A new series of EDOT based co-sensitizers for enhanced efficiency of cocktail DSSC: A comparative study of two different anchoring groups

Article abstract of DOI:10.3390/molecules24193554

Herein, we report the design and synthesis strategy of a new class of five EDOT based co-sensitizers (CSGR1-5) by introducing different donors (2,3,4-trimethoxypheny, 2,4-dibutoxyphenyl, and 2,4-difluorophenyl) and anchoring groups (rhodamine-3-acetic acid and cyanoacetic acid) systematically. The synthesized metal-free organic co-sensitizers were employed for cocktail dye-sensitized solar cells along with N749 (black dye). The DSSC devices with a mixture of co-sensitizers (CSGR1-5) and N749 have shown a 7.95%, 8.40%, 7.81%, 6.56% and 6.99% power conversion efficiency (PCE) respectively, which was more than that of single N749 dye PCE (6.18%). Enhanced efficiency could be ascribed to the increased short circuit current (J_sc) and open circuit voltage (V_oc). The increased J_sc was achieved due to enhanced light harvesting nature of N749 device upon co-sensitization with CSGR dyes and feasible energy levels of both the dyes. The V_oc was improved due to better surface coverage which helps in decreasing the rate of recombination. The detailed optical and electrochemical properties were investigated and complimented with theoretical studies (DFT).

Full text of DOI:10.3390/molecules24193554

molecules
Article
A New Series of EDOT Based Co-Sensitizers for
Enhanced Efficiency of Cocktail DSSC:
A Comparative Study of Two Different
Anchoring Groups
Ganesh Koyyada 1 , Ramesh Kumar Chitumalla 2 , Suresh Thogiti , Jae Hong Kim ,
1
1
Joonkyung Jang 2 , Malapaka Chandrasekharam
3,4,
* and Jae Hak Jung *
1,
1
Department of Chemical Engineering, Yeungnam University, 214-1, Dae-hakro 280, Gyeongsan,
Gyeongbuk 712-749, Korea; ganeshkoyyada@ynu.ac.kr (G.K.); sureshyu@ynu.ac.kr (S.T.);
jaehkim@ynu.ac.kr (J.H.K.)
Department of Nanoenergy Engineering, Pusan National University, Busan 46241, Korea;
rameshchitumalla@gmail.com (R.K.C.); jkjang@pusan.ac.kr (J.J.)
Inorganic and Physical Chemistry Division, CSIR-Indian Institute of Chemical Technology, Tarnaka,
Hyderabad 500007, India
Academy of Scientific & Innovative Research (AcSIR), CSIR-IICT, Tarnaka, Hyderabad 500007, India
Correspondence: csmalapaka@iict.res.in (M.C.); jhjung@ynu.ac.kr (J.H.J.)
2
3
4
*
ꢀ
ꢁꢂꢀꢃꢄꢅꢆꢇ
ꢀ
ꢁꢂꢃꢄꢅꢆ
Received: 11 August 2019; Accepted: 25 September 2019; Published: 30 September 2019
Abstract: Herein, we report the design and synthesis strategy of a new class of five EDOT based
co-sensitizers (CSGR1-5) by introducing different donors (2,3,4-trimethoxypheny, 2,4-dibutoxyphenyl,
and 2,4-difluorophenyl) and anchoring groups (rhodamine-3-acetic acid and cyanoacetic acid)
systematically. The synthesized metal-free organic co-sensitizers were employed for cocktail
dye-sensitized solar cells along with N749 (black dye). The DSSC devices with a mixture of
co-sensitizers (CSGR1-5) and N749 have shown a 7.95%, 8.40%, 7.81%, 6.56% and 6.99% power
conversion efficiency (PCE) respectively, which was more than that of single N749 dye PCE (6.18%).
Enhanced efficiency could be ascribed to the increased short circuit current (Jsc) and open circuit
voltage (Voc). The increased Jsc was achieved due to enhanced light harvesting nature of N749
device upon co-sensitization with CSGR dyes and feasible energy levels of both the dyes. The Voc
was improved due to better surface coverage which helps in decreasing the rate of recombination.
The detailed optical and electrochemical properties were investigated and complimented with
theoretical studies (DFT).
Keywords: 3,4-ethylenediox-thiophene; dye-sensitized solar cells; co-sensitizer; power conversion
effiecency; DFT
1
. Introduction
Confronted with the massive challenges of future energy demand and environmental safety,
scientific society and engineers are continuously struggling in finding and developing new energy
resources. Towards finding a solution, the solar energy is recognized as the most reliable and
promising candidate owing to its cleanliness, abundance and easy availability [
silicon-based solar cells, different device techniques such as organic photovoltaic [
cells [ ], Perovskite Solar Cells [ ], Copper Zink Tin Sulfide based solar cells (CZTS) [
both scientific and commercial visibility, among which dye-sensitized solar cells (DSSC) was considered
1
2
]. Recently, apart from
] Dye-sensitized solar
], have achieved
3
4
5
to be the most important device technique [
3,
6,
7]. Since the publication of the first report on DSSC by
Molecules 2019, 24, 3554; doi:10.3390/molecules24193554
www.mdpi.com/journal/molecules

Molecules 2019, 24, 3554
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O’Regan and Grätzal in 1991, the DSSCs have attracted significant attention due to their high-power
conversion efficiency (PCE) of converting incident light to electricity and low-cost production [ ].
Dye-sensitized solar cells (DSCs) could be effectively used in both outdoor and indoor applications.
A great amount of research has been focused on n-type DSC, where a sensitized TiO electrode acts as
8
2
photoanode, reaching an overall efficiency up to 14% [9–11], In a DSSC device, dye sensitizer plays
an essential role in converting the solar energy to electrical energy by harvesting the solar light and
injecting the excited electron into the TiO2 [12]. Wide absorption range of the solar spectrum, high
molar extinction coefficient (εmax), and feasible energy levels are found to be the key parameters
for achieving high efficiency [13
,
14]. Since the past decade, great efforts have been focused on the
advancement of dye-sensitizers [7]. Mostly two different types of sensitizers, namely, metal complexes
and metal-free sensitizers are being used as light harvesters in DSSC. N3, N719, and N749 dyes are
some of the benchmark sensitizers in metal complex-based sensitizers for DSSC, which obtained
more than 10% efficiency, because of their broad absorption range and high Jsc value [15]. However,
using ruthenium sensitizers for DSSC is not optimal because the molar extinction coefficient at higher
wavelength region (
Moreover, structural modifications on ruthenium dyes are limited because a smaller number of
chelating ligands are compatible with the synthesis of various Ru complexes [16 18]. Despifigte a
λmax) is lower than that of organic dyes which limits the light harvesting capacity.
–
higher efficiency, ruthenium dyes suffer with degradation issues due to electrolyte compositions such
as 4-tert-butylpyridine additive or nitrile based solvent molecules, which substitute the NCS ligand on
◦
ruthenium dyes at significant rate of increased temperature (80–100 C) [17,19].
On the other hand, organic dyes can be modified to be able to absorb from the UV-visible range to
near IR range (yellow [20] to red [21
,22] to blue [23,24]) possessing high molar extinction coefficient
than Ru dyes. Moreover, the D- -A type of arrangement of organic sensitizers facilitates infinity range
π
of potential structural modifications [25]. The majority of the reported organic dyes were synthesized
based on triphenylamine, phenothiazine, phenoxazine, carbazole, boron dipyrromethane, squaraine
and indolines [
than 650 nm of maximum absorption wavelength (
these metal-free organic dyes in terms of PCE was less than that of ruthenium-based dyes [16
3
,
26
–
29], in which squarine, phthalocyanines, and cyanine sensitizers have shown more
max) [30]. However, the DSSC performance of
18].
λ
,
To harvest the full solar spectrum using single organic dye, one needs to introduce various groups,
which would again complicate the synthesis and purification process—ultimately enhancing the device
cost [31].
Co-sensitization technology is one of the best alternative approaches to fulfill the limitations of
a single dye approach by sensitizing with a combination of two or more dyes in the DSSC device.
For example, ruthenium dye has lower absorption power with a low molar extinction coefficient at a
higher wavelength region, which would be complemented with the high molar extinction coefficient
of organic dye, thereby imparting panchromatic nature and high PCE to DSSC device. [28,32] Earlier,
numerous combinations have been reported for co-sensitization in DSSC such as Ruthenium dyes
with organic dye and porphyrin with organic dye or metal-free organic dyes, which have shown
an enhanced photovoltaic performance compared to that of single sensitizers. Yella et al., reported
an enhanced efficiency for YD2-O-C8 porphyrin dye from 11.9% to 12.3% after a careful evaluation
of DSSC in the process of co-sensitization using organic sensitizer. Moreover, porphyrins generally
required difficult synthetic procedures with lower yields, notably, when anchoring and a redox group
needs to be added at precise locations [33]. Apart from these, the co-sensitized DSSCs (cocktail DSSC)
using ruthenium complex and metal-free dyes in the DSSC device have been extensively examined in
the recent past. In our group, we have achieved a 11.4% certified record efficiency using a combination
of N749 dye and Y1 organic dye [34]. It was mostly because of a change in the molecular size of the
dyes, which was able to adequately adsorb on the surface of the TiO semiconductor, thereby enabling
2
the device to harvest a larger number of incident photons from the light [35
results various research groups, [35], in addition to our group [33 35 38], designed numerous organic
co-sensitizers using high electron donors such as triphenylamine, indole, carbazole, phenothiazine,
,36]. Inspired by these
,
–

Molecules 2019, 24, 3554
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thiophene, etc. [39]. So far, very little research has been focused on small size co-sensitizers (such as
Y1) possessing feasible optical and electrochemical properties with ruthenium complexes, which were
known to be more advantageous than that of various organic dyes, because of their ability to adsorb
into pores and gaps of TiO semiconductor surface, whereas the three dimensional ruthenium-based
2
dyes cannot get adsorbed [
of N749 and Y1 dyes by testing 1100 h of 1 sun light soaking at 55 C, which showed remarkable
enhancement in stability of the device by employing the Y1 as co-sensitizers [19].
7
,
40]. Moreover, in our group, we have reported a co-sensitized system
◦
3
,4-ethylenediox-thiophene (EDOT) unit has been widely used as a conjugated bridge unit between
the acceptor and donor groups of DSSC dyes, due to its capability to accelerate co-planarity and
enhance the light harvesting capacity [41]. So far, 6% efficiency has been reported with EDOT based
dyes, which were further extended to 8.2% by optimizing the anchoring group [30]. To carry forward
the advantages of small organic co-sensitizers in cocktail DSSC and emphasize the role of EDOT
central moiety, we have designed five small size new organic co-sensitizers coded as CSGR1-CSGRR5
in D-π-A manner. These five co-sensitizers (CSGR1-5), as shown in Figure 1, were synthesized by
changing the donating groups (2,3,4-trimethoxypheny, 2,4-dibutoxyphenyl, 2,4-difluorophenyl) and
anchoring groups (cyano-acrylic acid (CA) and rhodamine acetic acid (RA)) systematically and their
DSSC performance as co-sensitizer with the N749 dye was examined. The final structure of CSGR1-5
dyes and N749 were shown in Figure 1.
Figure 1. Chemical Structures of CSGR1-5 dyes.
2
. Experimental Section
2
.1. General
The 2,3-dihydrothieno[3,4-b][1,4]dioxine (EDOT), (2,3,4-trimethoxyphenyl)boronic acid (2,3,4-
trimethoxyphenyl)boronic acid, (2,4-difluorophenyl)boronic acid, and (2,4-dibutoxyphenyl)boronic
acid materials were bought from Sigma-Aldrich. The analytical grade solvents and chemicals were
utilized for the synthesis and all the chemical reactions were carried out in the argon atmosphere.
1
13
6
0-120 mesh silica gel was used for chromatographic separations. H-NMR and C -were performed
on a Varian Mercury NMR 300 MHz spectrometers in CDCl or C D O solvent, where TMS was used
3
3
6
as an internal reference. Absorption and emission spectra were recorded on an Agilent 8453 UV-vis
spectrophotometer and Jobin-Yvon Horiba model fluorolog3 spectrometer, respectively. The cyclic

Molecules 2019, 24, 3554
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(
CV) or deferential pulses voltammograms (DPV) were acquired in DMF solution containing 0.3 mM
dye and 0.1M tetrabutylammonium hexafluorophosphate (n-Bu NPF ). The three electrodes consisted
4
6
of Pt wire counter electrode and Ag/AgCl reference electrodes with a 50 mV/s scan rate.
2
.2. Solar Cell Fabrication and Photovoltaic Characterization
The transparent conducting glasses (fluorine-doped tin oxide (FTO)) were cleaned carefully using
ethanol, D.I water and acetone in an ultra-sonication process, respectively. The cleaned FTO glasses
2
(
Pilkington, 15
Ω
/cm ) were coated with transparent TiO pastes (20–30 nm, Dyesol Ltd.) using the
2
◦
doctor blade method, followed by calcination for 30 min at 450 C. The TiO scattering layer (200 nm,
2
Dyesol Ltd.) consists of rutile TiO , which was deposited on the transparent mesoporous TiO films,
2
2
◦
followed by sintering at 450 C for 30 min. Two layers of TiO films were dipped in a 40 mM aqueous
solution of TiCl at 70 C for 30 min and then sintered at 450 C for 30 min. The TiO thin films were
2
◦
◦
4
2
◦
immersed in the dye solution for 24 h in the dark at 25 C. Where dye solution was prepared using
.1 mM of CSGR dyes in THF and 0.2 mM N749 dye in tert-butanol and acetonitrile mixed solvent (1:1).
After 24 h of soaking, the residual dye was rinsed with acetonitrile and dried. The platinum catalyst
counter electrodes were prepared on FTO glasses using the doctor blade technique by H PtCl solution,
followed by pyrolysis at 450 C for 30 min. The working electrode and Pt counter electrodes were
assembled into a sealed sandwich cell with a 60 mm thick thermal adhesive film (Surlyn film, Dupont),
which was then introduced with a liquid electrolyte solution containing 1-butyl-3-methylimidazolium
iodide (0.7 M), lithium iodide (LiI, 0.2 M), iodine (I2, 0.05 M), and t-butylpyridine (TBP, 0.5 M) in
acetonitrile/ valeronitrile (85:15, v/v) through pre-drilled two holes on the counter electrode.
The photo-current density-voltage (J-V) characteristics of synthesized dyes were measured
0
2
6
◦
2
under AM 1.5 irradiation with an irradiance of 100 mW/cm (PEC-L11, Peccell Technologies,
Inc.). The incident monochromatic photon-to-current efficiencies (IPCEs) were measured using
IPCE measurement instrument (PEC-S20, Peccell Technologies, Inc.) as a function of wavelength.
Electrochemical impedance spectroscopy (EIS) was recorded using computer-controlled potentiostat
(IVIUMSTAT, IVIUM) software at the open circuit voltage with a 10 mV of amplitude and an AC
frequency range between 100 kHz and 0.1 Hz (PEC-L11, Peccell Technologies, Inc.)
2
.3. Procedures for the Synthesis of CSGR Dyes
The detailed synthesis procedure for intermediate steps of CSGR dyes have been discussed
supporting information.
(
(
i) 4(E)-2-cyano-3-(7-(2,3,4-trimethoxyphenyl)-2,3-dihydrothieno[3,4-b][
CSGR1) [2,39].
1,4]dioxin-5-yl)acrylic acid
A mixture of compound 3a (0.120 g, 0.2 mmol), 2-cyanoacetic acid (0.056 g, 0.6 mmol), ammonium
◦
acetate (3 mg), and acetic acid (11 mL) was heated at 120 C for 12 h. After cooling, water was added
to quench the reaction. The precipitate was filtered and washed with water. The residue was purified
by column chromatography on silica gel (CH Cl /methanol = 10/1, v/v) to yield CSGR1 as a red solid
2
2
1
(
4
118 mg, 88.5%). HNMR (300 MHz, CDCl , δppm) 8.93 (s, 1H), 7.89 (d, 1H), 6.61 (d, 1H), 4.42 (m, 2H),
.27 (m, 2H), 3.72(s, 3H), 3.69 (s, 3H), 3.61(s, 3H). C NMR (75 MHz, CDCl3,
3
13
δppm ): 162.7, 156.3, 146.5,
1
4
7
45.4, 139.8, 134.1, 130.9, 127.9, 114.7, 112.5, 103.1, 64.6, 62.2, 56.3. ESI-MS (C H NO S): calculated:
19
17
7
03.07, found: 402.06 (M
−
H). CHNS analysis calculated for C H NO S C: 56.57, H: 4.25, N: 3.47, S:
19 17 7
.95, found: C: 56.42, H: 4.11, N: 3.39, S: 7.83
(ii) (E)-2-cyano-3-(7-(2,4-dibutoxyphenyl)-2,3-dihydrothieno[3,4-b][
1,4]dioxin-5-yl)acrylic
acid (CSGR2).
Dye CSGR2 was synthesized by employing the same procedure as that for CSGR1 to yield red
1
solid (0.108 mg, 81%) HNMR (300 MHz, CDCl ,
1
δ
ppm) 8.96 (s, 1H), 7.61 (d, 1H), 6.98 (d, 1H), 6.62 (m,
3
13
H), 4.47 (m, 2H), 4.37–4.29 (m, 6 H), 1.83 (m, 4H), 1.41 (m, 4H), 0.93 (t, 6H). C NMR (75 MHz, CDCl3,

Molecules 2019, 24, 3554
5 of 18
δ
ppm): 163.1, 161.8, 155.6, 145.9, 144.5, 133.1, 131.8, 128.2, 114.7, 103.1, 99.5, 68.8, 67.6, 64.3, 31.4, 19.7,
4.2. ESI-MS: calcd 457.16, found: 356.14 (M H). CHNS analysis calculated for C H NO S C: 63.00,
H: 5.95, N: 3.06, S: 7.01, found: C: 62.97, H: 5.91, N: 2.98, S: 6.93.
1
−
24
27
6
(iii) (E)-2-cyano-3-(7-(2,4-difluorophenyl)-2,3-dihydrothieno[3,4-b][1,4]dioxin-5-yl)acrylic
acid (CSGR3).
Dye CSGR3 was synthesized by employing the same procedure as that for CSGR1 to yield red
1
solid (0.108 mg, 81%) HNMR (300 MHz, CDCl ,
1
1
δ
ppm) 8.93 (s, 1H), 7.78 (d, 1H), 7.31 (m, 1H), 7.11 (d,
ppm): 163.8, 162.3, 160.2, 145.9, 144.2,
33.0, 130.6, 127.7, 114.9, 104.7, 103.1, 64.6. ESI-MS: calculated: 349.02, found: 348.01 (M -H) CHNS
3
H), 4.56 (m, 2H), 4.41 (m, 2H). 13C NMR (75 MHz, CDCl3,
δ
analysis calculated for C H F NO S C: 55.01, H: 2.60, N: 4.01, S: 9.18, found: C: 54.97, H: 2.51, N: 3.88,
16
9
2
4
S: 9.07.
iv) (E)-2-(2-oxo-4-thioxo-5-((7-(2,3,4-trimethoxyphenyl)-2,3-dihydrothieno[3,4-b][
]dioxin-5-yl)methylene)thiazolidin-3-yl)acetic acid (CSGR4).
The CSGR4 was synthesized by following the procedure used for the synthesis of CSGR1, except
(
1,
4
the use of rhodanine-3-acetic acid (0.036 g, 0.376 mmol) anchoring group instead of 2-cyanoacetic acid
1
to afford CSGR4 (0.115 g, 86%) as a dark yellow solid. HNMR (300 MHz, CDCl ,
1
1
δ
ppm): 8.13 (s,
ppm): 196.2,
70.7, 169.6, 156.1, 144.9, 141.2, 133.5, 131.1, 128.6, 119.3, 113.1, 64.5, 60.9, 56.4, 51.8. ESI-MS: calculated:
09.03, found: 508.02 (M -H). CHNS analysis calculated for C H NO S C: 49.50, H: 3.76, N: 2.75, S:
3
13
H), 7.90 (d, 1H), 6.85 (d, 1H), 4.71 (m, 2H), 4.45 (m, 4H). C NMR (75 MHz, CDCl3, δ
5
21
19
8 3
1
8.88, found: C: 49.39, H: 3.65, N: 2.61, S: 18.79.
v) (E)-2-(5-((7-(2,4-dibutoxyphenyl)-2,3-dihydrothieno[3,4-b][
thioxothiazolidin-3-yl)acetic acid (CSGR5).
(
1,4]dioxin-5-yl)methylene)-2-oxo-4-
The CSGR4 was synthesized by following the procedure used for the synthesis of CSGR1, except
the use of rhodanine-3-acetic acid (0.036 g, 0.376 mmol) anchoring group instead of 2-cyanoacetic
1
acid to afford CSGR5 (0.121 g, 87%) as a dark yellow solid. HNMR (300 MHz, CDCl ,
(
δ
ppm): 8.10
3
d, 1H), 7.48 (s, 1H), 6.86 (m, 1H), 6.62 (s, 1H), 4.63 (m, 2H), 4.28-4.21 (m, 6H). 1 C NMR (75 MHz,
3
CDCl3,
δ
ppm): 196.2, 171.5, 170.2, 162.3, 155.7, 144.6, 133.1, 129.9, 127.7, 119.6, 114.7, 99.8, 69.3, 64.6,
H). CHNS analysis calculated for
C H2 NO S C: 55.40, H: 5.19, N: 2.48, S: 17.18, found: C: 55.37, H: 5.13, N: 2.36, S: 16.88.
5
2.2, 31.5, 19.4, 13.9. ESI-MS: calculated: 563.11, found: 562.11 (M
−
26
9
7 3
3
. Results and Discussion
3
.1. Synthesis
We have synthesized five organic molecules in D-π-A manner, by systematically replacing them
with the substituted benzenes as donors and the CA and RA as acceptors on ethylene dioxythiophene
center core moiety. All the sensitizers were well characterized with NMR and MASS spectroscopy.
The reaction path and conditions for the synthesis of CSGR1-5 sensitizers were shown in
Figure 2. The commercially accessible material 3,4-Ethylenedioxythiophene was subjected to
Vilsmeier-Haak Formylation reaction to acquire the intermediate Compound
Compound was brominated using N-Bromosuccinimide to obtain Compound
The desired compounds (3a 3d) were accomplished by condensation reaction via Suzuki coupling
1
with a 81% yield.
1
2 with a 64% yield.
–
with corresponding boronic acids, (2,3,4-trimethoxyphenyl)boronic acids, (2,4-dibutoxyphenyl)boronic
acid and (2,4-difluorophenyl)boronic acid with a 60% to 69% yield. The final compounds (CSGR1-5)
were synthesized from the 3a
–3d by following Knovanagal condensation with CA or RA anchoring
groups using NH OAC and acetic acid with good yields (89% to 91%).
4

Molecules 2019, 24, 3554
6 of 18
Figure 2. Synthesis of CSGR1-5 Sensitizers.
3
.2. Optical and Electrochemical Measurements
The electronic absorption spectra of co-sensitizers (CSGR1-5) in N,N-Dimethylformamide (DMF)
were shown in Figure 3a, and the resultant data were summarized in Table 1. CSGR1-5 dyes displayed
two major bands in the Figure 3a, the band present at the lower wavelength region corresponds to the
π
-
π
* transitions localized between auxiliary donors and EDOT center moiety and another band present
at the higher wavelength region (300–550) corresponds to the charge transfer (CT) between EDOT and
the CA or RA anchoring groups [42]. The wavelength maximum ( max) of the CSGR1-5 dyes in DMF
solution was 402, 408, 376, 450 and 482 nm, respectively. All the CSGR dyes have shown higher molar
λ
4
−1
−1
extinction co-efficient (εmax) than N749 (0.8725
×
10 M cm ) at 300 to 550 regions i.e., 4.3904, 4.1182,
4
−1
−1
3.3557, 4.7688 and 4.9522
×
10 M cm . It is worth mentioning that the high εmax demonstrated by
these co-sensitizers (CSGR dyes) at CT transition range was beneficial for harvesting maximum number
of photons from incident light at a particular wavelength region by a minimum amount of dye loading
so that it could facilitate enough space on the semiconductor (TiO ) for binding of other dye molecules.
2
Among CA and RA based dyes, high absorption property was observed for RA based dyes (25–80 nm),
which was attributed to the enhanced
anchoring group. Among 2,3,4-trimethoxybenzene (CSGR1 and CSGR4) and 2,4-dibutoxybenzene
CSGR2 and CSGR5) based dyes, a high absorption nature was observed for 2,4-dibutoxybenzene
π-conjugation due to 4-oxo-2-thioxothiazolidine ring in RA
(
based dyes, which indicates the low donating nature of 2,4-dibutoxybenzene donating group than that
of 2,4-dibutoxybenzene.
Figure 3b illustrates the absorption spectra of the CSGR dyes on TiO thin films in comparison
2
with N749 dye. The TiO film sensitized with CSGR dyes has displayed a
4
λ
max of 415, 437, 389,
36 and 471 nm respectively, which were found to be a red shift of CSGR1-3 dyes by 13, 29 and
3 nm upon adsorption on TiO . Generally, this type of red shifted absorption spectra on TiO
2
1
2
2
compared to the solution state absorption spectra have been observed for many dyes in organic,
which could be attributed to the J-aggregation that benefits the capture of photons from an extended
region [13] Whereas CSGR5 and 6 have shown blue shifted absorption spectra of about 14 and 11 nm,
which indicates the low energy transfer with TiO2.

Molecules 2019, 24, 3554
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Figure 3. (a) UV-visible Spectral analysis of CSGR1-5 in DMF solution and (b) on TiO thin film.
2
Table 1. Photophysical and electrochemical data of CSGR1-5 dyes.
λmax (Solution)
E
λmax (TiO2)
λem
(nm)
Stokes Shif
(nm)
E0X
(V)
E0-0
(V)
E0X*
(V)
HOMO
(eV)
LUMO
(eV)
Dye
nm) a
(M Cm
−1
−1
)
(nm) b
c
d
e
f
g
h
(
CSGR1
CSGR2
CSGR3
CSGR4
CSGR5
N749
402
408
376
450
482
623
41182
43904
33557
47688
49522
8725
415
437
389
436
471
618
526
533
478
528
574
101
114
85
92
78
0.773
0.829
0.789
0.793
0.785
2.56
2.53
2.81
2.55
2.33
−1.787
−1.701
−2.021
−1.757
−1.545
5.473
5.529
5.489
5.493
5.485
−2.913
−2.993
−2.679
−2.943
a
Absorption spectra were measured in DMF. b Absorption spectra were measured on TiO
thin film. c Emission in
2
DMF. d Oxidation potentials (E0X) were measured using CV and DPV method from onsite potentials. The bandgap
e
f
g
(E
0-0), was obtained from the UV-visible and emission intercept plots.
E
OX*= (Eox
−
E0-0). HOMO = e[Eox (V) +
−
h
4
.7 ev]. LUMO = −e[(Eox (v) + 4.7) − E0-0] eV.
In order to understand the effect of individual dye on overall light absorption profile of cocktail
dyes, we have performed the absorption spectra of cocktail dyes in solution state and on TiO2
thin film, which were displayed in Figures 4 and 5 by comparing with their individual absorption
properties. In the solution state, absorption spectra displayed enhanced absorbance profile for the
cocktail dye solution in the range 300–550 nm compared to their corresponding individual dyes, which
could be attributed to the strong molar extinction co-efficient of EDOT based CSGR dyes. Similarly,
the same enhanced absorption profile was observed when absorption spectra were analyzed on TiO2.
These results indicate that the cocktail dye system of N749 and CSGR dyes shows better light harvesting
efficiency than that of individual N749 dye in this wavelength region.
Figure 4.
(a–e) are comparative absorption spectra of CSGR (0.05 mm), N749 (0.1 mm) and mixture of
N749 and CSGR1-5 dyes (0.1 and 0.05 mm) in DMF.

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Figure 5.
(a–e) are comparative absorption spectra of CSGR (0.3 mm), N749 (0.3 mm) and mixture of
N749 and CSGR dyes (0.2 and 0.1 mm) on TiO2.
The emission spectra of CSGR dyes were measured in the DMF solvent upon excitation at their
λmax, and corresponding curves and data were shown in Figure S1 and Table 1. Figure S1 shows the
absorption fluorescence intercept plots, which were used for calculating their bandgap and stock shift
values. The observed large stock shift values (80–120 nm) suggests the efficient intramolecular charge
transfer [43].
The CV was performed to ensure the electrochemical nature and evaluate positions of the ground
state oxidation potential [GSOP (Eox)] and excited state oxidation potentials [ESOP (Eox*)] of the
CSGR dyes. CV and DPV were executed for CSGR dyes using DMF solution of 0.1 M TBAPF6
support electrolytes. The corresponding curves and data were presented in Figure 6 and Table 1.
The analyzed GSOP of CSGR1-5 dyes were 0.773, 0.829, 0.789, 0.793, and 0.785 V (versus NHE)
respectively, Here, onset oxidation potentials of oxidation peak of CV and DPV were used to calculate
−
−
the GSOP, which were highly positive enough than that of redox electrolyte (I /I3 ), i.e., 0.4 V (
eV) versus NHE [43] for efficient dye regeneration. The ESOP (Eox*) of CSGR1-5 dyes were 1.827,
.751, 2.021, 1.535 and 1.717 V, respectively, which were obtained by subtracting E0-0 from Eox (Eox
E0-0). Here E of CSGR dyes was measured from the intercept plots of absorption and fluorescence
−
5.2
1
−
−
–
0-0
(Figure 5) by using the following formula:
1
240
λ
E0
=
(1)
−0
Here, wavelength (
λ
) is considered from the absorption and emission intercept point. The obtained
*
E0-0 values of CSGR dye were 2.56, 2.53, 2.81, 2.55 and 2.33 eV, respectively. The ESOP (Eox ) of CSGR1-5
dyes were highly negative than that of TiO semiconductor conduction band, i.e., ~0.5 V versus NHE
2
(
−
4.2 eV), facilitating adequate electron injection. The schematic energy level diagram for CSGR dyes
was constructed based on the obtained results as shown in Figure 7.
3
.3. Computational Studies
To explore the structural, electrochemical, and photophysical properties of the CSGR1 to CSGR5
dyes, we have carried out a thorough computational investigation. All the reported calculations have
been performed by Gaussian 16 quantum chemistry software [44]. The ground state geometries of the
dyes were optimized using a hybrid B3LYP [45,46] functional in combination with the 6-31G(d) basis
set. The minima of the structures on the potential energy surface were confirmed from the vibrational
frequency analysis with no imaginary frequencies. The optimized geometries were then subjected

Molecules 2019, 24, 3554
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to time-dependent density functional theory (TDDFT) simulations to obtain UV-visible absorption
spectra of the dyes. The photophysical properties of the dyes for the first 25 excited states were
simulated in DMF solvent. The solvent effects in simulations were considered using the polarizable
continuum model [47,48] as implemented in Gaussian 16. The TDDFT simulations were performed
using TD-CAM-B3LYP function at the same level of a theory similar to that used for the ground state
optimization of the dyes.
Figure 6. CV and DPV voltammograms of CSGR1-5 dyes in DMF.
Figure 7. The schematic energy level diagram for CSGR1-5 based on UV-visible absorption and
electrochemical data.
Figure 8 shows the optimized geometries of five dyes, CSGR1 to CSGR5 along with the dihedral
angles between thiophene and attached phenyl ring. The observed dihedral angles were found to be
◦
around 50 . The substitutions present on the phenyl ring disturbed the planarity of the dye molecule.

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The nonplanar structure of the dye prevents the dye aggregation on TiO thereby resulting in the
2,
improved power conversion efficiency.
Figure 8. Optimized ground state geometries of the dyes CSGR1 to CSGR5 obtained at B3LYP/6-31G(d)
level of theory.
Electron density distribution plots of the dyes were obtained from the population analysis and
their frontier molecular orbitals along with their eigenvalues, as shown in Figure 9. The electron
density in HOMO was mainly located on the EDOT moiety and shifted towards the anchoring group
in LUMO. From Figure 8, it can be observed that the electron density transfer towards the anchoring
group was more in case of cyanoacetic acid (CA) based dyes over rhodamine acetic (RA) acid-based
dyes. The low electron density shift in RA anchoring dyes was due to the presence of a methylene
group between -COOH and EDOT moiety, which lowers the charge transfer. The low power conversion
efficiency exhibited by RA-based dyes over CA-based dyes could be attributed to their low electron
transfer to the anchoring group, thereby leading to poor electron injection to the TiO conduction band.
2
The theoretically obtained HOMO and LUMO values were in good agreement with the experimental
data obtained from the cyclic voltammetry.
Figure 9. Cont.

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Figure 9. Electron density distribution in frontier molecular orbitals of the dyes CSGR1 to CSGR5 and
the corresponding eigenvalues.
The optical properties of the dyes were obtained using TDDFT formalism, and the simulated
absorption spectra were shown in Figure 10. The theoretically calculated absorption spectra reproduced
the absorption bands that were observed in the experimental UV-visible absorption spectra. CSGR1 to
CSGR3 dyes have shown intense absorption maxima around 375 nm, whereas, CSGR4 and CSGR5
dyes have shown intense absorption maxima around 460 nm. Compared to the absorption of the
dye CSGR1, the dyes CSGR2 and CSGR3 have shown 8 nm bathochromic and 9 nm hypochromic
shifts, respectively. Among CSGR4 and CSGR5 dyes, CSGR5 has shown 9 nm bathochromic shifts
compared to that of CSGR4. These intense absorption peaks originated mainly from the HOMO
LUMO excitation. The observed shifts in the experimental absorption spectra were reproduced from
the simulations.
→

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Figure 10. Simulated UV-visible absorption spectra of the dyes CSGR1 to CSGR5 obtained in DMF
solvent at TD-CAM-B3LYP/6-31G(d) level of theory.
3
.4. Photovoltaic Properties
The photovoltaic performances of the co-sensitized DSSC devices (cocktail DSSC) were examined
to establish a relationship between structures of co-sensitizer and their performances with ruthenium
dyes. The addition of varying auxiliary substituents and anchoring groups (CA and RA) on the principal
moiety of EDOT have shown to have a profound influence on the incident photon-to-current conversion
efficiency (IPCE) and photovoltaic properties of the cocktail DSSC devices. The photovoltaic properties
of the DSSC devices sensitized with N749 and co-sensitizers (CSGR1-5 dyes) on a TiO semiconductor
2
−
2
electrode have been analyzed in standard AM 1.5 irradiations (100 mW/cm ). The resultant
current-voltage (J-V) plots have been presented in Figure 11b and the related data was summarized in
Table 2. By using CSGR dyes as co-sensitizers instead of N749 dye alone, the photovoltaic performance
of DSSC was enhanced as observed in J-V curves and Table 2. The overall conversion efficiency (ï)
of N749 alone was 6.18, whereas by using EDOT co-sensitizers (CSGR1-5) the efficiency has been
enhanced to 7.95%, 8.40%, 7.81%, 6.56% and 6.99% respectively. The observed enhanced efficiency
could be attributed to the improved photovoltaic parameters i.e., short-circuit current density (Jsc),
−2
open-circuit voltage (Voc) and fill factor (FF). The Jsc and Voc of N749 alone were 14.73 mA cm and
.648 V, whereas after employing CSGR1-5 co-sensitizers the Jsc was enhanced to 18.51, 18.55, 18.15,
0
-
2
15.72, and 16.59 mA cm , respectively, and the Voc was enhanced to 0.659, 0.674, 0.658, 0.634 and
0
3
.651 V, respectively. The enhanced Jsc might be ascribed to the increased light harvesting nature at
00–500 nm regions due to the addition of CSGR co-sensitizers, which possess a high molar absorption
coefficient. The observed enhanced Voc of cocktail DSSC devices could be attributed to the decreased
recombination rate between the injected electrons in the conduction band of TiO semiconductor and
2
-
I3 species in the redox electrolyte. Owing to their small size, the co-sensitizers provide better surface
coverage [19,34,37] by getting adsorbed into the pores and gaps on TiO , whereas the ruthenium-based
2
dye molecules cannot get absorbed (discussed in detail in dye loading section). Though RA based
co-sensitizers have shown high absorption properties in DMF solvent than CA based dyes, it could not
be transformed into high efficiency. As mentioned by Weihong Zhu et al. [49], this might be due to the
methylene group present between EDOT center moiety and carboxylic acid, which would prevent
efficient electron injection into the conduction band of TiO by breaking the conjugation. Therefore,
2
the resulting unfavourable distribution of LUMO may possibly lead to low PCE for RA based dyes.
Among all the co-sensitizers, CSGR2 and N749 based cocktail DSSC device has shown highest Jsc, Voc
and efficiency due to high light harvesting nature of CSGR2.
,

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Figure 11.
(a) IPCE and integrated current density plots and (b) are the J-V plots of DSSCs based on
N749 dye with CSGR1-5 dyes.
Table 2. Photovoltaic measurement data of fabricated DSSC devices.
JSC (mA cm 2)
−
Dye
VOC (V)
FF
η (%)
N749
14.73
4.32 + 0.41
18.51
7.84 + 0.58
18.55
8.34 + 0.44
18.15
7.51 + 0.41
15.72
5.10 + 0.45
16.59
0.648
0.637 + 0.008
0.659
0.641 + 0.010
0.674
0.659 + 0.009
0.658
0.648 + 0.008
0.634
64.74
64.08 + 0.55
65.18
66.802 + 1.24
67.08
66.90 + 0,74
65.42
65.27 + 1.04
65.83
6.18
5.84 + 0.13
7.95
7.62 + 0.19
8.40
8.07 + 0.12
7.81
7.39 + 0.13
6.56
1
1
1
1
1
1
N749 + CSGR1
N749 + CSGR2
N749 + CSGR3
N749 + CSGR4
N749 + CSGR5
0.632 + 0.005
0.651
0.647 + 0.010
65.95 + 0.90
64.68
64.18 + 1.05
6.29 + 0.22
6.99
6.66 + 0.22
5.99 + 0.53
Average values and the error bars are calculated based on five cells and samples. Parameters of the best cell are
highlighted in bold.
The IPCE for the DSSC sensitized with N749 and cocktail DSSC devices (co-sensitizers and N749)
have been measured and plotted in Figure 11a. All the DSSC devices have shown broad coverage
of IPCE spectra from visible range to near IR range. The DSSC devices sensitized with N749 and
CSGR1-CSGR3 have shown impressive IPCE in the 300 to 500 region, compared to N749 alone, with an
unfavourable 72%, 73% and 60%, respectively. This might be because of the high molar extinction
− −1
1
coefficient of CSGR1-CSGR3 dyes than that of the I3- (2.5
×
104 m cm ) at this particular wavelength.
Therefore, these co-sensitizers reduced the competitive absorption with electrolyte resulting in the
enhancement of IPCE [50], whereas RA based co-sensitizers failed to enhance the IPCE as expected
because of the low electron injection efficiency due to the methylene group and unfavourable LUMO
distribution [49]. According to the IPCE spectra, the integrated current density of CSGR and N749
2
dyes were 19.76, 20.91, 19.12, 17.16, 17.70 and 17.01, mA/cm , respectively. The obtained Jsc values
trend has matched with their respective J-V characteristics, within the error range.
To further understand the recombination rate and charge recombination lifetime in the DSSC device
by employing CSGR1-5 co-sensitizers along with N749, the electrochemical impedance spectroscopy
(EIS) was executed under dark condition. The Nyquist and bode plots for N749 and co-sensitized
devices of CSGR1-5 were shown in Figure 12a,b, and the equivalent circuit fitting results were
summarized in Table 3. In the EIS Nyquist plots, three semicircles were observed, the first and small
semicircle at higher frequency region corresponds to the charge transfer process (R2) at the counter
electrode and electrolyte interfaces. The large or mid-frequency region signifies the recombination

Molecules 2019, 24, 3554
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resistance (R3) at the working electrode of the TiO /dye/electrolyte interface [39
(
,
49]. The third semicircle
2
− −
low-frequency range) indicates the Warburg diffusion process of I /I . The obtained recombination
3
resistance values (R3) in dark impedance analysis of DSSC devices with N749 and CSGR dyes were
9.38, 20.37, 15.28, 12.6, and 15.64 , respectively. As a matter of fact, the higher the R3 values, the lower
1
Ω
the charge recombination rate between the conduction band of TiO semiconductor and the electrolyte
2
will be. The R3 values of cocktail DSSC devices with N749 and CSGR dyes decreased in the order of
CSGR2 > CSGR1 > CSGR3 > CSGR5 > CSGR4 > N749. The obtained R3 values were consistent with
the Voc values obtained in J-V curves. Among all the CA and RA based co-sensitizers, the dye with
the 2,4-dibutoxyphenyl group showed higher R3 values, which indicates that the introduction of the
dibutoxy group on the donor group of EDOT dyes has greatly enhanced the charge recombination
resistance compared to other donating groups in CSGR dyes. Furthermore, the Bode phase plots
(
Figure 12b) were analyzed to determine the injected electron recombination lifetime of eTiO by
2
following the relation,
τ
= 1/2πƒ in which
τ
is electron lifetime in TiO and ƒ is the peak frequency
CB 2
CB
from bode plots. The electron lifetime for the CSGR co-sensitized DSSC devices and N749 dye was
found to be 4.46, 4.75, 3.89, 2.43, 3.08 and 2.17 ms, respectively. The observed trend of the recombination
lifetime was in par with the EIS results and VOC. These results clearly portray the advantage of using
co-sensitizers in obtaining decreased recombination rate and increased recombination life time owing
to their small size and strong anchoring groups [40,51].
Figure 12. (a) EIS Nyquist plots of cocktail DSSC devices of N749 and CSGR dyes measured under a
dark condition. (b) Bode-Phase plots for cocktail DSSC devices of N749 and CSGR dyes.
Table 3. EIS analysis data obtained by fitting in an equivalent circuit.
Dye
R1
R2
R3
τe (ms)
N749 + CSGR1
N749 + CSGR2
N749 + CSGR3
N749 + CSGR4
N749 + CSGR5
N749
7.138
6.785
6.763
7.124
6.393
7.139
3.165
3.197
3.328
3.439
3.538
3.206
19.38
20.37
15.28
12.6
15.64
11.72
4.46
4.75
3.89
2.43
3.08
2.17
3
.5. Dye Loading Analysis
In order to quantify the dye loading on the co-sensitized TiO thin film, adsorption-desorption
2
studies were carried out for CSGR and N749 dyes both individually and in combination as well. Initially,
the individually sensitized TiO films were dipped into 0.02 M NaOH solution, and the approximate
2
amount of dye loading was calculated by analysing the absorption spectra of NaOH solution by
−
7
monitoring the peak at their
λmax [42]. The dye loading amount of CSGR dyes were 4.17
×
10 , 4.21

Molecules 2019, 24, 3554
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−
−7
−7
−7
−2
−
×
10 7, 3.92
×
10 , 3.11
×
10 and 3.22
×
10 mol cm , respectively, while N749 has 2.45
×
10 mol
−
2
−7
−7
−7
cm . The total dye loading of co-sensitized photoanode was 3.43
×
10 , 3.51
×
10 , 3.28
×
10 , 2.92
−
7
−7
×
10 , 3.09
×
10 mol. These results could be explained by the differences in molecular sizes and
anchoring groups of N749 and CSGR dyes. Increased dye loading was accomplished by the adsorption
of larger size N749 molecules onto TiO initially followed by the adsorption of smaller size CSGR
2
molecules in such a way that it would fill the gaps between larger N749 molecules in the process of
sensitization. In comparison to N749 molecules, CSGR dyes exhibit higher binding capacity to the TiO2
surface owing to their small size and strong anchoring group [51]. The back–electron recombination
with the electrolyte or dye molecules was further prevented by the formation of a blocking layer
covering the complete TiO nanoparticle due to increased dye loading [42,51]. This eventually led to
2
decreased recombinations and increased Voc values, as evidently observed in case of experimentally
co-sensitized DSSC.
4
. Conclusions
In summary, a new series of EDOT based co-sensitizers (CSGR1-5) have been synthesized and
explored along with the N749 for cocktail DSSC, and their relative performances were compared.
The efficiencies were significantly enhanced from 6.18% to 7.95%, 8.40%, 7.81%, 6.99% and 6.56%,
respectively. The corresponding enhancement in the efficiencies could be attributed to the increased
IPCE at 300–550 nm regions, possibly due to the complementary absorption property of the co-sensitizers
with the electrolyte and N719 dye, thereby harvesting a larger number of photons at this region,
which in turn enhanced the Jsc and PCE. Moreover, improved Voc values were observed for cocktail
DSSC devices than N749 based dyes, most likely due to the small size of co-sensitizers, which may
occupy the pores and gaps between the three-dimensional ruthenium-based dyes resulting in the
suppression of back electron recombination by preventing the interaction between TiO semiconductor
2
and I3- electrolyte ions—evidently observed in EIS analysis. Among the co-sensitizers, RA based
dyes have shown low PCE than CA-based dyes, which might be ascribed to the low electron injection
efficiency due to the presence of methylene group between the anchoring group and EDOT center
moiety of RA based dyes. This eventually led to the unfavourable LUMO distribution—evidently
observed from the electron density distribution plots (Figure 9). Among CA based dyes, observed PCE
performance decreased in the order of CSGR2 > CSGR1 > CSGR3, which depicted the donating nature
of auxiliary groups (2,4-dibutoxyphenyl, 2,3,4-trimethoxyphenyl, and 2,4-difluorophenyl).
Supplementary Materials: The Supplementary Materials are available online.
Author Contributions: G.K.: Synthesis, manuscript preparation, and contribution to all other measurement
S.T.: Contribution to synthesis and all other measurement; R.K.C.: Performed the theoretical studies (DFT);
J.J.; supervision of the DFT studies; J.H.K.: supervision of the device fabrication and contributed the concepts
in manuscript preparation; J.H.J.: Project leader, concepts and contribution in manuscript preparation; M.C.:
supervision of the synthesis part and conceptual contribution in manuscript preparation.
Funding: This research was funded by “Human Resources Program in Energy Technology” of the Korea Institute
of Energy Technology Evaluation and Planning (KETEP), granted financial resource from the Ministry of Trade,
Industry & Energy, Republic of Korea. (No. 20174030201760). This work was supported by the Korea Institute of
Energy Technology Evaluation and Planning (KETEP) and the Ministry of Trade, Industry & Energy (MOTIE)
of the Republic of Korea (No. 20163010012310). Fundamental R&D program for Core Technology of Materials
(
10050966) funded by the Knowledge Economy, Republic of Korea. MC thank DST, New Delhi for funding
the project No. DST/TMC/SERI/FR/92 and Director CSIR-IICT for the support (CSIR-IICT communication No.
IICT/pubs./2019/225)
Conflicts of Interest: The authors declare no conflict of interest.

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Sample Availability: Samples of the compounds are available upon request
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