Screening the effects of additional donors, numbers and positions of π-spacers on perylene- based sensitizers in dye-sensitized solar cell applications

doi:10.21203/rs.3.rs-2603551/v1

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Screening the effects of additional donors, numbers and positions of π-spacers on perylene- based sensitizers in dye-sensitized solar cell applications

https://doi.org/10.21203/rs.3.rs-2603551/v1

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The novel sensitizers are framed by perylene as donor with diphehylamine as auxiliary donor, thiophene and cyanovinyl as π-spacers and cyano acrylic acid as an acceptor unit. The optimised structure for the designed sensitizers was determined utilizing density functional theory, and the electronic structure was determined utilizing time-dependent density functional theory through the B3LYP/6-311G (d, p) basis set in the gas phase and Dimethylformamide (DMF) phase. The frontier molecular orbital results have significantly lower HOMO-LUMO energy gap values for better electron injection and electron regeneration. All designed sensitizers have absorption spectra values in the range of visible to near IR region. In the present work, the position and number of π-spacers reduces the HOMO-LUMO gap, the redshift of the absorption spectrum, and increases the high light harvesting efficiency. The findings reveal that the number of π-spacers improves the power conversion efficiency (PCE) of the solar cells.

Diphenylamine

perylene

LHE

DFT

The dye-sensitized solar cell (DSSC) was first introduced by O'Regan and Gratzel in 1991[1] and has a comprehensive mechanism. The photosensitizer absorbs the photon from solar radiation and injects the electron into the photo anode, such as TiO2, ZnO, etc., is the mechanism of the DSSC [2] and generates electric current in the circuit. The photo sensitizers are categorised into two types: metal sensitizers and metal-free organic sensitizers. The metal sensitizers like Ru complex and zinc phoperynin achieved a higher photon to current conversion efficiency (PCE) of > 11% [3]. In comparison to metal-free organic sensitizers, metal sensitizers have some drawbacks, such as high cost, environmental risk, and challenging purification. [4]. The metal-free organic sensitizers have received the most attention in DSSC due to their lower cost, modification of structure, and ease of fabrication [5]. The metal-free organic sensitizers achieved a higher PCE of 14.5% with the silyl anchor group [6]. The D-π-A structure of the sensitizers has the donor, π-spacers and acceptor units, which are broadly used to design dye sensitizers [7, 8]. The D-π-A structured sensitizers were easily modified by the numbering and positions of the donors, π-spacers and acceptor units. The sensitizers has donor groups such as triphenylamine [9], perylene [10], carbazole [11], indoline [12], and coumarin [13]. The sensitizers possess aromatic hydrocarbons and delocalization properties which helps in electron donate nature. The π-spacers such as thiophene, cyanovinyl and thionothiophene are commonly used for photosensitizers [14, 15], and their major role in the optical properties is to reduce the HOMO-LUMO energy gap of the sensitizers. The computational calculations were used to analyse the sensitizers in the theoretical method, which helps to develop highly efficient sensitizers without waste of time and cost [16, 17]. In the theoretical method, DFT and TD-DFT theory functions were used to analyse the optical properties, optimised geometry, and electronic properties [18]. In the current work, perylene donor-based sensitizers were combined with thiophene and cyanovinyl as π-spacers. Perylene is an aromatic hydrocarbon that is used as a donor due to its planar structure and electron delocalization properties [19]. Thiophene and cyanovinyl are employed as π-spacers because of their high electron transfer nature. In diphenylamine, the additional donor for the donor part has two aromatic rings linked with nitrogen, which helps to improve the donating ability of the donor part [20]. Cyanoacryic acid is used as an acceptor group. In previous work, it was reported that the combination of π-spacers configurations combined with perylene donor [21]. This work focuses on the effects of numbering and positions of the π-spacers and the presence of additional donors for the donor part. Intramolecular charge transfer and electronic properties were analysed through coplanarity, frontier molecular orbital, natural bonding orbital, electron injection, and electron regeneration. The optical properties of the sensitizers were analysed by absorption maximum, light harvesting efficiency, and molar extension coefficient studies.

The entire set of computational calculations are calculated using the Gaussian 09w package and Gauss View 5.0 software [22, 23]. The optimization of the chosen sensitizers were done by using Density Functional Theory (DFT) through the Becke's three-parameter hybrid functional of Lee-Yang Parr (B3LYP)/6-311G(d,p) basis set in the gas and DMF phase [24, 25]. Utilising, the DFT calculations the HOMO-LUMO and dipole moment were used to describe the intramolecular charge transfer. The absorption spectrum and vertical excitation energy are determined by the polarizable continuum model (PCM) and investigated by Time Dependent-Density Functional Theory with CAM-B3LYP/6-311G(d,p) basis set in gas and DMF phases. The absorption maximum, vertical excitation energy, and oscillator strength can be predicted using TD-DFT functions. The excitation properties of the sensitizers were analysed by using the Gauss sum 3.0 program [26].

Structure of the sensitizers

The diphenylamine functionalized perylene donor is linked with cyanoacrylic acid through different numbers and positions of thiophene and cyanovinyl groups. The π-spacers are positioned into the six configurations. The configuration of the designed sensitizers listed in Table 1, and the structural arrangement of sensitizers are,

Table 1

Structural arrangement of DPP sensitizers
Dyes	Configurations	Combinations of Donor-π-Acceptor
DPP-1	Configuration − 1	D-P-CA
DPP-2	Configuration − 2	D-P-C-T-CA
DPP-3	Configuration − 3	D-P-T-C-CA
DPP-4	Configuration − 4	D-P-C-T-C-T-CA
DPP-5	Configuration − 5	D-P-C-T-T-C-CA
DPP-6	Configuration − 6	D-P-T-T-C-C-CA
D-Diphenylamine, P-Perylene, T-Thiophene, C-Cyanovinyl,CA-Cyanoacrylicacid

Configuration 1: D-P-CA

Configuration 2: D-P-C-T-CA

Configuration 3: D-P-T-C-CA

Configuration 4: D-P-C-T-C-T-CA

Configuration 5: D-P-C-T-T-C-CA

Configuration 6: D-P-T-T-C-C-CA

The six configurations include models with and without π-spacers. Configuration 1 has only donor and acceptor parts. In configurations 2 and 3, the mono thiophene and cyanovinyl as a π-spacers and their positions were changed. Then configurations 4,5 and 6 have the double pair of thiophene and cyanovinyl groups which have different positions were analysed. The chemical structure of the sensitizers is depicted in Fig. 1 and geometrical structure of the sensitizers is depicted in Fig. 2.

Nbo Analysis

The charge population of the sensitizer is predicted using natural bond orbital analysis, which demonstrates that intramolecular charge transfer from the donor to acceptor happens through π-spacers [27–32]. The total charge population of the donor part is indicated as q^D and the positive value of q^D represents that the donor part has more electrons to donate to the acceptor. The q^A represents the charge population of the acceptor part, and the charge population of the π-spacer part is represented as q^π. The negative q^A value indicates that the acceptor has accepted an electron from the donor through π-spacer. The q^π values are negative, the π-spacers act as acceptor units, and positive q^π values indicate the π-spacers act as donor units. The q^D−A represents the charge separation between the donor part to acceptor part. The positive q^D−A value of the sensitizers has the best charge separation between the donor and acceptor parts, and values are listed in Table 2. The DPP-2 has the highest q^D−A values compared to the other sensitizers. DPP-1 has a q^D−A value of 0.24167. The addition of π-spacers in DPP-2 increases the q^D−A value, and changing the position of the π-spacers decreases the q^D−A value in DPP-3. Then an increased number of π-spacer units decreases the q^D−A value in DPP-4 compared to DPP-2. The higher positive value of q^D−A value of DPP-2 is the better candidate for DSSC applications.

Table 2

NBO analysis of DPP group of sensitizers.
Dye	q^D	q^π	q^A	q^D−A
DPP-1	0.1208	-	-0.1208	0.2416
DPP-2	0.1230	0.0264	-0.1494	0.2724
DPP-3	0.0548	0.0394	-0.0942	0.1490
DPP-4	0.1190	0.0269	-0.1459	0.2649
DPP-5	0.1010	-0.0078	-0.0932	0.1942
DPP-6	0.0312	0.0490	-0.0801	0.1113

Frontier Molecular Orbitals

The charge distribution of the donor to acceptor is influenced by frontier molecular orbital analysis. The photoexcitation process of the solar cell, involves the injection of electrons into the semiconductor diode [33]. The HOMO, LUMO, and HOMO-LUMO energy gap are determined by the charge separation process. Figure 3 depicts the charge distribution of the developed sensitizers. In HOMO, the density of the electron is delocalized into donor and π-spacer units. In LUMO, the density of electrons is delocalized into π-spacer and acceptor parts. The charge separation of the HOMO-LUMO improves the ICT of the solar cell. The examined sensitizers' HOMO and LUMO values, as well as the HOMO-LUMO energy gap, are given in Table 3 and depicted in Fig. 4. The charge separation that took place during the photoexcitation procedure, the HOMO-LUMO energy gap values is minimized. The HOMO is below the redox electrolyte and the LUMO is above the CB of the TiO₂ semiconductor, according to the energy level diagram [34]. A Polarizable continuum model is used to optimize the studied sensitizer in the DMF phase. The energy gap of the sensitizers is reduced compared to the gas phase because of solvent polarisation. The energy levels are stabilised by solvent polarisation, which also causes a reduction in the energy gap. At 2.303 eV, DPP-1 has a larger band gap. Inclusion of π-spacers reduces the energy gap in DPP-2 compared to DPP-1. The positions of the π-spacers were changed and electron withdrawing (CN) groups lie near to the acceptor, which helps to decrease the energy gap of the sensitizers. Similarly, the configurations 4,5 and 6 have the number of π-spacers increases and the π-spacers positions were changed, which it is helps to reducing the energy gap. As a result, the energy gap of the sensitizers is affected by the increasing number and varied positions of π-spacers, and electron withdrawing groups close to the acceptor group. According to the aforementioned data, DPP-6 is ideal for DSSC applications since it has the lowest energy gap value when compared to other proposed sensitizers.

Table 3

HOMO-LUMO values of DPP group of sensitizers in Gas and DMF phase .
Dyes	Gas phase (eV)		E_H−L	DMF phase (eV)		E_H−L
Dyes	HOMO	LUMO	E_H−L	HOMO	LUMO	E_H−L
DPP-1	-5.2956	-2.9922	2.3035	-5.3174	-3.1092	2.2082
DPP-2	-5.2592	-3.3130	1.9462	-5.2785	-3.3563	1.9222
DPP-3	-5.2472	-3.3253	1.9220	-5.2554	-3.3647	1.8907
DPP-4	-5.2679	-3.5182	1.7497	-5.2660	-3.5032	1.7628
DPP-5	-5.3027	-3.5707	1.7320	-5.2559	-3.5261	1.7298
DPP-6	-5.2853	-3.7059	1.5794	-5.2312	-3.6698	1.5614

Optical Properties

The absorption spectrum of the D-π-A structured sensitizers is in the range of visible to near IR. Maximum absorption and oscillator strength are critical for ICT because they improve absorption during the photoexcitation process [3, 24]. The CAM-B3LYP/6-311G(d,p) basis set in gas and DMF phase is used in TD-DFT calculations to determine the absorption maximum, oscillator strength, and vertical excitation energy. Figure 5 depicts the sensitizers' absorption spectra. Table 4 lists the molar extinction coefficient (ε) and the absorption maximum (λ_max), whereas Table 5 lists the oscillator strength (f) and transition assignment. From Fig. 5 and Table 4, It can be seen that the absorption maximum of DPP-1 is 470nm. In addition of π-spacers, the λ_max values are red shifted by 53 nm, whereas the position of π-spacers is changed λ_max is blue shifted by 34 nm. Similarly, the configurations 4,5 and 6 the number of π-spacers have been increased, induced the redshift of the spectrum, and changed the position of the π-spacers, induced the blueshift of the spectrum. Therefore, the number of π-spacers and position of π-spacers influence the absorption spectrum. The absorption maximum of the designed sensitizers is calculated by the DMF phase. The λ_max is increased compared to the gas phase because of the solvent effect. Whereas the redshift and blueshift of the absorption maximum are similar to that of the gas phase. The molar extension coefficient (ε) is another important factor in absorbing the photons from sunlights to inject into the semiconductor conduction band. The ε values of DPP sensitizers are depicted in Table 4. The ε values are in the range of 5.116 x 10⁴ to 16.603 x 10⁴ in the gas phase. When compared to the other configurations, configuration 6 has the highest value. In the DMF phase, all configurations have a higher value of ε compared to the gas phase due to the solvent effect. The higher value of ε for configuration 6 shows it as a more efficient sensitizer compared to other configurations. Light harvesting efficiency (LHE) is an important parameter to enhance the short circuit current (J_sc). The higher value of LHE indicates that the efficiency of the solar cell will be enhanced. The LHE value of the sensitizers is calculated by using the equation in the literature [35]. The LHE values of the designed sensitizers are summarized in Table 5. From Table 5, the LHE value of the DPP group of sensitizers is 0.7940 to 0.9948. The DPP-1 has the lower value of LHE. The number of π-spacers is increased, allowing the LHE to be increased. The electron withdrawing (CN) group lying near to the acceptor group enhances the LHE value. The above results reveal that the greater number of π-spacers and position of the π-spacers affect the absorption maximum, ε and LHE. As a result of its higher ε and LHE values, the DPP-6 is a more proficient candidate for DSSC applications.

Table 5

Oscillator strength (f), Light harvesting efficiency of the DPP group of sensitizers.
Dye	f	LHE	TRANSITION ASSIGNMENT
Dye	f	LHE	Major	Minor
DPP − 1	0.6862	0.7940	H->L (86%)	H-2->L (10%)
DPP − 2	1.1993	0.9368	H->L (73%)	H-2->L (14%), H->L + 1 (7%)
DPP − 3	1.1288	0.9257	H->L (65%), H-2->L (15%)	H->L + 1 (12%), H-3->L (4%)
DPP − 4	1.8911	0.9872	H->L (57%), H-2->L (19%)	H->L + 1 (13%), H-3->L (4%)
DPP − 5	2.2295	0.9941	H->L (46%), H-2->L (20%)	H->L + 1 (19%), H-3->L (8%)
DPP − 6	2.2875	0.9948	H->L (37%), H-3->L (25%)	H-2->L (24%), H->L + 1 (9%)

Electrochemical Properties

Electron injection (ϕ_inj) is the process of injection of electrons into the CB of the TiO₂ from LUMO during the photoexcitation process. The electron injection is determined by the thermodynamic driving force (ΔG_inject). ΔG_inject is calculated from the oxidation potential, vertical excitation energy of the sensitizers and reduction potential of the semiconductor.

ΔG_inject of the sensitizers is determined from the equation [9],

$${{\Delta }G}_{inject }=OPES - {E}_{CB}^{SC}$$

…………………………..

Where,

OPES is the oxidation potential of the sensitizer in excited state

${E}_{CB}^{SC}$ is reduction potential of the semiconductor conduction band.

$$OPES= RPGS- {\lambda }_{max}$$

…………………………..

Where,

RPGS is the reduction potential in ground state

λ_max is the vertical excitation energy of the sensitizers.

Electron regeneration is determined by the following equation [36],

ΔG_reg = RPGS – E_redox ………………………….. (3)

Where,

E_redox is the oxidation potential of the redox electrolyte.

The electron injection and electron regeneration of the sensitizers are listed in Table 6. All the designed sensitizers have a negative value of ΔG_inject and a positive value of ΔG_reg, which means they possess the position of LUMO is above the conduction band of the semiconductors and the position of the HOMO is below the redox electrolyte. The lower negative value of ΔG_inject and the lower positive ΔG_reg indicate that the DSSC is more efficient. The electron injection of the designed sensitizers is in the range of -0.970 to -1.344. Configuration 4 has the lower negative value of ΔG_inject and it has the greater number of π-spacers units. Configuration 3, on the other hand, has a lower positive value of ΔG_reg. The above results reveal that the DPP-4 has the lower negative value of ΔG_inject and the DPP-3 has the lower positive value of ΔG_reg value compared to other sensitizers.

Table 6

Electron injection (ΔG_inject), electron regeneration (ΔG_reg) of the DPP group of sensitizers.
Dyes	E_Ox	λ_max	OPES	ΔG_inject	ΔG_reg
DPP − 1	5.2956	2.6400	2.656	-1.344	0.496
DPP − 2	5.2592	2.3691	2.890	-1.110	0.459
DPP − 3	5.2472	2.5355	2.712	-1.288	0.447
DPP − 4	5.2679	2.2375	3.030	-0.970	0.468
DPP − 5	5.3027	2.3014	3.001	-0.999	0.503
DPP − 6	5.2853	2.4000	2.885	-1.115	0.485

Nlo Properties

The NLO properties are determined by the electronic properties of the sensitizers. The higher values of dipole moment and polarizability generate the electron hole pair in the DSSC [37]. From Table 7, the dipole moment value of DPP-1 is found to be 7.9521debye. Configuration 6 has the higher value of µ 18.5055 debye compared to the other configurations. One of the key criteria for greater polarizability is electron density. The polarizability values of the DPP sensitizers are increased in the order: DPP-1 < DPP-2 < DPP-3 < DPP-4 < DPP-5 < DPP-6. With configuration 1, which has the lower value of α and the inclusion of π-spacers in configuration 2, the value was increased due to the increased electron density of the sensitizers. Similarly, because of the increased number and changed positions of π-spacers, configurations 4,5 and 6 have higher values. The configuration 6 of the DPP sensitizers has a higher value of α compared to the other configurations. According to the aforementioned findings, configuration 6 has a greater dipole moment and polarizability value, which makes it a better fit for DSSC applications.

Table 7

NLO properties of the DPP group of sensitizers.
Dye	Dipole moment	Polarizability
Dye	Dipole moment	(au)	x10^− 23esu
DPP − 1	7.9521	303.168	4.493
DPP − 2	4.6716	346.692	5.138
DPP − 3	11.7348	364.861	5.407
DPP − 4	8.9936	417.273	6.184
DPP − 5	16.5646	464.125	6.878
DPP − 6	18.5055	484.457	7.179

DFT and TD-DFT functions in the B3LYP/6-311G(d,p) basis set are used to investigate six diphenylamine functionalized perylene-based sensitizer configurations. The NBO analysis reveals that configuration 2 has the higher positive value of q^D−A and possesses better electron donating ability when compared with the other configurations. Frontier molecular orbital analysis and NLO properties results reveal that the numbering and changed positions of the π-spacers are influenced by the HOMO-LUMO energy gap, dipole moment, and polarizability values. The absorption spectrum analysis reveals that configuration 6 has the red shift of the absorption spectrum, a higher molar extension coefficient, and higher LHE values, so configuration 6 is the better candidate for DSSC applications. The electron injection and electron regeneration results reveal that configuration 4 and configuration 3 have the best ΔG_inject and ΔG_reg values compared to the other configurations. All the above discussion reveals that configuration 6 has the lower HOMO-LUMO energy gap, higher µ and α values, red shift of the absorption spectra, higher ε value and higher LHE values and it reveals that DPP-6 is the better candidate for DSSC applications.

Author Contributions:

1) D.Nicksonsebastin

conception or design of the work,
acquisition, analysis, or interpretation of data,
drafted the work or revised it critically for important intellectual content,
approved the version to be published

2) P.Pounraj

conception or design of the work,

3) E. Isac Paulraj

acquisition, analysis, or interpretation of data

4) N.Mani

drafted the work or revised it critically for important intellectual content

5) M.Prasath

conception or design of the work
acquisition, analysis, or interpretation of data
drafted the work or revised it critically for important intellectual content
approved the version to be published

The first draft of the manuscript was written by D.Nicksonsebastin and all authors commented on previous versions of the manuscript. All authors read and approved the final manuscript

The authors declare that no funds, grants, or other support were received during the preparation of this manuscript.

Competing Interests

The authors have no relevant financial or non-financial interests to disclose.

Availability of data and material: Not Applicable

Code availability: Not Applicable

Ethics approval: Not Applicable

Panan H, Beibei A, Hehe R, Yuhang H, Xugeng G, Lemin M, Li W, Jinglai Z (2020) Influence of Different Molecular Design Strategies on Photovoltaic Properties of a Series of Triphenylamine-Based Organic Dyes for Dye-Sensitized Solar Cells: Insights from Theoretical Investigations J. Phys. Chem. C 124:15036-15044. https://doi.org/10.1021/acs.jpcc.0c04119
Govindaraj R, Santhosh N, Senthil Pandian M, Ramasamy P, Sumita M (2018) Fabrication of stable dye-sensitized solar cell with hydrothermally synthesized titanium dioxide nanorods as a photoanode material. J. Mater. Sci. Mater.Electron. 29:3736-3743. https://doi.org/10.1007/s10854-017-8307-2
Chowdhury F I, Buraidah M H, Arof A K, Mellander B E, Noor I M (2020) Impact of tetrabutylammonium, iodide and triiodide ions conductivity in polyacrylonitrile based electrolyte on DSSC performance. Sol. Energy 196: 379-388. https://doi.org/10.1016/j.solener.2019.12.033
Ji Z, Hai Bin L, Shi Ling S, Yun G, Yong. W, Zhong Min S (2012) Density functional theory characterization and design of high-performance diarylamine-fluorenedyes with different π spacers for dye-sensitized solar cells. J. Mater. Chem. 22: 568-576. https://doi.org/10.1039/C1JM13028E
Mohankumar V, Pounraj P, Senthil Pandian M, Ramasamy P (2019) Tuning the lifetime from molecular engineering of carbazole donor based metal-free organic dyes for dye sensitized solar cells – A computational approach. J. Mol. Struct 1195: 494-505. https://doi.org/10.1016/j.molstruc.2019.05.116
Kakiage K, Aoyama Y, Yano T, Oya K, Fujisawa J, Hanaya (2015) Highly-efficient dye-sensitized solar cells with collaborative sensitization by silyl-anchor and carboxy-anchor dyes. M Chem. Commun. 51:15894-15897. https://doi.org/10.1039/C5CC06759F
Pounraj P, Mohankumar V, Pandian M S, Ramasamy P (2018) Donor functionalized quinoline based organic sensitizers for dye sensitized solar cell (DSSC) applications: DFT and TD-DFT investigations. J. Mol. Model. 24: 343. https://doi.org/10.1007/s00894-018-3872-8
Nithya R, Senthilkumar K (2014) Theoretical studies on the quinoidal thiophene based dyes for dye sensitized solar cell and NLO applications. Phys Chem Chem Phys 16: 21496-21505. https://doi.org/10.1039/C4CP02694B
Krishnan R A, Pounraj P, Govindaraj R, Pandian M S, Ramasamy P (2022) Investigating the effect of π-configurations and methoxy substitution on donor and π- spacers based dyes for dye-sensitized solar cell applications–computational approach. Res Chem Intermed 48: 1877-1906. https://doi.org/10.1007/s11164-022-04698-6
Nicksonsebastin D, Pounraj P, Srinivasan M, Sathya B, Prasath M (2021) Exploring the screening of perylene based organic sensitizers with different lengths and functional groups of acceptors via computational spectroscopic analysis. Chemical Data Collections 34: 100729. https://doi.org/10.1016/j.cdc.2021.100729
Naik P, Elmorsy M R, Su R, Babu D D, El-Shafei A, Adhikari A V (2017) New carbazole based metal-free organic dyes with D-π-A-π-A architecture for DSSCs: Synthesis, theoretical and cell performance studies. Solar Energy 153: 600–610. https://doi.org/10.1016/j.solener.2017.05.088
Ito S, Zakeeruddin S M, Humphry-Baker R, Liska P, Charvet R, Comte P, Nazeeruddin M K, Péchy P, Grätzel (2006) High-Efficiency Organic-Dye- Sensitized Solar Cells Controlled by Nanocrystalline-TiO₂ Electrode Thickness. M Adv Mater 18:1202–1205. https://doi.org/10.1002/adma.200502540
Wang Z, Cui Y, Hara K, Dan-Oh Y, Kasada C, Shinpo A (2007) A High-Light-Harvesting-Efficiency Coumarin Dye for Stable Dye-Sensitized Solar Cells. Adv Mater 19:1138–1141. https://doi.org/10.1002/adma.200601020
Gao Z, Hao H, Li Z (2021) Theoretical study on thienothiophene core hole-transporting materials in perovskite solar cells: S atom position effect. Chem. Phys. Lett. 764: 138264. https://doi.org/10.1016/j.cplett.2020.138264
Fahim Z M E, Bouzzine S M, Ait Aicha Y, Bouachrine M, Hamidi M (2018) The bridged effect on the geometric, optoelectronic and charge transfer properties of the triphenylamine–bithiophene-based dyes: a DFT study. Res Chem Intermed 44: 2009–2023. https://doi.org/10.1039/D0EE02838J
Mahmood A, Wang J L (2021) Machine learning for high performance organic solar cells: current scenario and future prospects. Energy Environ. Sci. 14: 90-105. https://doi.org/10.1039/D0EE02838J
Mahmood A, Wang J L (2021) A time and resource efficient machine learning assisted design of non-fullerene small molecule acceptors for P3HT-based organic solar cells and green solvent selection. J. Mater. Chem. A 9: 15684-15695. https://doi.org/10.1039/D1TA04742F
Slimi A, Hachi M, Fitri A, A, Benjelloun A T, Elkhattabi S, Benzakour M, Mcharfi M, Khenfouch M, Zorkani I, Bouachrine M (2020) Effects of electron acceptor groups on triphenylamine-based dyes for dye-sensitized solar cells: Theoretical investigation. J. Photochem. Photobiol. A Chem. 398, 112572. https://doi.org/10.1016/j.jphotochem.2020.112572
Yang Z, Shao C, Cao D (2015) Screening donor groups of organic dyes for dye-sensitized solar cells. RSC Adv., 5: 22892–22898. https://doi.org/10.1039/C4RA17261B
Salimi Beni A R, Karami M, Hosseinzadeh B,. et al (2018) New organic dyes with diphenylamine core for dye-sensitized solar cells. J Mater Sci: Mater Electron 29: 6323–6336. https://doi.org/10.1007/s10854-018-8612-4
Nicksonsebastin D, Pounraj P, Prasath M (2022) Donor functionalized perylene and different π-spacer based sensitizers for dye-sensitized solar cell applications - a theoretical approach. J Mol Model 28: 102 https://doi.org/10.1007/s00894-022-05087-x
Frisch M J, Trucks G W, Schlegel H B, Scuseria G E. et al (2009) Gaussian 09, revision D.01. Gaussian Inc., Wallingford.
Dennington R, Keith T, Millam J (2009) GaussView, version 5. Semichem Inc., Shawnee Mission
Govindarasu R, Subramanian M K, Arunkumar A, Shanavas S, Anbarasan P M, Ahamad T, Alshehri S M (2021) Acceptor substituent effect on triphenylamine-based organic dye sensitizers for DSSCs: quantum chemical study. J. Iran. Chem. Soc. 18: 1279-1288. https://doi.org/10.1007/s13738-020-02112-9
Lazrak M, Toufik H, Bouzzine S M, Lamchouri F (2020) Bridge effect on the charge transfer and optoelectronic properties of triphenylamine-based organic dye sensitized solar cells: theoretical approach. Res. Chem. Intermed. 46: 3961- 3978. https://doi.org/10.1007/s11164-020-04184-x
Grätzel M Recent advances in sensitized mesoscopic solar cells (2009) Acc Chem Res 42:1788–1798. https://doi.org/10.1021/ar900141y
Govindammal M, Prasath M, Kamaraj S, Muthu S, Selvapandiyan M (2021) Exploring the molecular structure, vibrational spectroscopic, quantum chemical calculation and molecular docking studies of curcumin: A potential PI3K/AKT uptake inhibitor. Heliyon 7(4):e06646. https://doi.org/10.1016/j.heliyon.2021.e06646
Govindammal M, Prasath M (2020) Vibrational spectra, Hirshfeld surface analysis, molecular docking studies of (RS)-N,N-bis(2-chloroethyl)-1,3,2-oxazaphosphinan-2-amine 2-oxide by DFT approach. Heliyon 6(8):e04641. https://doi.org/10.1016/j.heliyon.2020.e04641
Govindammal M, Prasath M, Selvapandiyan M (2021) Spectroscopic (FT-IR, FT-Raman) investigations, quantum chemical calculations, ADMET and molecular docking studies of phloretin with B-RAF inhibitor Chem Pap 75:3771–3785. https://doi.org/10.1007/s11696-021-01576-0
Govindammal M, Kannan S, Srinivasan P, Prasath M (2022) Quantum chemical calculations, spectroscopic studies and molecular docking investigations of the anti-cancer drug quercitrin with B-RAF inhibitor. Heliyon 8: e09539. https://doi.org/10.1016/j.heliyon.2022.e09539
Mohankumar V, Pounraj P, Pandian M S. et al. (2021) Role of π conjugation in n-hexylphenothiazine dyes for solar cell—a density functional theory approach. J Mol Model 27: 151. https://doi.org/10.1007/s00894-021-04769-2
Nicksonsebastin D, Pounraj P, Mani N. et al. (2022) Screening the influence of methoxy and anisyl groups to perylene based sensitizers for dye-sensitized solar cell applications: a computational approach. J Mol Model 28, 373. https://doi.org/10.1007/s00894-022-05363-w
Gupta V D, Tathe A B, Padalkar V S, Umape, P G, Sekar N, (2013) Red emitting solid state fluorescent triphenylamine dyes: Synthesis, photo-physical property and DFT study. Dye. Pigment. 97:429-439. https://doi.org/10.1016/j.dyepig.2012.12.024
Mahmood A, Khan S UD, Rana U A. (2014) Theoretical designing of novel heterocyclic azo dyes for dye sensitized solar cells. J Comput Electron 13, 1033–1041. https://doi.org/10.1007/s10825-014-0628-2
Mahmood A, Hussaintahir M, Irfan A, Khalid B, Al-Sehemi A G (2015) Computational Designing of Triphenylamine Dyes with Broad and Red-shifted Absorption Spectra for Dye-sensitized Solar Cells using Multi-Thiophene Rings in π-Spacer. Bull. Korean Chem. Soc. 36, 2615-2620. https://doi.org/10.1002/bkcs.10526
Bai Y, Zhang J, et al. (2011) Engineering Organic Sensitizers for Iodine-Free Dye-Sensitized Solar Cells: Red-Shifted Current Response Concomitant with Attenuated Charge Recombination. J Am Chem Soc 133:11442–11445. https://doi.org/10.1021/ja203708k
Prakasam M, Anbarasan PM (2016) Second order hyperpolarizabilityof triphenylamine based organic sensitizers: a first principle theoretical study. RSC Adv 6:75242–75250. https:// doi. org/ 10.1039/ C6RA1 1200E

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Screening the effects of additional donors, numbers and positions of π-spacers on perylene- based sensitizers in dye-sensitized solar cell applications

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Abstract

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Introduction

Computational Details

Results And Discussion

Structure of the sensitizers

Nbo Analysis

Frontier Molecular Orbitals

Optical Properties

Electrochemical Properties

Nlo Properties

Conclusion

Declarations

References

Additional Declarations

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