,
276−283.
(20) Zheng, X.; Wang, Y.; Hu, J.; Yang, G.; Guo, Z.; Xia, J.; Xu, Z.;
Fang, G. Octamethyl-Substituted Pd(II) Phthalocyanine with Long
Carrier Lifetime as a Dopant-Free Hole Selective Material for
Performance Enhancement of Perovskite Solar Cells. J. Mater. Chem.
A 2017, 5, 24416−24424.
(21) Cheng, M.; Li, Y.; Safdari, M.; Chen, C.; Liu, P.; Kloo, L.; Sun,
L. Efficient Perovskite Solar Cells Based on a Solution Processable
Nickel(II) Phthalocyanine and Vanadium Oxide Integrated Hole
Transport Layer. Adv. Energy Mater. 2017, 7, 1602556.
(22) Javier Ramos, F.; Ince, M.; Urbani, M.; Abate, A.; Grätzel, M.;
Ahmad, S.; Torres, T.; Nazeeruddin, M. K. Non-Aggregated Zn(II)
Octa(2,6-diphenylphenoxy) Phthalocyanine as a Hole Transporting
Material for Efficient Perovskite Solar Cells. Dalton Trans 2015, 44,
10847−10851.
(23) Cho, K. T.; Rakstys, K.; Cavazzini, M.; Orlandi, S.; Pozzi, G.;
Nazeeruddin, M. K. Perovskite Solar Cells Employing Molecularly
Engineered Zn(II) Phthalocyanines as Hole-Transporting Materials.
Nano Energy 2016, 30, 853−857.
(24) Gao, P.; Cho, K. T.; Abate, A.; Grancini, G.; Reddy, P. Y.;
Srivasu, M.; Adachi, M.; Suzuki, A.; Tsuchimoto, K.; Grätzel, M.;
Nazeeruddin, M. K. An Efficient Perovskite Solar Cell with
Symmetrical Zn(II) Phthalocyanine Infiltrated Buffering Porous
Al2O3 as the Hybrid Interfacial Hole-Transporting Layer. Phys.
Chem. Chem. Phys. 2016, 18, 27083−27089.
(25) Nouri, E.; Krishna, J. V. S.; Kumar, C. V.; Dracopoulos, V.;
Giribabu, L.; Mohammadi, M. R.; Lianos, P. Soluble Tetratriphenyl-
amine Zn Phthalocyanine as Hole Transporting Material for
Perovskite Solar Cells. Electrochim. Acta 2016, 222, 875−880.
(26) Cho, K. T.; Trukhina, O.; Roldán-Carmona, C.; Ince, M.;
Gratia, P.; Grancini, G.; Gao, P.; Marszalek, T.; Pisula, W.; Reddy, P.
Y.; Torres, T.; Nazeeruddin, M. K. Molecularly Engineered
Phthalocyanines as Hole-Transporting Materials in Perovskite Solar
Cells Reaching Power Conversion Efficiency of 17.5%. Adv. Energy
Mater. 2017, 7, 1601733.
(27) Majeed, S. A.; Ghazal, B.; Nevonen, D. E.; Goff, P. C.; Blank, D.
A.; Nemykin, V. N.; Makhseed, S. Evaluation of the Intramolecular
Charge-Transfer Properties in Solvatochromic and Electrochromic
Zinc Octa(carbazolyl)phthalocyanines. Inorg. Chem. 2017, 56,
11640−11653.
(28) Milan, R.; Selopal, G. S.; Cavazzini, M.; Orlandi, S.; Boaretto,
R.; Caramori, S.; Concina, I.; Pozzi, G. Dye-Sensitized Solar Cells
Based on a Push-Pull Zinc Phthalocyanine Bearing Diphenylamine
Donor Groups: Computational Predictions Face Experimental
Reality. Sci. Rep. 2017, 7, 15675.
(29) Yang, L.; Guo, L.; Chen, Q.; Sun, H.; Yan, H.; Zeng, Q.; Zhang,
X.; Pan, X.; Dai, S. Substituents Effects on Zinc Phthalocyanine
Derivatives: a Theoretical Calculation and Screening of Sensitizers for
Dye-Sensitized Solar Cells. J. Mol. Graphics Modell. 2012, 38, 82−89.
(30) Staub, F.; Hempel, H.; Hebig, J.-C.; Mock, J.; Paetzold, U. W.;
Rau, U.; Unold, T.; Kirchartz, T. Beyond Bulk Lifetimes: Insights into
Lead Halide Perovskite Films from Time-Resolved Photolumines-
cence. Phys. Rev. Appl. 2016, 6, 044017.
DOI: 10.1021/acsaem.9b00637
ACS Appl. Energy Mater. 2019, 2, 6195−6199