A supramolecular assembly of metal-free organic dye with zinc porphyrin chromophore for dye-sensitized solar cells

Article abstract of DOI:10.1039/c7dt03373g

Two porphyrin chromophores, P1 and P2, were prepared and used as antenna units to coordinate with a metal-free organic dye, JH1, containing pyridine groups. This supramolecular self-assembly strategy can not only effectively improve the light-harvesting ability of the devices but also effectively reduces electron recombination by preventing I₃^- of the electrolyte from penetrating into the TiO₂ surface. The DSSC based on JH1 showed a PCE of 2.46%, with a V_oc of 615 mV, J_sc of 6.54 mA cm^-2, and FF of 61.18%. After supramolecular self-assembly, the J_sc and V_oc of the device were greatly improved. Specifically for the device based on JH1 + P2, the PCE reached 4.39%, which is about 78% greater than the PCE of the device based on JH1; this is mainly due to the J_sc increase of 2.85 mA cm^-2 and the V_oc increase of 93 mV. Compared to co-sensitization, supramolecular self-assembly does not require tedious optimization steps; thus, this may be a promising and convenient way to improve the overall performance of DSSCs.

Full text of DOI:10.1039/c7dt03373g

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A supramolecular assembling of metal-free organic dye with zinc
porphyrin chromophore for dye-sensitized solar cells
Hai-Lang Jia,*ab Mao-Zhan Huang,a Zhi-Jie Peng,a Dong-Ming Wang,a Guo-Hua Zhanga and Ming-
Yun Guana
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Two porphyrin chromophores P1 and P2 were prepared and have been used as antenna units to coordinate with metal-
free organic dye JH1 containing pyridine groups, this supramolecular self-assembly strategy can not only effectively
www.rsc.org/
-
improve the light-harvesting ability of the devices, but also effectively reduce electron recombination by preventing the I3
of the electrolyte penetrating into the TiO2 surface. The DSSC based on orgnaic dye JH1 showed a PCE of 2.46%, with the
V
oc of 615 mV, Jsc of 6.54 mA cm-2, and FF of 61.18%. After supramolecular self-assembly, the Jsc and Voc of the device were
both greatly improved. Especially for the device based on JH1+P2, the PCE reached 4.39%, which increased about 78%
compared with the PCE of the device based on JH1, this is mainly due to the Jsc increase of 2.85 mA cm-2 and the Voc
increase of 93 mV. Compared to co-sensitization, supramolecular self-assembly does not require tedious optimization
steps, thus, this may be
a
promising and convenient way to improve the overall performance of DSSCs.
such dyes.13 Porphyrin dyes hve excellent optical properties, which
show broad absorption at the Soret band (400–450 nm) and
moderate absorption at the Q-bands (550–600 nm), have become
Introduction
one of the hottest studied sensitizers for DSSCs.14,15 The DSSC based
on porphyrin dye SM315 showed a very high PCE of 13.0% by
Grätzel in 2014.16 The organic dyes have developed very rapidly in
recent years, the cheap and easy to design features attract more
and more attention. Some excellent dyes, such as SGT-137, C281,
IQ21, YA422 have been successfully prepared.17-21 However, most
excellent dyes require complex synthetic steps, the yield is not high.
As we know, excellent light harvesting capability is an important
prerequisite for efficient dyes. For single layer dyes, in order to
achieve this goal, the researchers have to design lengthy synthetic
routes. Supramolecular self-assembly may be one of the more
convenient ways to increase the light harvesting capability.22-27 The
porphyrins, phthalocyanines and ruthenium complexes are often
used as building blocks for assembling supramolecular systems.
Compared with the cosensitization method,28,29 supramolecular
self-assembly can eliminate lengthy optimization steps and no need
have to be tedious to find the suitable adsorption conditions. The
conditions for cosensitization need to be carefully explored, many
factors influence the final result, such as types of cosensitizers,
cosensitization mode, cosensitization solvent, cosensitization time,
in addition, competitive adsorption often occurs between the main
dye and cosensitizer. In contrast, supramolecular self-assembly is
very easy to operate, which can be accomplished by metal
coordination, H- bond and so on. Moreover, this method does not
reduce dye loading, what’s even more surprising is that the antenna
unit of the supramolecular systems can not only improve the
spectral response, but also reduce charge recombination by their
steric effect. Up to now, there are not many reports related to this,
It is well known that the world is facing an energy crisis, the search
for new energy is imminent for mankind. Dye-sensitized solar cells
(DSSCs) as a promising optoelectronic technology have aroused the
interest of many researchers, owing to their low manufacturing
costs and simple fabrication techniques.1,2 Since Grätzel and co-
workers first reported DSSCs in 1991,3 the power conversion
efficiency (PCE) has made a series of key breakthroughs. The initial
PCE was only 7.1%, in 2015, Toru Yano and co-workers prepared the
alxoxysilyl-anchor dye ADEKA-1, the PCE of the DSSC based on
ADEKA-1 and co-photosensitizer LEG4 reached up to 14.3%.4
As a wide band gap semiconductor with innocuity, stabilization
and cheapness, TiO2 is one of the best materials for preparing the
anodes of DSSCs, however, the absorption of light from the
ultraviolet region is a major defect. The sensitizers play a very
important role in improving spectral response range and initiating
electron transfer, the developing of efficient sensitizers is seen as
one of the most direct and effective ways to improve the PCE of
DSSCs.5-8 Up to now, many excellent dyes have been developed, the
most important of these are ruthenium complexes, porphyrin dyes
and metal-free organic dyes.9-12 Ruthenium complexes were studied
earlier, N3 and N719 are both excellent high efficiency dyes, a great
deal of work has focused on the improvement of the kind of dyes,
however, the expensive metal ruthenium limits the development of
a.School of Chemical and Environmental Engineering, Jiangsu University of
Technology, Changzhou 213001, P. R. China, E-mail: jiahailang85@126.com.
b.State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing
210093, P. R. China.
Electronic Supplementary Information (ESI) available: synthesis details and
characterization data; Details for all physical characterizations. See
DOI: 10.1039/x0xx00000x
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Han and co-workers increased the PCE of the DSSC based on ZnPA The absorption spectra of JH1, P1 and P2 in THF are shown in Fig. 2a.
by about 47% by using this method.30
The D-π-A type dye JH1 shows an unsatisfactory spectral response,
In this work, in order to study the influence of supramolecular the highest molar extinction coefficient at 399 nm is 1.40×104 M-1
systems on the performance of DSSCs, we prepared a basic DꢀπꢀA cm-1. The two znic porphyrin chromophores P1 and P2 exhibit
metal-free organic dye JH1. In the donor of JH1, two pyridine typical porphyrin absorption characteristics. The absorption below
groups were introduced, which can enhance the electron donating 400 nm may be attributed to electronic transitions from π-π*, and
ability, more importantly, the two pyridine groups can coordinate the 400-650 nm range may be attributed to intramolecular charge
with many metal complexes chromophores. Herein, we used two transfer (ICT). P1 shows
a high molar extinction coefficient
porphyrin intermediates P1 and P2 of YD2-o-C8 as antenna units to (2.00×105 M-1 cm-1) at 426 nm in Soret band, and shows the molar
coordinate with triphenylamine dye JH1 containing pyridine groups extinction coefficient of 0.05×105 M-1 cm-1 at 596 nm in Q band.
(Fig. 1).14 The DSSC based on JH1 showed a PCE of 2.46%, with the Compared with P1, the absorption spectra of P2 show
a
Voc of 615 mV, Jsc of 6.54 mA cm-2, and FF of 61.18%. After pronounced red shift. At 431 nm in Soret band, P2 shows a high
supramolecular self-assembly, the overall performance of the molar extinction coefficient of 2.04×105 M-1 cm-1, and the lowest-
device has been greatly improved. Especially for the DSSC based on energy Q-band absorption of P2 was redshifted to 608 nm. After
JH1+P2, the device showed a PCE of 4.39%, with the Voc of 708 mV anchored on TiO2 substrate, the absorption spectra became
and Jsc of 9.39 mA cm-2. The supramolecular systems effectively broader (Fig. 2b). The ICT bands of JH1 showed a significant red
improve the light harvesting capability of the device, so the Jsc shift, the spectral response exceeds 600 nm, this may be attributed
increases from 6.54 to 9.39 mA cm-2. In addition, both P1 and P2 act to J-aggregation.31,32 After supramolecular self-assembly, the
-
as antenna units, they can effectively prevent the I3 of the absorption spectra of JH1+P1 and JH1+P2 have changed
electrolyte penetrating into the TiO2 surface, thereby reducing the dramatically compared to JH1. Since P1 and P2 have no anchoring
charge recombination and improving the Voc. The supramolecular groups, the two chromophores can not be adsorbed on TiO2. We
self-assembly strategy is very beneficial to improve the overall tried to immerse TiO2 into P1 and P2 solution for 24 h (Fig. S1), as a
performance of the DSSCs, we studied the optical properties and result, the absorption spectra showed no change (Fig. S2).
photovoltaic performance of the DSSCs based on the
supramolecular systems.
Fig. 1 Schematic diagram of supramolecular self-assembly of JH1 with P1 or
P2.
Results and discussion
Synthesis
The chemical structures of JH1, P1, P2 and the synthetic route
were shown in Scheme S1. The synthesis details and
characterization data were shown in supporting information.
Fig. 2 (a) UV-Vis absorption spectra of JH1, P1 and P2 in THF, (b) UV-Vis
absorption spectra of JH1, JH1+P1 and JH1+P2 anchored on TiO2 surface.
Optical properties
2 | J. Name., 2012, 00, 1-3
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If we immersed the TiO2 which have been sensitized with JH1
ARTICLE
Table 1 Photovoltaic parameters of the DSSCs obtained from the J-V curves
into P1 and P2 solution for 24 h, obviously, great changes have
taken place in the surface of TiO2 (Fig. S3). As shown in Fig. 2b,
compared with JH1, the absorption spectra of JH1+P1 and JH1+P2
became broader and higher, their spectral response are both over
650 nm, such superior light harvesting capability is very beneficial
to improve the short-circuit current of the device. But in Soret band,
we found that the absorption intensity of JH1+P1 is lower than that
of JH1+P2, in view of this, we further measured the dye loading
under the same conditions. After supramolecular self-assembly, the
dye loading for P1 is about 5.36×10-8mol cm-2, and the dye loading
for P2 is about 7.65×10-8mol cm-2, the larger dye loading for P2 can
compensate the absorption ability, this may be the main reason for
the difference in Soret band.
Dye
Jsc (mA cm-2)
6.54
8.16
9.39
Voc (V)
0.615
0.664
0.708
FF (%)
61.18
67.91
65.99
η (%)
2.46
3.68
4.39
JH1
JH1+P1
JH1+P2
The size of the active area for each cell is 0.25 cm2, the DSSCs were all
measured under standard global AM 1.5G solar irradiation.
Electrochemical studies
The cyclic voltammetry curves of JH1, JH1+P1 and JH2+P2 anchored
on TiO2 was measured to study the proprety of electron transfer
form excited dyes to the conduction band of TiO2.33 As shown in Fig.
S4, we used phtoanode as working electrode, Pt as counter
electrode, Ag/Ag+ as reference electrode. From the Fig. 3, we can
see that the ground state oxidation potentials (EOX) of JH1, JH1+P1
and JH1+P2 were 1.19 V, 1.12 V and 1.15 V (versus NHE),
respectively. Obviously, they are all positive than the redox
-
potential of the I-/I3 couple (0.4 V), this shows that the oxidized
dyes can be effectively recycled.34,35 The zero-zero excitation energy
(E0-0) was estimated from their absorption spectra, the values of JH1,
JH1+P1 and JH1+P2 are 2.54 eV, 1.98 eV and 1.91 eV, respectively.
Therefore, the excited oxidation potentials (E*OX) of JH1, JH1+P1
and JH1+P2 are -1.35 V, -0.92 V and -0.80 V, respectively. They are
all negative than the conduction band of TiO2 (-0.5 V versus NHE),
this illustrates that the electron from the excited dyes of JH1,
JH1+P1 and JH1+P2 all can efficiently inject into the conduction
band of TiO2.36
Fig. 4 (a) The J–V curves of DSSCs based on JH1, JH1+P1 and JH1+P2; (b) The
IPCE curves of DSSCs based on JH1, JH1+P1 and JH1+P2.
of DSSCs is shown in Fig. S5, the PCE of DSSC based on JH1 is 2.46%,
with the Voc of 615 mV, Jsc of 6.54 mA cm-2, and FF of 61.18%. In
order to improve the overall performance of the DSSCs, we
designed to use the pyridine groups of JH1 to coordinate with
porphyrin chromophores P1 and P2, just as expected, the Jsc and Voc
of this type of supramolecular DSSCs are both successfully improved.
Compared to JH1, the Jsc of DSSC based on JH1+P1 was increased
from 6.54 to 8.16 mA cm-2, this should be attributed to
improvements in the light harvesting capability. Surprisingly, the Voc
has also been greatly improved, the value was increased from 615
to 664 mV, we inferred that the main reason was that antenna units
can effectively prevent the I3- of the electrolyte penetrating into the
TiO2 surface, thereby reducing the charge recombination.37-39
When P2 as antenna unit, the PCE of the device reached the highest
value of 4.39%, which increased about 78% compared with the PCE
of the device based on JH1. Because P2 has better optical
properties, the corresponding Jsc reached 9.39 mA cm-2. The
Fig. 3 Schematic energy diagram of JH1, JH1+P1 and JH1+P2.
Photovoltaic performance of DSSCs
In order to investigate the photovoltaic property of the
supramolecular systems, we fabricated the DSSCs based on JH1,
JH1+P1 and JH1+P2 under the same conditions. The photovoltaic
parameters are collected in Table 1, and the photocurrent-density-
photovoltage (J–V) curves of are shown in Fig. 4a. Histogram of PCE
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supramolecular systems of JH1+P2 may be more conducive to analyzed the electron lifetimes of the devices by bode phase plots
reducing electron recombination, as we known that we can improve (Fig. 5b). We can get the peak frequency (f) at lower frequency
the Voc by increasing the electron injection rate or reducing electron region from the bode phase plots and the electron lifetime (τ) can
recombination, so the Voc increased from 615 to 708 mV.
be calculated by τ=1/(2πf).44,45 The bode phase plots show that the f
For further analysis the differences of Jsc, we measured the of JH1, JH1+P1 and JH1+P2 is 16.5, 12.1 and 5.0 Hz, respectively.
incident photon-to-current conversion efficiency (IPCE) spectra of Thus, the corresponding electron lifetime value of JH1, JH1+P1 and
the devices (Fig. 4b). Light harvesting capability affects the Jsc, from JH1+P2 is 9.7, 13.2 and 31.8 ms, respectively. This also explains why
Table 1 we can see that the Jsc of the DSSCs follow the order: the DSSCA based on JH1+P2 has the highest Voc.
JH1<JH1+P1<JH1+P2, this trend is consistent with the IPCE spectra
of the devices. As shown in Fig. 4b, the IPCE curves of JH1 exhibited
narrower response range, the photocurrent generation up to about
550 nm. In the visible region, the highest value of JH1 is only 49.7%
at 405 nm. The introduction of P1 as antenna units on the donors
segment improve the spectral response range of the device,
obviously, consequently the Jsc is improved. The IPCE spectrum of
JH1+P1 is more broader than that of JH1, although the values of
JH1+P1 is slightly lower than that of JH1 in the shortwave region,
this may be due to a slight decrease of dye loading for JH1 during
the supramolecular self-assembly process. However, the IPCE
spectrum of JH1+P1 is much higher than that of JH1 after 425 nm,
this should be attributed to the contribution of P1 in light
harvesting performance. The photocurrent of JH1+P1 generation
up to about 650 nm, in the long-wave region, the value is about
16.3% at 596 nm. The device based on JH1+P2 exhibits broader and
higher IPCE curve from 400 to 650 nm range, especially in the long-
wave region, the value is about 29.5% at 615 nm, this is consistent
with the Jsc of the DSSCs.
Electrochemical impedance spectroscopy measurements
The electrochemical impedance spectroscopy (EIS) under dark was
often measured to study the electron recombination dynamics of
the DSSCs, under the same conditions (with the same electrode
materials and electrolyte), electron recombination rate has an
important influence on the open-circuit voltage (Voc) 40-43
In order
.
to analyze the difference between open-circuit voltages of the
DSSCs, we measured the EIS under the applied voltage of -0.7 V and
scanned from 105 to 1 Hz. The equivalent circuit was presented in
Fig. 5c, Rh in the high frequency range corresponds to the sheet
resistance of FTO and the contact resistance between the FTO and
TiO2, R1 and R2 in the high and middle frequency regions are
assigned to charge transfer resistance at Pt/electrolyte and
TiO2/dye/electrolyte interface, respectively. Nyquist plots of DSSCs
are shown in Fig. 5a, we can see two semicircles, the small
semicircle corresponds to the transport resistance at the
Pt/electrolyte and the large semicircle corresponds to the charge
transfer resistance at the TiO2/dye/electrolyte interface. It is clear
that radius of the large semicircle of JH1+P1 is larger than that of
JH1, the obvious enhancement of R2 for JH1+P1 indicates that the
supramolecular systems is effective in TiO2/dye/electrolyte
interface modification, and this implies that the supramolecular
systems effectively reduces the electron recombination rate, this
also explains why Voc of JH1+P1 increased by 49 mV. In addition, the
R2 of JH1+P2 is larger than that of JH1+P1, this shows that the P2
unit is more conducive to suppressing electron recombination, it is
in agreement with the Voc of the DSSCs. In generally, the longer
electron lifetime represents the lower dark current, this is beneficial
to improve the open-circuit voltage of the devices. We further
Fig. 5 (a) Nyquist plots of DSSCs based on JH1, JH1+P1 and JH1+P2; (b) Bode
phase plots of DSSCs based on JH1, JH1+P1 and JH1+P2; (c) The equivalent
circuit (Rh, R1, and R2 are the series resistance, charge transfer resistance at
Pt/electrolyte, and at TiO2/dye/electrolyte interface, respectively; CPE1 and
CPE2 are the constant phase element for the TiO2/dye/electrolyte and
Pt/electrolyte interface, respectively).
Conclusions
In summary, we have prepared a metal-free organic dye JH1
containing pyridine groups and two porphyrin chromophores P1
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DOI: 10.1039/C7DT03373G
Table of contents entry
The supramolecular system has superior performance in improving spectral response and reducing
charge recombination, this may be a promising and convenient way to improve the performance of
DSSCs.