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Title: An Azulene-Containing Low Bandgap Small Molecule for Organic Photovol-

taics with High Open Circuit Voltage

Authors: Yao Chen; Youqin Zhu; Daobin Yang; Suling Zhao; Lei Zhang; Lin Yang;
Jianglin Wu; Yan Huang; Zheng Xu; Zhiyun Lu

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An Azulene-Containing Low Bandgap Small Molecule for Organic
Photovoltaics with High Open Circuit Voltage
Yao Chen,[a, d] Youqin Zhu, [b, d] Daobin Yang, [a] Suling Zhao,[b] Lei Zhang,[a] Lin Yang,[a] Jianglin Wu,
[a]
Yan Huang*,[a, c] Zheng Xu[b] and Zhiyun Lu[a]
Abstract: A simple azulene-containing squaraine dye (AzUSQ)
showing bandgap of 1.38 eV and hole mobility up to 1.25 × 10 -4 cm2
V-1 s-1 was synthesized. Considering of its low band gap, organic
photovoltaic (OPV) device based on it exhibits an impressive V oc of
0.80 V. Hence azulene might be a promising structural unit to
construct OPV materials with simultaneous low bandgap, high hole
mobility and high Voc.
Owing to its low-cost, light-weight and flexibility, rapid energy
payback time, organic photovoltaic (OPV) has received
[1]
increasing attention, while small molecular (SM) OPV
materials are more attractive than their polymeric counterparts
due to their well-defined molecular structure, definite molecular
[2]
weight and high purity without batch to batch variations. To
achieve high power conversion efficiency (PCE), an ideal
[3]
bandgap (Eg) of 1.2-1.6 eV is necessary, and donor(D)-
acceptor(A) interactions are often used to reduce the bandgap.
For low bandgap small molecules, one either needs a platform
that allows greater conjugation lengths or very strong D-A
interactions. So far, high performance low bandgap SM-OPVs
materials are usually constructed by the former way, such as D-
[4] [5]
A-D-A-D, or oligomer(such as oligothiophene), which would
generally result in the complex synthesis. The synthesis of low
bandgap materials constructed by the latter way are simple, but
they are often difficult to obtain high open circuit voltage (Voc),
because the reduction of the bandgap are often accompanied
with the rising of the highest occupied molecular orbital (HOMO)
level, while Voc is found to correlate with the difference between
HOMO of the donor and LUMO (lowest unoccupied molecular
[2]
orbital) of the acceptor in the photoactive layer. Therefore, it is
necessary to explore novel D or A building blocks for
construction of simple low bandgap SM-OPVs materials with
[6]
high Voc.
Azulene, a 10 π-electron isomer of naphthalene and
resonance-stabilized non-alternant aromatic hydrocarbon with
an electrically positive seven-membered ring and an electrically
negative five-membered ring, is a simple aromatic compound
with a dipole moment of 1.08 D and possesses a narrow energy
[7]
gap. More importantly, azulene derivatives have much lower
bandgaps than naphthalene derivatives, which was mainly due
[8]
to the significantly decreasing LUMO, and this characteristic is
beneficial to get the low bandgap materials without the
drastically rising of the HOMO. Additionally, azulene-containing
molecules and polymers have been used to develop high charge
[9]
mobility material. In view of the easy availability and low-cost
of some azulene derivatives, it is reasonable to speculate that
azulene might be a simple but promising D structural unit to
construct OPV donor materials with low bandgap, high Voc as
Supporting information for this article is given via a link at the end of the
document.
10.1002/chem.201603399
well as good hole mobility. Yet up to now, there were only two
relative reports on azulene-containing OPV polymers;
[7b, 10]
Although plenty of azulene-based small molecules have been
reported, to the best of our knowledge, hitherto there is no one
has been applied to OPV field.
Recently, squaraine-based (SQ) SM-OPV materials with the
squaric acid core acting as the A subunit have aroused much
research enthusiasm due to their intense absorption in the
visible-NIR region with very high molar extinction coefficients,
excellent photochemical/photophysical stability,
[11]
and facile
synthesis as well.
[6]
In comparison with unsymmetrical
squaraines (USQs) bearing a D-A-D' molecular skeleton, D-A-D
structured symmetrical squaraines (SSQs) possess less plentiful
room for molecular tailoring.
[12]
Hence we aimed at the
exploitation of novel SQ OPV material with azulene as the D
subunit, then designed and synthesized an unsymmetrical
azulene-based SQ derivative AzUSQ (Scheme 1), in which an
easily available guaiazulene was chosen as the D subunit to
[13]
endow the compound with low-cost and good solubility, and
an excellent N-(3,5-dihydroxyphenyl)benzoindoline group was
[14]
selected as the D' subunit according to our previous works. To
gain insight to the structure-property correlation, a symmetrical
reference compound AzSQ was also prepared. AzSQ is a known
dye, first reported in 1966, and recently De Leeuw and
coworkers reported its carrier mobilities in organic light emitting
transistor (OLET),
[15]
but it has not been applied in OPV.
The absorption spectra of AzUSQ in dilute chloroform solution
and thin film is depicted in Figure 1, and data are summarized in
Table 1. In dilute solutions, AzUSQ exhibit intense absorption
bands (log ɛ > 5.00) with full width at half maxima (FWHM) of
~70 nm. In neat film states, the λabs of AzUSQ is 813 nm, which
is red-shifted significantly than its solution sample, together with
much broadened FWHM of ~200 nm. From the threshold (901
nm for AzUSQ) in the low energy absorption edge of the thin-film
samples, the optical bandgap of it is estimated to be 1.38 eV,
[3]
which fall into the ideal Eg range for OPV applications. Hence
by using azulene as the D unit, SQ dyes with not only
satisfactory Eg, but also broad and intense absorption ensuring
efficient light harvesting could be constructed. According to cyclic
voltammetry (CV) measurements (Figure 2), the HOMO level of
AzUSQ is calculated to be ‒5.09 eV, and this is a deep HOMO
level relative to other small molecules with very low bandgap.
The hole mobility of AzUSQ and AzSQ were investigated by
the space-charge-limited current (SCLC) method, and the device
structure is: ITO/MoO3 (8 nm) / SQ (50 nm) / MoO 3 (8 nm)/Al
(100 nm). The hole mobility (μh) of the neat AzUSQ film was
-4 2 -1 -1
calculated to be 1.25 × 10 cm V s , which is one of the
[11]
highest values among OPV SQ derivatives. SQs often show
-5 2 -1
low hole mobility (10 cm V s ) in neat film and lower in blend
film with fullerene derivatives, which have been the limiting
Scheme 1 Molecular structure of AzUSQ and AzSQ.
Chemistry - A European Journal 10.1002/chem.201603399

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Figure 1. Absorption spectra of AzUSQ in solution and thin film state. Figure 3. J-V characteristic of SQ hole-only devices.

Table 2 Mobility data of the two compounds.

SQ μh μe μe/μh
(cm2 V-1 s-1) (cm2 V-1 s-1)
AzUSQ 1.25×10-4 2.79×10-6 0.02
AzUSQ:PC71BM 3.96×10-5 5.10×10-5 1.29
AzSQ 3.15×10-5 6.00×10-7 0.19
AzSQ:PC71BM 1.17×10-5 3.00×10-5 2.56

diketopyrrolopyrrole (DPP) porphyrin Zinc derivative which

exhibit Voc of 0.78 V with a very low bandgap of 1.37 eV. It
should be noted that optical band gap of the solid thin film is
[18a]
calculated based on the onset of the absorption spectra. In
Figure 2. Cyclic voltammogram of AzUSQ. addition to the higher Voc, device II also shows higher Jsc (6.47
-2
vs 1.75 mA cm ) and FF (0.40 vs 0.35) than the reference
device I, which should be attributed to the higher carrier mobility
Table 1 Optical, electrochemical and electric properties of AzUSQ. and more balanced charge transport in the AzUSQ/PC71BM than
λ
a
(nm) λ
b
FWHM (nm) E
opt
E HOMO
AzSQ/PC71BM composite film. Owing to the simultaneously
abs abs g ox
-2
Compd (log ɛ) (nm) Solution film (V) (V) (eV) enhanced Voc, Jsc (6.47 vs 1.75 mA cm ) and FF, the AzUSQ-
AzUSQ 750(5.46) 813 67 205 1.38 0.29 -5.09 based device II shows a much higher PCE than the reference
-6 b
aMeasured in dilute chloroform solution (2.00×10 M); Measured in thin device (2.09% vs 0.36%). Upon thermal treating at 80 °C for 10
film state; min, the PCE of AzUSQ-based device (III) could be further
increased to 2.23% (Figure 4).
[11] Despite the fact that AzUSQ-based devices were found to
factor in development of SQ materials for OPV application. show moderate PCE of 2.23%, in view of the high charge
-5 2 -1 -1
AzSQ exhibits the hole mobility of 3.15 × 10 cm V s , much mobility of the active layer as well as the ideal low bandgap and
[15b]
lower than the reported value, which may ascribe to the deep HOMO energy level of AzUSQ, the OPV performance of
different testing method, preparation of films and molecular AzUSQ is not satisfactory. To probe the origin of the relative low
[16]
orientation. The hole mobility of the AzUSQ/PC71BM and efficiencies of AzUSQ-based devices, AFM characterization
-5 2 -1 -1
AzSQ/PC71BM composite film are 3.96 × 10 cm V s and 1.17 × were carried out on the active layers, and the leakage currents
-5 2 -1 -1 -
10 cm V s , while their electron mobility are 5.10 × 10 of the devices were examined. As illustrated in Figure 5, both
2 -1 -1 -5 2 -1 -1
5 cm V s and 3.00 × 10 cm V s , respectively. AzUSQ/PC71BM and AzSQ/PC71BM blending films show quite
Although all the mobility are rather low and inferior to smooth surface (root-mean-square: 0.14~0.20 nm) together with
photovoltaic performance, AzUSQ/PC71BM composite film well-mixed morphology in the surface, indicative of the very good
exhibits more balanced charge transport(1.29 via 2.56), resulting miscibility between SQ and PC71BM, which may suggesting the
[17] [19]
in more efficient charge extraction compared to AzSQ. lacking of favorable interpenetrating networks. In addition,
Using AzUSQ or AzSQ as the electron donor material, although the AzUSQ-based device II shows a much higher PCE
solution-processed BHJ devices with a conventional structure of in comparison with the reference device I, it also shows an
ITO/MoO3 (8 nm)/SQ:PC71BM (60 nm)/BCP (6 nm)/Al (100 nm) unexpected higher dark current (Figure 6), implying the
were fabricated. The representative photovoltaic data of these presence of more charge recombination in device II. This
devices are summarized in Table 3, and the current density- deduction is further confirmed by the shunt resistance (Rsh)
voltage (J-V) and external quantum efficiency-wavelength (EQE) measurement of the devices, because Rsh is highly correlated
curves are shown in Figure 4. Although the AzSQ-based with the charge recombination process in the photoactive layer.
reference device I just exhibits a moderate Voc of 0.58 V, the [20]
As shown in Table 3, in spite of the lower series resistance
AzUSQ-based device II, despite the relatively low Eg of of (Rs) of AzUSQ-based devices II and III arising from the higher
AzUSQ (1.38 eV), shows an impressive Voc of 0.80 V. Note that charge mobility of their photoactive layers, these two devices
a low-bandbap donor material will generally accompanied with a show lower Rsh than the reference device, which suggests the
relatively high HOMO energy level, leading to a relatively low Voc presence of more serious charge recombination in devices II and
in its corresponding OPV device. There are limited examples of III.
[21]
Therefore, the unsatisfactory OPV performance of devices
low bandgap (<1.5 eV) SMs in OPV field, and they often show II and III might be ascribed to the poor interpenetrating networks
reported best example is a complex SM based on modest Voc (~ and high charge recombination within the photoactive layer,
[18]
0.7 V). To the best of our knowledge, the which would be enhanced via molecular tailoring.

Table 3 Photovoltaic performance of BHJ-OPVs based on AzSQ and AzUSQ.

b b c b b c c c
Device Active layer Voc Jsc Jsc-EQE FF PCE (%) Rsh Rs Eloss (eV)
2 -2 2 2
(V) (mA/cm ) (mA cm ) (Ω cm ) (Ω cm )
Ⅰ AzSQ: PC71BM=1:3 0.58±0.01 1.75±0.04 1.55 0.35±0.01 0.36±0.01 459.81 66.68 0.74
Ⅱ AzUSQ:PC71BM=1:3 0.80±0.01 6.47±0.05 6.14 0.40±0.01 2.09±0.05 234.72 25.15 0.58
Ⅲ a 0.79±0.01 6.81±0.04 6.70 0.41±0.01 2.23±0.06 240.12 22.50 0.59
AzUSQ:PC71BM=1:3
b c
a Device annealed at 80 °C for 10 min Datas obtained from 8 devices; Data from best device
Chemistry - A European Journal
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Figure 4. J-V characteristics (a) and EQE characteristics (b) of the OPV
devices.
Figure 5. 3D Height images (5 × 5 μm, tapping-mode) of (a)
AzSQ:PC71BM (1:3) composite film (RMS=0.20 nm); and (b)
AzUSQ:PC71BM (1:3) composite film (RMS= 0.14 nm). Phase images (5
µm × 5 µm) of blend films(c) AzSQ:PC 71BM (1:3) composite film; and (d)
AzUSQ:PC71BM (1:3) composite film
Figure 6. The current-voltage response measured in the dark of device I
and device II.
In summary, an azulene-containing squaraine dye AzUSQ
was designed and synthesized. This simple molecule shows a
low bandgap of 1.38 eV, which is comparable with those small
molecules bearing much more complicated structure or D/A
subunits. In addition, it possesses a deep HOMO of ~ ‒5.1 eV,
endowing its corresponding OPV devices with impressive high
Voc of 0.80 V and small energy loss (Eloss) of 0.58 eV. In fact, the
Voc of AzUSQ-based device is among the highest values in
OPVs bearing low-bandgap donors; while the Eloss of AzUSQ-
based device is among the smallest values for OPVs and
[18a]
approaches the value for inorganic solar cells. Although
AzASQ only show modest PV performance, we believe that
azulene unit could be used as a simple and promising block for
facile construction of OPV materials with low bandgap, high
mobility and high Voc at the same time, and the azulene-
containing materials will be fascinating when the morphologies
and charge recombination of photoactive layer could be
optimized through rational molecular tailoring.
Acknowledgements
We acknowledge the financial support for this work from the
National Natural Science Foundation of China (project No.
51573108, 61575019 and 21372168), the Research Fund for the
Doctoral Program of Higher Education (No. 20130009130001)
10.1002/chem.201603399
and Fujian Key Laboratory of Polymer Materials (Fujian Normal
University) (FJKL-POLY 201502). We also thank the Analytical &
Testing Center, Sichuan University and Comprehensive Training
Platform of Specialized Laboratory, College of Chemistry,
Sichuan University for providing NMR and HRMS data for the
intermediates and target molecules.
Keywords: azulene • organic photovoltaics • low bandgap •
squaraine dye • open circuit voltage
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Chemistry - A European Journal 10.1002/chem.201603399

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Entry for the Table of Contents (Please choose one layout)

Layout 1:

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Azulene might be a promising Yao Chen, Youqin Zhu, Daobin Yang,
structural unit to construct OPV Suling Zhao, Lei Zhang, Lin Yang,
materials with simultaneous low Jianglin Wu, Yan Huang*, Zheng Xu,
bandgap, high hole mobility and high Zhiyun Lu
Voc.
Page No. – Page No.

An Azulene-Containing Low Bandgap

Small Molecule for Organic
Photovoltaics with High Open Circuit
Voltage