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A strategy to improve the efficiency of hole

Cite this: Nanoscale, 2016, 8, 17752
transporting materials: introduction of a highly
Received 2nd August 2016, symmetrical core†
Accepted 22nd September 2016
DOI: 10.1039/c6nr06116h Wei-Jie Chi, Ping-Ping Sun and Ze-Sheng Li*
www.rsc.org/nanoscale

The electronic, optical and hole transport properties of three new
hole transporting materials (HTMs) with a planar core have been
investigated by using density functional theory and Marcus theory.
A reliable semi-rational formula was adopted to calculate the
highest occupied molecular orbital (HOMO) levels of new HTMs.
The results showed that the HOMO levels of new HTMs were
0.07–0.30 eV lower than those of Spiro-OMeTAD, and their
absorption peaks appeared outside or close to the visible region
and overlapped slightly with the absorption band of perovskites.
Moreover, the Stokes shifts of the designing molecules were calcu-
lated to lie in a range from 72 to 124 nm, meaning that they could
undergo large geometrical changes on excitation. More impor-
tantly, the hole mobility of new HTMs (0.099–0.27 cm2 v−1 s−1)
was approximately two orders of magnitude higher than that of
Spiro-OMeTAD (0.0056 cm2 v−1 s−1) due to strong hole coupling
from a face-to-face packing pattern. Our results indicated that
planar core-based HTMs could become potential candidates to
replace the widely established Spiro-OMeTAD.
Since the first report in 2009,1 organic–inorganic halide
perovskite solar cells (PSCs) have attracted much attention due
to their low material cost, simple configuration, and excellent
photovoltaic performance. In subsequent years, devices based
on such materials have shown an unparalleled increase of
power conversion efficiency (PCE) from 3.8% to 22.1%.2–4
In PSCs, a hole-transporting material (HTM) plays an
important role in facilitating hole transport from the valence
band of perovskites to the back contact and impeding back
electron transfer as well.5 Until now, small organic molecule
2,2-7.7-tetrakis(N,N′-di-para-methoxy-phenyl-amine) 9,9′-spiro-
bifluorene (Spiro-OMeTAD) has been widely utilized for the
fabrication of PSCs, exhibiting a high PCE surpassing 20%.6–8
However, Spiro-OMeTAD suffers from the expensive synthetic
cost and poor hole mobility, which limits its practical appli-
cations. Therefore, it is imperative to design and synthesize
more efficient and economical alternatives for successful com-
mercialization of PSCs. Recently, a rich body of HTMs have
been reported in combination with perovskites from polymers
to organic small molecules. For the latter, different cores have
been used in the state-of-the-art HTMs, such as 3,4-ethylene-
dioxythiophene,9 truxene,10 benzotrithiophene,11 1,3,4-oxa-
diazole,12 fluorene-9,9′-xanthene,13 triazine,14,15 azulene,16
thiophene,17 and so on.
In this study, we present a new family of easily designed
HTMs based on an anthrax-[1,2-b:4,3-b′:5,6-b″:8,7-b′′′]tetrathio-
phene (ATT)18 as a core endowed with p-methoxydiphenyl-
amine (ATT-1), p-methoxytriphenylamine (ATT-2), and N,N-bis
(4-methoxyphenyl)-amino-N-diphenyl (ATT-3). The ATT core
shows a D2 symmetry, and the coplanar structure of ATT is
foreseen to promote an effective π–π intermolecular inter-
action, which could eventually lead to efficient hole transport
behavior. All new designing molecules are shown in Fig. 1. The
molecular neutral ground-state geometries are optimized by
density functional theory with B3LYP functional (UB3LYP for
cations) and 6-31G(d,p) basis set in dichloromethane solvent,

Key Laboratory of Cluster Science of Ministry of Education, Beijing Key Laboratory of

Photoelectronic/Electrophotonic Conversion Materials, School of Chemistry, Beijing Fig. 1 The chemical structures of ATT-1, ATT-2, and ATT-3. R denotes
Institute of Technology, Beijing 100081, China. E-mail: zeshengli@bit.edu.cn p-methoxydiphenylamine, p-methoxytriphenylamine, and N,N-bis(4-
† Electronic supplementary information (ESI) available. See DOI: 10.1039/ methoxyphenyl)-amino-N-diphenyl for ATT-1, ATT-2, and ATT-3,
c6nr06116h respectively.

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based on the conductor-like polarizable continuum model
(C-PCM), as implemented in the Gaussian 09 program.19
In order to maximize the hole injection processes and open
circuit voltage of the device, it is essential to have a good
energy alignment between the HTM and the perovskite. The
highest occupied molecular orbital (HOMO) levels of all the
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investigated molecules are calculated by using a reliable semi-
rational formula.20 The lowest unoccupied molecular orbital
(LUMO) level can be estimated by adding its excitation energy
to the HOMO level.20 Fig. 2 displays HOMO and LUMO distri-
butions and energy levels of HTMs. As shown in Fig. 2, the
HOMOs are fully delocalized within the whole molecules for
Spiro-OMeTAD, ATT-1, and ATT-2, while the HOMO of ATT-3 is
mostly localized across the four N,N-bis(4-methoxyphenyl)-
amino-N-diphenyl units. In terms of LUMOs, all investigated
molecules show similar distribution diagrams, which is
mainly localized on the central Spiro-unit or ATT core. The cal-
culated HOMO levels given in Fig. 2 indicate that an additional
phenyl ring between the ATT core and an electron donating
moiety stabilized HOMO levels by 140 meV and 90 meV,
moving from ATT-1 to ATT-2 and from ATT-2 to ATT-3, respect-
ively. The result implies that the size of the electron donating
moiety plays an important role in adjusting the HOMO levels
of materials, and a larger electron donating moiety provides
lower HOMO levels. The tendency can also be found in an
experimental study.21 Furthermore, the HOMO levels are calcu-
lated as −5.16, −5.30, and −5.39 eV for ATT-1, ATT-2, and
ATT-3, respectively, suggesting that the HOMO levels of new
designing molecules are more stabilized compared with that
of Spiro-OMeTAD. On the other hand, the HOMO levels of ATT
derivatives are higher than the valence band maximum of
CH3NH3PbI3 (−5.43 eV), indicating that they have an efficient
hole extraction capability. Hence, when used as new HTMs in
the PSCs, higher open circuit voltages are expected as the
open-circuit voltage is relative to the difference between the
quasi-Fermi levels of TiO2 and the HOMO level of HTM, a
bigger difference implies a higher open-circuit voltage.
Fig. 2 Calculated frontier molecular orbital distributions and energy
alignments of HTMs and CH3NH3PbI3.
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Additionally, PSC based-new HTMs may also yield large short-
circuit current density, which have a superlinear increase as
the HOMO levels of HTMs decrease.22
For LUMO levels, it is found that their value gradually
decreases as the size of the electron donating moiety increases.
Moreover, the calculated LUMO levels are −2.22, −2.67, and
−2.75 eV for ATT-1, ATT-2, and ATT-3, respectively. As a conse-
quence, we believe that this larger energy barrier (1.16–1.90 eV)
between the conduction band of perovskites (such as
CH3NH3PbI3, −3.91 eV) and the LUMO of HTMs would block
the electrons efficiently from perovskites to the metal electrodes
and thus largely reduce the recombination chance.
Taking into consideration the appropriate HOMO and
LUMO levels, the three new ATT derivatives seem to be good
candidates as HTMs to improve the performance of PSCs.
Except suitable energy levels, transparency in the visible
region of the electromagnetic spectrum and large Stokes shift
are also typical features for a good HTM. To characterize the
optical properties of the investigated molecules, we performed
time dependent-DFT calculations on the ground-state and
excited-state structures optimized in dichloromethane. The
excited-state geometries of new HTMs are optimized at the
CAM-B3LYP/6-31G(d,p) level. The absorption properties are
evaluated with the MPW1K functional and 6-31G(d,p) basis
set. The method is reasonable and capable of evaluating the
absorption properties of phenylamine-type molecules.23,24 The
maxima absorption peak position (vertical solid lines with
arrow, λabs), maxima emission peak position (vertical dotted
lines with arrow, λemi), and Stokes shifts (horizontal dotted
lines with arrow) of the investigated molecules are shown in
Fig. 3. As shown in Fig. 3, the calculated maxima absorption
peak of Spiro-OMeTAD is at 346 nm, which is close to the
experimental value with 383 nm.25 For new HTMs, we find that
the maxima absorption peaks of ATT derivatives range from
364 to 420 nm, which are shown to be red-shifted by 18–74 nm
Fig. 3 The maxima absorption peak (MAP, vertical solid lines with
arrow), maxima emission peak (MEP, vertical dotted lines with arrow),
and Stokes shifts (horizontal dotted lines with arrow) of the investigated
molecules at the MPW1 K/6-31G(d,p) level.
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compared with that of Spiro-OMeTAD. The results imply that
in all cases the absorption takes place outside or close to the
visible region and overlaps slightly with the absorption band
of perovskites. The maxima emission peaks are at 488, 492,
and 481 nm for ATT-1, ATT-2, and ATT-3, respectively, which is
91–102 nm red-shifted compared with the maxima emission of
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Spiro-OMeTAD with 390 nm (experimental value with 419 nm).
According to the maxima absorption peak and maxima emis-
sion peak, the Stokes shift can be calculated by using the fol-
lowing expression: Stokes shift = λemi − λabs.
Stokes shift can reflect the degree of structural deformation
between the ground state and excited state geometries. A
larger Stokes shift is beneficial for pore-filling of HTM.9,26 As
shown in Fig. 3, the Stokes shift of Spiro-OMeTAD is 44 nm,
which is in good agreement with the experimental value of
33 nm.27 Stokes shifts follow the trend ATT-1 (124 nm) > ATT-3
(75 nm) > ATT-2 (72 nm) > Spiro-OMeTAD (44 nm). The result
suggests that new designing ATT derivatives as HTMs are
better for increasing the performance of PSCs compared with
Spiro-OMeTAD. Interestingly, we also find that although Spiro-
OMeTAD and ATT-1 have the same arms as p-methoxydiphenyl-
amine, the Stokes shift of ATT-1 is larger than that of Spiro-
OMeTAD by 80 nm. The result allows us to conclude that the
planar core is more beneficial to increasing the Stokes shift of
the HTM compared with the Spiro-core since the Spiro-unit
ensures a great rigidity.
Many studies28,29 have pointed out that the faster hole
mobility is responsible for larger short-circuit current density
and higher fill factor of PSC. Hence, obtaining reliable hole
mobility is an important step to develop efficient HTM.
Marcus theory and the Einstein relationship are employed to
calculate the hole mobility of HTMs. The Einstein relationship
has been widely used to analyze the carrier mobility of organic
molecules, and reliable results can be reproduced, especially
for planar organic molecules. For example, Shi et al. calculated
the carrier transport properties of tetrathiafulvalene deriva-
tives, and they found that the calculated electron and hole
mobilities agree reasonably well with the experimental one for
DB-TTF and DN-TTF.30 In the present work, the hole transport
pathways are simplified from three-dimension to one-dimen-
sion. It should be pointed out that the one-dimensional
pathway selected has the lowest energy of dimers in all poss-
ible hole transport pathways. A previous study20 has shown
that the more stable dimers have larger hole transfer integrals.
The hole transport pathway with large hole transfer integral
determines the hole mobility of a molecule. The compu-
tational methods of obtaining stable dimers and calculating
molecular hole mobility are listed in the ESI.† To further deter-
mine the reliability of the simplified method, we take Spiro-
OMeTAD, tris[N,N-bis(4-methoxyphenyl)-N-biphenyl]amine
(OMeTPA-TPA),31 and HTM132 as models to calculate their
hole mobility. The relevant data are listed in Table S1.† The
result shows that the predicted (uc(Spiro-OMeTAD) = 5.56 ×
10−3 cm2 v−1 s−1, uc(HTM1) = 1.33 × 10−6 cm2 v−1 s−1, and
uc(OMeTAD-TPA) = 5.75 × 10−4 cm2 v−1 s−1) and experimental
hole mobility (ue(Spiro-OMeTAD) = 1.30 × 10−3 cm2 v−1 s−1,
17754 | Nanoscale, 2016, 8, 17752–17756
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ue(HTM1) = 6.00 × 10−6 cm2 v−1 s−1, and ue(OMeTAD-TPA) =
1.08 × 10−4 cm2 v−1 s−1) are of the same order of magnitude. It
is obvious to conclude that the simplified method is reason-
able and capable of evaluating the hole mobility of organic
materials. Su’s study33 also supports our conclusion above,
their calculation pointed out that the carrier mobility obtained
by the optimized geometry of the major pathway is in good
agreement with the experimental value. The stable dimers of
ATT derivatives are shown in Fig. S1 of the ESI.† The hole
mobility of ATT derivatives and Spiro-OMeTAD is shown in
Fig. 4 and Table S2 of the ESI.† As shown in Fig. 4, the hole
mobilities of ATT-1 (0.13 cm2 v−1 s−1), ATT-2 (0.27 cm2 v−1 s−1),
and ATT-3 (0.099 cm2 v−1 s−1) are approximately 2 orders of
magnitude higher compared with Spiro-OMeTAD (0.0056
cm2 v−1 s−1). This can be explained by the fact that the ATT
derivatives with a planar core have a large transfer integral (see
Table S2†) between adjacent dimers due to short centroid to
centroid distances and strong π–π interactions. A previous
study also has proved that the planar and fully conjugated
molecule enables investigated materials to have ordered
assemblies for better charge transport in the film state.10
Additionally, sulfur–sulfur interactions can also strongly affect
the packing model of molecules and are beneficial to enhance
the charge transport rate, which is consistent with a previous
work that the corresponding S⋯S distances in stacked dimers
are inversely proportional to hole mobility.34 The higher hole
mobility of new designing molecules allows them to function
as effective HTMs without the need of an extra doping process,
which significantly simplifies device fabrication and improves
the stability of PSC.
For new designing materials, the solubility and stability
should also be considered. The solubility of a material can be
predicted by using solvation free energy (ΔGsolv). The defi-
nition of solvation free energy is the difference in free energy
of the solute in the solution and gas phases.35 The more nega-
tive solvation free energy is, the more soluble the material is.
In the present work, the solvent is dichloromethane and the
solvation free energy is calculated according to the Coote’s
report.35 The calculated ΔGsolv value of Spiro-OMeTAD is
Fig. 4 Calculated hole mobility of new HTMs.
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−23.9 kcal mol−1, the ΔGsolv values of ATT-1, ATT-2, and ATT-3
are −23.1, −27.2, and −31.8 kcal mol−1, respectively. The result
shows that ATT-1 has similar solubility with Spiro-OMeTAD,
while ATT-2 and ATT-3 possess higher solubility than Spiro-
OMeTAD. The stability of an organic semiconductor can be
estimated by absolute hardness (η),36 which is calculated using
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the operational definition given by: η = (IP − EA)/2.37 EA rep-
resents the adiabatic electron affinity and IP denotes the adia-
batic ionization potential. We calculate the absolute hardness
of Spiro-OMeTAD and ATT derivatives, and the relevant data
are listed in Table S3 of the ESI.† As shown in Table S3,† ATT
derivatives have approximate η values (1.23–1.25 eV), which
implies that they have similar stability. Moreover, we also find
that the η values of ATT derivatives are slightly smaller com-
pared with that of Spiro-OMeTAD (1.62 eV). The difference
between the η values of Spiro-OMeTAD and ATT derivatives
only is about 0.38 eV. The result indicates that the stability of
ATT derivatives is comparable to that of Spiro-OMeTAD.
From an experimental viewpoint, we believe that newly
designed HTMs can be synthesized, and the conjectural syn-
thetic pathways are given in Fig. 5 according to previous
reports.11,15 As shown in Fig. 5, p-methoxydiphenylamine can
be introduced by the Buchwald–Hartwig amination reaction to
obtain ATT-1. Three p-methoxytriphenylamine units can be
covalently linked to the ATT core by a Suzuki cross-coupling
reaction to obtain ATT-2. The ATT-3 can be synthesized by the
Stille coupling reaction of N,N-bis(4-methoxyphenyl)-4′-(tri-
methylstannyl)biphenyl-4-amine with bromination of ATT.
Fig. 5 Conjectural synthetic pathways for new HTMs.
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Conclusions
In conclusion, three new HTMs were designed by introducing
p-methoxydiphenylamine, p-methoxytriphenylamine, and N,N-
bis(4-methoxyphenyl)-amino-N-diphenyl units onto the D2
ATT-core. The frontier molecular orbital energies and optical
properties were studied by using density functional theory and
time dependent density functional theory. Results suggested
that three ATT derivatives have deeper energy levels and larger
Stokes shifts compared to Spiro-OMeTAD. The planar and fully
conjugated D2 HTMs resulted in more excellent hole mobility
than Spiro-OMeTAD, the hole mobility of new HTMs
(0.099–0.27 cm2 v−1 s−1) was approximately 2 orders of magni-
tude higher compared to Spiro-OMeTAD (0.0056 cm2 v−1 s−1).
According to the above data, we believe that ATT derivatives
can be used as efficient candidates to replace the state-of-the-
art Spiro-OMeTAD. Our work opens up the potential incorpo-
ration of the planar core into HTMs to explore high-efficiency
PSCs in the future.
Acknowledgements
This work is financially supported by the Major State Basic
Research Development Programs of China (2011CBA00701)
and the National Natural Science Foundation of China
(21473010, 21303007).
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