Novel Absorber Material Design Based on Thiazole Derivatives Using DFT/TD-DFT Calculation Methods for High-Performance Dye Sensitized Solar Cell ...
←
→
Page content transcription
If your browser does not render page correctly, please read the page content below
Research Article 16
Indones. J. Chem. Stud.
2022, 1(1), 16–23
Available online at journal.solusiriset.com
e-ISSN: 2830-7658; p-ISSN: 2830-778X
Novel Absorber Material Design Based on Thiazole Derivatives
Using DFT/TD-DFT Calculation Methods for High-Performance
Dye Sensitized Solar Cell
Naufan Nurrosyid1,2*, Mirad Fahri1, Yusuf Bramastya Apriliyanto1, Rahmat Basuki1
1
Department of Chemistry, Faculty of Military Mathematics and Natural Sciences, Republic of Indonesia Defense University,
Kawasan IPSC, Sentul, Bogor 16810, Indonesia
2
Department of Materials Science & Engineering, Monash University, 20 Research Way, Clayton VIC 3800, Australia
Received: 15 May 2022; Revised: 9 Jun 2022; Accepted: 10 Jun 2022;
Available online: 15 Jun 2022; Published regularly: 30 Jun 2022
Abstract— Thiazole derivative molecules with a low energy gap have been successfully designed using the DFT/TD-DFT
calculation methods. The calculations were simulated by adding varied numbers of thiophenes (1, 2, 3, and 10) and electron
donating molecules of –H, -NH2, -OCH3, and –COOH in the ethanol solvent. The best thiazole derivative was the molecule
constructed using a long-conjugated bridge of 10-thiophenes, the carboxyl anchoring site, and an amine addition as the
electron donating molecule with an energy gap of 1.66 eV and a strong UV-Vis absorption in the red light region (673.20 nm).
These designed molecules are beneficial to be applied in the equator area such as Indonesia. Further, the profound effects of
the thiophene bridge in terms of the structural and energy gaps, and the variation of electron-donating molecules affected the
photonic properties have been demonstrated in this paper.
Keywords— Thiazole derivatives design; Photonic material; DFT/TD-DFT; Dye sensitized solar cell.
are employed, or less than 0.08% of the total potential
1. INTRODUCTION
used [5]. The low realization proportions are due to
Energy security is one of the main factors unclear regulations, unavailable markets, and weak
determining the strength of a country because of its research on product development [6]. Therefore,
vital function [1]. The International Energy Agency (IEA) studies focussing on photovoltaic technology and its
defines energy security as the availability of an device as a solution to the latest problem are
abundant energy source in a nation at an affordable significantly substansial in Indonesia.
price with a benign supply for 90 days of oil equivalent The photovoltaic device is an instrument that
imports [2]. Indonesia, a country with immense converts sunlight into electrical energy utilizing
renewable energy potential, has to rely on the utility of engineered semiconductor materials, which have been
fossil energy, with the usage rate reaching ~90% [3]. developed since 1954 using silicon-based solar panels
Furthermore, some crucial predictions from the 2019 [7]. Although it is a senescent technology, Indonesia
Energy Outlook published by the Indonesia National does not yet have an industrial plant that produces
Energy Council stated that the national oil production silicon panels due to its complexity and high
is estimated to be low at 53.8 million barrels in 2050, production costs. One alternative in photovoltaic
with only 71 years remaining for the coal stockpile [4]. technology that is widely studied is dye sensitized
Therefore, the transition to the employment of solar cells (DSSC). This technology has been at the
renewable energy is a straightforward strategy for the center of attention of researchers for the last 30 years
country. because of its potential as an effective, economical,
Although the potential of renewable energy in flexible, highly reproducible, and scalable power
Indonesia is abundant, the energy mix target of 23% in conversion device for industry [8]. Since O'Regan and
2025 merely can be achieved by 10% at this time. Data Gratzel first report in 1991, the exploitation of dyes has
from the Institute for Essential Service Reform (IESR) been very high to replace silicon-based solar cells
in 2019 shows the solar power potential in Indonesia that act as light harvesters to generate electricity. To
isup to 208 gigawatts. However, only 159 megawatts date, the power conversion efficiency (PCE) of DSSC
*Corresponding author.
Email address: naufannurrosyid@gmail.com
DOI: 10.55749/ijcs.v1i1.5
17 Indones. J. Chem. Stud., 2022, 1(1), 16–23
has reached over 14% due to various optimizations component of the gradient was less than the
such as their film formation, charge transport, optimization tolerance and the root mean square
electrolyte system, and dyes enhancement, most gradient was less than a third of the optimization
importantly [9]. tolerance. The initial geometry optimization was
Curcumin, phenylalanine, dithienopyrrole, and performed under an ethanol solvent environment (ε =
thiazole are used actively as sensitizers in DSSC 24.55) with no symmetry restriction to produce an
devices [10]. Numerous studies using thiazoles have optimal ground state structure of the designed
obtained promising results due to their intrinsic molecules. Moreover, all of the obtained geometries
properties, such as intense intramolecular charge were confirmed to be the minima value on the
transfer, strong absorption of visible light, and broad potential energy surface (PES) by performing
molecular derivatives [11]. In addition, the selection of vibrational frequencies calculations.
thiazoles is determined strongly by the nature of the In the next step, the optoelectronic properties of
extendable conjugated bridge based on the stable the designed molecules were simulated and precisely
structure of the donor-conjugated bridge-acceptor (D- calculated through the TD-DFT method using a
π-A). Therefore, further studies, from molecular to correlation-consistent basis set up to the 1d electron
mechanical aspects, are always required to optimize orbital (cc-pVDZ) as implemented in the Gaussian 09
thiazoles in DSSC. Fortunately, the computational software. It is globally accepted that the TD-DFT
approach continues to be an essential method in approximation, despite its shortcomings, is still
predicting the potential of particular sensitizers for recognized as a decent compromise to evaluate
DSSC concerning cost-effective research. Both vertical excitation energies and it’s results are
density functional theory (DFT) and time-dependent comparable to the experimental optical spectra.
density functional theory (TD-DFT) have been adopted Thus, based on the mentioned methods, we could
optimally as standard investigative tools on the possibly obtain some valuable data regarding the
optoelectronic properties of molecules in dyes optical and electronical properties of the excited
involving the ground and excited states, respectively molecules such as excitation energy or frontier
[12]–[14]. orbital’s energy gap, excitation symmetry, and
In this work, we employed the DFT and TD-DFT percentage of excitation, electron density in both of
methods and the results were analyzed to establish a highest occupied (HOMO) and lowest unoccupied
reproducible roadmap in designing some novel molecular orbitals (LUMO). Finally, we demonstrated
molecules based on thiazole derivatives focusing on the possible UV-vis absorption spectra and the
the sum of the effects of the thiophene acting as resulting molecular orbitals using GausSum and
expandable conjugated bridge. Furthermore, GabEdit, respectively.
particular added electron donating molecules were
2.2. Calculation Roadmap Details
also simulated to optimize their optoelectronic
properties. This type of computational study is crucial, The ultimate purpose of this research was to
especially in this Covid-19 pandemic situation, because demonstrate a detailed workflow when designing a
computational approach is an ultimate solution to certain molecule as a sensitizer in DSSC. To obtain a
obtaining high quality and cost-effective research. precise result, the first step was to create a z-matrix
from the thiazole as the main molecule using a simple
2. COMPUTATIONAL DETAILS
molecular software such as Avogadro followed by
2.1. Calculations Methods optimization of its ground state structure via DFT
calculation using Gaussian 09.
In this study, both the geometric and optoelectronic
Further, various of thiophene functional groups as
properties of the designed molecule as a novel
an expandable conjugated bridge was added and
sensitizer in DSSC were deeply investigated and
optimized using the previously mentioned method.
calculated using the standard Gaussian 09 package.
After the optimized ground state geometries of
Firstly, a 3D molecular structure was generated via
thiazole derivatives with various thiophens bridge
Avogadro software. The Merck molecular force field
were obtained, further calculations employing the TD-
(MMFF94), as a precise molecular mechanics tool that
DFT method were performed to reveal the
freely available in the software, was adopted to
optoelectronic properties in their excited states.
minimize the conformational energies [15].
To enhance the previous models, several electron
A full geometry optimization was performed further
donating groups were attached to the latest thiazole
using a DFT calculation based on Becke’s three
with the optimized thiophene numbers and their
parameters gradient-corrected exchange potential
excited states were calculated using the identical
and the Lee-Yang-Parr gradient correlation potential
method as before. Finally, combining these two
(B3LYP) hybrid functional using a common basis set of
parameters will reveal the best performed thiazole
6-31G(d). The parameters and basis set were found to
derivative as a sensitizer in DSSC.
be quite stable and already established in the
aforementioned package [16]. The convergence of a
geometry search was reached when the largest
Nurrosyid et al.
18 Indones. J. Chem. Stud., 2022, 1(1), 16–23
3. RESULT AND DISCUSSION yield amine 4-(4-metoxy-2-(thiophen-2yl)thiazole-5-
yl)aniline as presented in scheme 3.
In this study, we designed molecules based on the
Finally, the reference molecule for further
well-known chemical reaction of thiophene-2-
modification was obtained by reacting the last yielded
carbothioamide with ethyl 2-bromo-2-(4-
molecule with hydrochloric acid at -50 °C to form
nitrophenyl)acetate via Hantzsch cyclization as
diazonium compound, and later be deaminated using
demonstrated in scheme 1, in Fig. 1. Next, the obtained
hypophosphorous acid as shown in the latest scheme
material, which was 4-hydroxy-1,3-thiazole then
(4). This final product was labelled as a reference
alkylated with K2CO3 and methyl iodide succeeding a
thiazole in this report for simplification. Based on its
Williamson-type etherification to get 4-methoxy-5-(4-
common synthesis route and high resonance
nitrophenyl)-2-(thiophen-2-yl)thiazole as witnessed in
opportunity provided by conjugated bonding, further
scheme 2. Furthermore, the reduction reaction of the
analysis developed with a reproducible computational
nitro group in the previous results was conducted by
calculation were presented in this report.
hydrazine hydrate solution and a Nickel substrate to
Fig. 1. Schematic synthesize route of reference thiazole [17]
The first modification on this thiazole main molecule molecules can stabilize their structure since they will
started by adding thiophene as a π-conjugated bridge. act as conjugated bridge [18]. A total SCF energy of -
It is already reported in several studies that the longer 1.77 × 10-7 kJ mol-1 was obtained with the 10 thiophene
the bridge the lower the molecular energy gap, while a single thiophene had an energy of -0.47 × 10-7
producing a red-shifted electronic absorption kJ mol-1. Although ten thiophenes can decrease the
spectrum [18]. Even though decreasing the energy gap total SCF energy more than three times that of the
can improve the light-harvesting ability of the reference structure, it should be noted that creating a
photoactive materials, it should be noted that the long π-bridge is experimentally challenging.
HOMO position needs to be matched with the TiO 2
Table 1. Total SCF energy with thiophens variation
semiconductor, especially in the D-π-A structure.
Therefore, a careful analysis involving structure and Thiophene Amount* Total SCF Energy (kJ mol-1)
excitation states of the active material is extremely 1 -0.465 × 10-7
2 -0.610 × 10-7
imperative.
3 -0.755 × 10-7
In term of structural study, we calculated different 10 -1.769 × 10-7
number of thiophene to modify the π-bridge length. *The structure of four designed molecules with the different of
The total energy (kJ mol-1) of 1, 2, 3, and 10 number of thiophens amount is depicted in the Supporting Information, Fig. S1.
thiophenes were calculated using the self consistent
field (SCF) method in the Hartree-Fock (HF) Regarding the energetical results by the DFT
approximation in conjugation with an augmented investigation to obtain the favourable structure, the
valence triple-zeta basis set, 6-311G(d,p), to ensure a excited state geometries and their optical properties
correct description of the H-bond system. The stable of designed photoactive molecules were calculated
B3LYP hybrid functional was used as a reliable energy using the TD-DFT method with the cc-pVDZ basis set
calculation in terms of structural optimization [19]. As in the ethanol phase. From this higher-level theory,
shown in the Table 1, the more thiophene added in the energy gaps information is obtained which is a
molecule, the lower the total energy. This result is essential for designing any molecule to be a sensitizer
because the thiophene in the designed photoactive in DSSC. The Gaussian software also facilitates us to
Nurrosyid et al.19 Indones. J. Chem. Stud., 2022, 1(1), 16–23
obtain excitation symmetry and their composition All designed molecules are based on organic
which are important for excitation analysis during the compounds with π-conjugated bridge, thus, the
photo incident. excitation energy shown in the calculation is mainly an
energy different (HOMO-LUMO energy gap) between π
Table 2. Vertical excitation profile of excited thiazole
molecules with thiophens variation to π* orbitals. Table 2 shows that the variation of π-
bridge length provide meaningful results. The longer
Vertical Excitation Profile the bridge, the lower the energy gap. The ten
Thiophene Energy thiophens were recorded to have 1.86 eV energy gap,
Composition
Amount Gap Symmetry while the reference had 2.58 eV. These results are
(%)
(eV)
quite promising in DSSC, since the decreasing energy
1 2.58 HOMO LUMO 100
can simply be achieved by adding a conjugated π
2 2.35 HOMO LUMO 100
3 2.23 HOMO LUMO 99 bridge. With these early data, we confidently
HOMO-1 LUMO+1 1 recommend to design photoactive planar molecule
10 1.86 HOMO LUMO 91 with higher conjugated value to achieve 1.4 eV as the
HOMO-1 LUMO+1 6 most ideal energy gap for photovoltaic devices [20].
HOMO-2 LUMO+2 3
1 Thiophene 2 Thiophens 3 Thiophens
LUMO
HOMO
10 Thiophens
LUMO
HOMO
Fig. 2. The molecular orbital density in HOMO and LUMO states of thiazole molecules with thiophens variation. The phase of
wave functions is shown as red and blue colors of the represented molecular orbitals
The excitation symmetry and its composition deexcitation phenomena, which later reducing the final
presented in Table 2 showed that one and two current in the devices.
thiophenes provided a hundred percent excitation Although there is a branching in the excitation
from the HOMO to LUMO symmetry, while the three symmetry of the thiazole with ten thiophens, the
thiophenes with 2.23 eV had branched excitations. designed molecules still have a tendency to be a great
Furthermore, ten thiophens showed a triple excitation photoactive material since the majority of excitations
symmetry with the majority of HOMO to LUMO is conducted in the HOMO to LUMO symmetry, with
excitation (91%), HOMO-1 to LUMO+1 of 6%, and only 3% more than 90% composition. The localization orbital
from HOMO-2 to LUMO+2 symmetry. The excitation states play a crucial role in this phenomenon [21].
symmetry branching will further increase due to the Despite majority of orbitals seems to be overlapped as
overlapping orbitals between the ground and excited shown in Fig. 2, the density in LUMO is relatively high
states [21]. This typical condition should be tackled in its methoxy group. In contrast, the orbital density
down in the designing decent sensitizer in DSSC since also increases in the aromatic rings for the HOMO
the cumulative overlapping orbitals lead to state. Based on this simulation, a clear electron
Nurrosyid et al.20 Indones. J. Chem. Stud., 2022, 1(1), 16–23
separation between its ground and excited states will Furthermore, the electron donating groups were
be beneficial for DSSC. varied as an additional step to show the effect of each
Moreover, from the absorbance prediction by TD- molecules attracted in one thiophene based structure.
DFT, it is clearly stated that all designed molecules To make the effect stronger, the anchoring site was
have the potential to be used as dyes in DSSC due to modified using a thiophene as the reference. One
their absorbance in the range of 480.33 to 667.54 nm. thiophene is chosen due to the calculation complexity
The oscillator frequency (foscillator) also witnessed a that might contribute to the accuracy. Three molecules
great increase as the rise of the number of thiophens, were employed at the terminal benzene, -NH2, -OCH3,
because it actively transfers excited electrons after and -COOH to demonstrate a uniform attraction on the
the photo incident. Thus, it is imperative to design whole sensitizer molecules. Similar to the previous
several photoactive molecules with the longest simulation, a higher amount of electrons results in a
possible of conjugated bridge as the trade-off more negative total SCF energy, leading to a more
between the stability, cost-efficient procedure, and the stable structure. Hence, -COOH witnessed the lowest
photoactive performance. energy, -5.28 × 10-8 kJ mol-1 compared to the control (-
Absorbance study is one of the fundamental 4.79 × 10-8 kJ mol-1). The detail results are available in
properties to be directly observed when designing Fig. S2 and Table S1 of the Supporting Information.
photoactive materials. The peaks in the absorption Interestingly, although all electron donating
spectra, or usually showed as a spectrum edge, molecules witnessed a 100% excitation profile from
provide important information about the energy gap HOMO to LUMO, the energy variations were clearly
(Eg), which is easily calculated from Eg = hν. A lower observed. Based on the TD-DFT calculation for each
gap will induce more photons to be absorbed by the excited molecule, -NH2 shows a dramatical reduction
materials, thus more electricity will be produced in the in the energy, 1.96 eV compared to the -COOH, 2.31 eV,
device. A higher energy gap means a highly which is quite high and is still similar with the control
transmittance material, leading less incident light to (-H), 2.59 eV. It is clearly shown that all of electron
potentially be converted into electricity [22]. It has donating molecules provide a good agreement for the
been calculated from the black body radiation and the HOMO and LUMO states.
Shockley-Queisser limit that the ideal gap of To clearly investigate the effect of electron donating
semiconductor materials to absorb the maximum molecules in thiazole derivatives, the UV-Vis
number of photons from solar radiation was 1.4 eV [20]. absorption was evaluated using TD-DFT calculations
This calculation becomes the foundation to design any and revealed a huge redshift in the -NH2 sample. The
novel materials in a single photovoltaic device to absorbance peak dramatically shifts from 479.11 nm to
obtain an energy gap as close as possible to 1.4 eV. 632.57 nm, consequently reducing the band energy gap
The TD-DFT calculation has become a robust from 2.58 to 1.96 eV, as shown in Table 4. These
approach to simulate UV-Vis absorption spectra with a results indicate that the addition of –NH2 in the
precise maximum absorption value. Table 3 reveals a sensitizer, especially in the term can provide a benefit
strong effect of the thiophene bridges in designed due to effective electron donating effect to the whole
photoactive materials in both of maximum wavelength system. However, experimental should be carefully
(λMAX) and foscillator. A strong redshift spectrum was designed to attach the amine site into the benzene
observed when the amount of thiophene increase, side which is quite tricky.
from 480.33 to 667.54 nm by ten of thiophene additions.
Table 4. Absorption profile of thiazole with a thiophen and
The higher number of excited electrons in the different electron donating molecule
conjugated chain causes massive increase in the
oscillator frequency, whereas the redshift phenomena Electron
λMAX (nm) foscillator (Hz) Eg (eV)
occurs due to the weaker anchoring site effect in the Donating
longer bridge. These result indicate that π-junction -H 479.11 0.90 2.58
-NH2 632.57 1.05 1.96
could effectively reduce the gap up to 71.7%, from 2.58
-OCH3 584.49 1.05 2.12
to 1.85 eV, which is closer to the ideal energy gap of -COOH 536.33 1.23 2.31
photovoltaics device. It should be noted that a normal
carboxyl is performing the anchoring effect inside the Finally, by optimizing the thiophene bridges by its
molecule. number and electron donating molecule, the results
were combined to deeply investigate the best
Table 3. Absorption profile of thiazole molecules with
thiophens variation performed molecule, a thiazole with a 10-thiophenes
bridge and an amine at the edge. Two types of
Thiophens molecules were simulated with the reference model
λMAX (nm) foscillator (Hz) Eg (eV)
Amount and highly ordered trans structure. Fig. 3 depicts the
1 480.33 1.12 2.58 mentioned structure, with a slightly different
2 525.62 1.42 2.36 stabilization energy. A trans-thiazole recorded -1.797 ×
3 556.25 1.99 2.23
10-7 kJ mol-1 while the reference showed a higher value
10 667.54 4.24 1.85
of -1.799 × 10-7 kJ mol-1. This ultra-small different
Nurrosyid et al.21 Indones. J. Chem. Stud., 2022, 1(1), 16–23
indicates a stable structure to be obtained in the high number of electron repulsion inside the system
synthesis without any notable risk to increase can also leads to the reference structure instead of a
complexity to get the highly ordered structure. The trans-thiazole structure.
(a)
(b)
Fig. 3. (a) Reference and (b) the best performed thiazole derivative
Remarkable results showed by the excitation profile amine group as an electron donating group. Therefore,
investigation through the best performed structure this type of doping is highly recommended for
compared to the 10-thiophenes based molecule. designing a low energy gap absorber material. The
Interestingly, a 1.66 eV of bandgap energy gap was excitation mapping between the ground and excited
recorded with the 79% of HOMO LUMO excitation states of the best performed thiazole molecule are
symmetric compared to 1.85 eV of the later structure. presented in Fig. 4, with the HOMO-1 LUMO and
This 11.37% decrement is a significant result since it HOMO LUMO+1 excitation symmetric contributing to
will lead to the higher number of photons absorbed by the 12% and 7% of the total composition, respectively.
thiazole, and it was obtained by simply adding an
LUMO+1
LUMO
HOMO
HOMO-1
Fig. 4. The HOMO-1, HOMO, LUMO, and LUMO+1 orbital density states of the best performed thiazole derivative model
In addition, the simulated UV-Vis spectrum reported oscillator frequency of 2.29 Hz should be noted as the
in Fig. 5 clearly presents a strong absorbance around intrinsic advantage to manage the photon incident
625 and 720 nm, that is a reddish sunlight. This result is through the photoactive material. Thus, the designed
extremely important because the majority sunlight in molecule will be beneficial to be prepared as a high-
equatorial is in the red region (above 620 nm). performance absorber material in DSSC applied in
Moreover, the strongest peak at 673.20 nm with an Indonesia.
Nurrosyid et al.22 Indones. J. Chem. Stud., 2022, 1(1), 16–23
CONFLICT OF INTEREST
We declare that there is no conflict of interest among
authors.
AUTHOR CONTRIBUTIONS
NN conducted the experiment and DFT/TD-DFT
calculations; NN, YBA, MF, & RB wrote and revised the
manuscript. All authors agreed to the final version of
this manuscript.
REFERENCES
[1] Gasser, P. 2020. A review on energy security indices to compare
country performances. Energy Policy. 139(111339). 1-17 doi:
10.1016/j.enpol.2020.111339.
[2] Ali, F., Khan, K.A., & Jahan, S. 2020. Evaluating energy security
performance in Pakistan and India through aggregated energy
security performance indicators (AESPI). Eur. Online J. Nat. Soc.
Sci. 9(2). 425–442.
Fig. 5. Simulated UV-Vis absorption spectrum for the best [3] Supriadi, E., Basuki, R., Prajitno, D.H., & Mahfud, M. 2021.
performed of designed thiazole Produksi Biofuel Berbantuan Ultrasonik dari Minyak Kelapa
Terkatalisis Ca/γ-Al2O3 dan K/γ-Al2O3. Walisongo J. Chem. 4(1).
4. CONCLUSION 45–56. doi: 10.21580/wjc.v4i1.7861.
[4] Morris, N., Miharjana, D., Gubbi, S., Halim, A., Prabowo, A.,
To conclude, we had successfully designed a novel Napitupulu, D., & others. 2015. Sustainable Infrastructure
photoactive material with a low energy gap of 1.66 eV Assistance Program: Technical Assistance for Energy RPJMN
and strong UV-Vis absorption in the red light region 2015-2019: Energy Sector White Paper, Asian Development Bank.
(673.20 nm). The results were beneficial to be applied in [5] Silalahi, D.F., Blakers, A., Stocks, M., Lu, B., Cheng, C., & Hayes, L.
2021. Indonesia’s Vast Solar Energy Potential. Energies. 14(17).
an equatorial area such as Indonesia. The best 5424. doi: 10.3390/en14175424.
performed thiazole derivative molecule was [6] Gunawan, F.E. et al. 2022. Design and energy assessment of a
constructed using a long-conjugated bridge of 10- new hybrid solar drying dome-Enabling Low-Cost, Independent
thiophenes, the carboxyl anchoring site, and the and Smart Solar Dryer for Indonesia Agriculture 4.0, in IOP
Conference Series: Earth and Environmental Science, 2022,
addition of an amine as the electron donating molecule. 998(1), 12052.doi: 10.1088/1755-1315/998/1/012052.
Furthermore, the considerable effect of thiophene [7] Shiyani, T. & Bagchi, T. 2020. Hybrid nanostructures for solar-
bridge was demonstrated in terms of structural and energy-conversion applications. Nanomater. Energy. 9(1). 39–46.
energy gap, as well as the variation of electron donating doi: 10.1680/jnaen.19.00029.
[8] Gong, J., Liang, J., & Sumathy, K. 2012. Review on dye-sensitized
molecule that strongly affected the photonic properties. solar cells (DSSCs): fundamental concepts and novel materials.
A robust roadmap design was constructed here from Renew. Sustain. Energy Rev. 16(8). 5848–5860. doi:
the structural analysis to the photonic properties 10.1016/j.rser.2012.04.044.
employing the DFT and TD-DFT level of calculation that [9] Devadiga, D., Selvakumar, M., Shetty, P., & Santosh, M.S. 2021.
Recent progress in dye sensitized solar cell materials and
could be used for other research related to any photo-supercapacitors: a review. J. Power Sources. 493. 229698.
molecular design for photovoltaic application. Finally, doi: 10.1016/j.jpowsour.2021.229698.
since all the results had been conducted by [10] Soto-Rojo, R., Baldenebro-López, J., & Glossman-Mitnik, D. 2016.
computational studies, we encouraged others to carry Theoretical Study of the $π$-Bridge Influence with Different
Units of Thiophene and Thiazole in Coumarin Dye-Sensitized
out a significant research in the field of renewable Solar Cells. Int. J. Photoenergy. 2016(6479649). doi:
energy even in the pandemic situation or in the future of 10.1155/2016/6479649.
digital society. [11] Kumar, R.S., Jeong, H., Jeong, J., Chitumalla, R.K., Ko, M.J.,
Kumar, K.S., Jang, J., & Son, Y.-A. 2016. Synthesis of porphyrin
SUPPORTING INFORMATION sensitizers with a thiazole group as an efficient $π$-spacer:
potential application in dye-sensitized solar cells. RSC Adv.
The supporting information related to the present 6(47). 41294–41303. doi: 10.1039/C6RA00353B.
work can be downloaded here. [12] Kooh, M.R.R., Yoong, V.N., & Ekanayake, P. 2014. Density
functional theory (DFT) and time-dependent density functional
ACKNOWLEDGEMENTS theory (TDDFT) studies of selected ancient colourants as
sensitizers in dye-sensitized solar cells. J. Natl. Sci. Found. Sri
The authors highly acknowledge Mr. Muhamad A. Lanka. 42(2). doi: 10.4038/jnsfsr.v42i2.6996.
Martoprawiro, Ph.D., who has guided this research and [13] Zanjanchi, F. & Beheshtian, J. 2019. Natural pigments in dye-
Dr. Bunbun Bundjali for granting permission to use the sensitized solar cell (DSSC): a DFT-TDDFT study. J. Iran. Chem.
Soc. 16(4). 795–805. doi: 10.1007/s13738-018-1561-2.
research facilities at the Department of Chemistry, ITB. [14] AL-Temimei, F.A. & Alkhayatt, A.H.O. 2020. A DFT/TD-DFT
The authors also acknowledge the Republic of investigation on the efficiency of new dyes based on ethyl red
Indonesia Defense University for funding under the dye as a dye-sensitized solar cell light-absorbing material.
LPPM internal research program. Optik (Stuttg). 208(163920). 1–7. doi: 10.1016/j.ijleo.2019.163920.
[15] Tosco, P., Stiefl, N., & Landrum, G. 2014. Bringing the MMFF
force field to the RDKit: implementation and validation. J.
Cheminform. 6(1). 1–4. doi: 10.1186/s13321-014-0037-3.
Nurrosyid et al.23 Indones. J. Chem. Stud., 2022, 1(1), 16–23
[16] Hernandez-Haro, N., Ortega-Castro, J., Martynov, Y.B., chromophores for dye-sensitised solar cells. Dye. Pigment.
Nazmitdinov, R.G., & Frontera, A. 2019. DFT prediction of band 94(3). 469–474. doi: 10.1016/j.dyepig.2012.02.015.
gap in organic-inorganic metal halide perovskites: An [20] Tong, J. et al. 2021. High-performance methylammonium-free
exchange-correlation functional benchmark study. Chem. Phys. ideal-band-gap perovskite solar cells. Matter. 4(4). 1365–1376.
516. 225–231. doi: 10.1016/j.chemphys.2018.09.023. doi: 10.1016/j.matt.2021.01.003.
[17] Wu, Y.J. & Yang, B. V. 2011. Chapter 5.5: Five-membered ring [21] Krauter, C.M., Möhring, J., Buckup, T., Pernpointner, M., &
systems: with N and S (Se). Prog. Heterocycl. Chem. 23. 685–714. Motzkus, M. 2013. Ultrafast branching in the excited state of
doi: 10.1016/B978-0-08-096805-6.00009-7. coumarin and umbelliferone. Phys. Chem. Chem. Phys. 15(41).
[18] Gao, P., Tsao, H.N., Yi, C., Grätzel, M., & Nazeeruddin, M.K. 2014. 17846–17861. doi: 10.1039/C3CP52719K.
Extended $π$-Bridge in Organic Dye-Sensitized Solar Cells: the [22] Pulli, E., Rozzi, E., & Bella, F. 2020. Transparent photovoltaic
Longer, the Better? Adv. Energy Mater. 4(7). 1301485. doi: technologies: Current trends towards upscaling. Energy
10.1002/aenm.201301485. Convers. Manag. 219. 112982. doi: 10.1016/j.enconman.2020.112982.
[19] Seo, K.D., Choi, I.T., Park, Y.G., Kang, S., Lee, J.Y., & Kim, H.K. 2012.
Novel D-A-π-A coumarin dyes containing low band-gap
Nurrosyid et al.You can also read
