DFT/TD-DFT study of novel T shaped phenothiazine-based organic dyes for dye-sensitized solar cells applications

Xu, Zhijie; Li, Yuanyuan; Zhang, Wenjiong; Yuan, Shundong; Hao, Lanzhong; Xu, Tao; Lü, Xiaoqing

doi:10.1016/j.saa.2019.01.002

Cited by 69 publications

(27 citation statements)

References 52 publications

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“…Next, the key parameters affecting J sc and V oc from the view of molecular design and evaluation will be discussed. The following expressions (3)–(6) are from references [ 44 , 45 , 46 , 47 ]. The V oc can be described by:

where q is the unit charge, E CB is the conduction band edge of the semiconductor substrate, ΔE CB is the level shift of conduction band edge of TiO 2 due to dye adsorption, k B is the Boltzmann constant, T is the absolute temperature, n c is the number of electrons in the conduction band, N CB is the density of accessible states in the conduction band, and E redox is the electrolyte Fermi level.…”

Section: Resultsmentioning

confidence: 99%

Theoretical Analysis on Heteroleptic Cu(I)-Based Complexes for Dye-Sensitized Solar Cells: Effect of Anchors on Electronic Structure, Spectrum, Excitation, and Intramolecular and Interfacial Electron Transfer

et al. 2020

Molecules

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Two groups of heteroleptic Cu(I)-based dyes were designed and theoretically investigated by density functional theory (DFT) and time-dependent DFT (TD-DFT) methods. Different anchors were integrated into the dye skeleton to shed light on how the type of anchor influenced the electronic structure, absorption spectrum, electron excitation, and intramolecular and interfacial electron transfer of dyes. The results indicated that, compared with other dyes, the dyes with cyanoacrylic acid and nitric acid exhibited more appropriate electron distributions in frontier molecular orbitals (FMOs), lower HOMO (the highest occupied molecular orbital) –LUMO (the lowest unoccupied molecular orbital) energy gaps, broader absorption spectral ranges as well as improved spectral characteristics in the near-infrared region and better intramolecular electron transfer (IET) characteristics with more electrons transferred to longer distances, but smaller orbital overlap. Among all the studied Cu(I)-based dyes, B1 and P1 (with cyanoacrylic acid anchoring group) exhibited the best interface electronic structure parameters with a relatively short electron injection time (τinj) and large dipole moment (μnormal), which would have a positive effect on the open-circuit photovoltage (Voc) and short-circuit current density (Jsc), resulting in high power conversion efficiency (PCE) of dye-sensitized solar cells (DSSCs). Our findings are expected to provide a new insight into the designing and screening of high-performance dyes for DSSCs.

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Section: Resultsmentioning

confidence: 99%

Theoretical Analysis on Heteroleptic Cu(I)-Based Complexes for Dye-Sensitized Solar Cells: Effect of Anchors on Electronic Structure, Spectrum, Excitation, and Intramolecular and Interfacial Electron Transfer

et al. 2020

Molecules

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“…One obvious reason is that such a complex could only consider bidentate chelate anchoring, in contrast with the vast experimental and computational data, indicating bidentate bridging [25]. Moreover, we warn that small clusters, such as Ti 5 O 20 H 22 [26], (TiO 2 ) 6 [27,29,30], Ti 6 O 21 H 18 [28] (TiO 2 ) 9 [31,84], and even (TiO 2 ) 15 [32] or (TiO 2 ) 16 [85], may not reproduce sufficiently well the electronic structure and optical spectra of the small molecules bound to the substrate.…”

Section: Discussionmentioning

confidence: 98%

Structure and Electronic Properties of TiO2 Nanoclusters and Dye–Nanocluster Systems Appropriate to Model Hybrid Photovoltaic or Photocatalytic Applications

Oprea

Gîrţu

2019

Nanomaterials

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We report the results of a computational study of TiO2 nanoclusters of various sizes as well as of complex systems with various molecules adsorbed onto the clusters to set the ground for the modeling of charge transfer processes in hybrid organic–inorganic photovoltaics or photocatalytic degradation of pollutants. Despite the large number of existing computational studies of TiO2 clusters and in spite of the higher computing power of the typical available hardware, allowing for calculations of larger systems, there are still studies that use cluster sizes that are too small and not appropriate to address particular problems or certain complex systems relevant in photovoltaic or photocatalytic applications. By means of density functional theory (DFT) calculations, we attempt to find acceptable minimal sizes of the TinO2n+2H4 (n = 14, 24, 34, 44, 54) nanoclusters in correlation with the size of the adsorbed molecule and the rigidity of the backbone of the molecule to model systems and interface processes that occur in hybrid photovoltaics and photocatalysis. We illustrate various adsorption cases with a small rigid molecule based on coumarin, a larger rigid oligomethine cyanine dye with indol groups, and the penicillin V antibiotic having a flexible backbone. We find that the use of the n = 14 cluster to describe adsorption leads to significant distortions of both the cluster and the molecule and to unusual tridentate binding configurations not seen for larger clusters. Moreover, the significantly weaker bonding as well as the differences in the density of states and in the optical spectra suggest that the n = 14 cluster is a poor choice for simulating the materials used in the practical applications envisaged here. As the n = 24 cluster has provided mixed results, we argue that cluster sizes larger than or equal to n = 34 are necessary to provide the reliability required by photovoltaic and photocatalytic applications. Furthermore, the tendency to saturate the key quantities of interest when moving from n = 44 to n = 54 suggests that the largest cluster may bring little improvement at a significantly higher computational cost.

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“…The optimization molecular ground-state geometry and absorption spectra of the PTZ-3 and PTZ-5 were obtained in the THF using density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculation at B3LYP/6-311G(d,p)//B3LYP/6-311G(d) level with Gaussian 09 software, respectively. The detailed methods were described in the previous article. ,,− …”

Section: Experimental Sectionmentioning

confidence: 99%

Comparative Studies on the Structure–Performance Relationships of Phenothiazine-Based Organic Dyes for Dye-Sensitized Solar Cells

Jiang

et al. 2021

ACS Omega

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A D–A−π–A dye ( PTZ-5 ) has been synthesized by introducing a benzothiadiazole (BTD) unit as an auxiliary acceptor in a phenothiazine-based D−π–A dye( PTZ-3 ) to broaden its spectral response range and improve the device performance. Photophysical properties indicate that the inclusion of BTD in the PTZ-5 effectively red-shifted the absorption spectra by reducing the E gap . However, the device measurements show that the open-circuit voltage ( V oc ) of PTZ-5 cell (640 mV) is obviously lower than that of the PTZ-3 cell (710 mV). This results in a poor photoelectric conversion efficiency (PCE) (4.43%) compared to that of PTZ-3 cell (5.53%). Through further comparative analysis, we found that the introduction of BTD increases the dihedral angle between the D and A unit, which can reduce the efficiency of intramolecular charge transfer (ICT), lead to a less q CT and lower molar extinction coefficient of PTZ-5 . In addition, the ESI test found that the lifetime of the electrons in the PTZ-5 cell is shorter. These are the main factors for the above unexpected result of PCE. Our studies bring new insights into the development of phenothiazine-based highly efficient dye-sensitized solar cells (DSSCs).

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DFT/TD-DFT study of novel T shaped phenothiazine-based organic dyes for dye-sensitized solar cells applications

Cited by 69 publications

References 52 publications

Theoretical Analysis on Heteroleptic Cu(I)-Based Complexes for Dye-Sensitized Solar Cells: Effect of Anchors on Electronic Structure, Spectrum, Excitation, and Intramolecular and Interfacial Electron Transfer

Theoretical Analysis on Heteroleptic Cu(I)-Based Complexes for Dye-Sensitized Solar Cells: Effect of Anchors on Electronic Structure, Spectrum, Excitation, and Intramolecular and Interfacial Electron Transfer

Structure and Electronic Properties of TiO2 Nanoclusters and Dye–Nanocluster Systems Appropriate to Model Hybrid Photovoltaic or Photocatalytic Applications

Comparative Studies on the Structure–Performance Relationships of Phenothiazine-Based Organic Dyes for Dye-Sensitized Solar Cells

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