Probing the effect of acceptor engineering in benzothiadiazole-based D-A-D-typed hole-transporting materials for perovskite solar cells

Sun, Zhu-Zhu; Feng, Shuai; Ding, Wei‐Lu; Yang, Jie; Zhu, Xiao-Rui; Liu, Jinglun; Xu, Xing-Lei

doi:10.1016/j.synthmet.2022.117136

Cited by 19 publications

(8 citation statements)

References 49 publications

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“…As reported in the previous works, 27,42,43 the functional BMK coupled with the 6-31G** basis set is suitable for the description of the neutral geometries of the HTMs, and can provide an accurate estimation of the HOMO energy levels of D–A–D type HTMs. And thus, this method is adopted in this work.…”

Section: Resultsmentioning

confidence: 82%

“…41 To further illustrate the structure–property relationship of D–A–D-type HTMs, we designed two series of HTMs by extending and rigidifying the BT acceptor, and the results from theoretical calculations show that the bulky π-conjugated acceptor groups and the better molecular planarity are helpful for improving the intermolecular orbital overlapping and hole-transporting ability. 42,43 Therefore, rational tailoring of the acceptor in the D–A–D scaffold is a primary strategy to promote the cell performance of HTMs.…”

Section: Introductionmentioning

confidence: 99%

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Donor engineering of a benzothiadiazole-based D–A–D-type molecular semiconductor for perovskite solar cells: a theoretical study

Sun,

Li,

2024

Phys. Chem. Chem. Phys.

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Section: Resultsmentioning

confidence: 82%

Section: Introductionmentioning

confidence: 99%

Donor engineering of a benzothiadiazole-based D–A–D-type molecular semiconductor for perovskite solar cells: a theoretical study

Sun,

Li,

2024

Phys. Chem. Chem. Phys.

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“…The mobility of the MPA-BT-CA is based on the theoretical structure. This calculational method has been identified to be reliable in our previous works, 38,50,58 and the detailed procedures are provided in the Supporting Information. The predicted crystal clusters and the Marcus parameters calculated from the possible hole transport pathways are shown in Figures S5− S9 and Tables S2−S6.…”

Section: Hole Mobilitymentioning

confidence: 97%

“…Besides developing new helicene-type π-linkers, rational tailoring of the molecular architecture, including D−π–A- (or D–A), − D−π–D-, ,, D–A–D-, ,− and D–A−π–A–D-type scaffolds, is an effective approach to enhance the performance of HTMs and to passivate the surface trap states of the perovskite. In contrast to traditional planar-type and spiro-type HTMs, the HTMs with the D–A-type architecture usually exhibit a variety of fascinating properties, such as the tunable energy levels, easy purification, effortless charge transport, and stable electron-rich arylamine system. , Particularly, a low-cost and eco-friendly D–A-type molecule MPA-BT-CA was reported by Guo et al through structural engineering with cyanoacrylic acid .…”

Section: Introductionmentioning

confidence: 99%

Thia[5]helicene-Based D−π–A-type Molecular Semiconductors for Stable and Efficient Perovskite Solar Cells: A Theoretical Study

Sun

Long

2023

J. Phys. Chem. C

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Development of ideal small-molecule hole-transporting materials (HTMs) is one of the most effective means to improve the performance of perovskite solar cells. Meanwhile, the theoretical chemistry method is an efficient pathway to optimize the molecular structure and to probe the structure−property relationship. To further find new HTMs, thia[5]helicene and its counterpart perylothiophene are introduced into the D−π−A-type molecular scaffold of MPA-BT-CA, and the results show that helicene-type HTMs (SM46 and SM48) exhibit obvious advantages in comparison with that of the planar SM45 and SM47. The matched energy levels with the mixed perovskite provide a precondition for the easy hole transfer at the interface, and the blueshifted adsorption spectra can effectually decrease the optical competition between the perovskite and HTMs. More importantly, the helicene-type HTMs show the higher mobilities than that of the planar counterparts, which is mainly contributed by the enlarged hole transfer integrals via compact molecular stacking. Fluorine addition can also stabilize the highest occupied molecular orbitals and enhance the hole transport ability of HTMs. Moreover, a simplified adsorption model for the MPA-BT-CA is constructed to investigate the interfacial properties of adsorbed systems, and the results demonstrate that bidentate adsorption displays more stable adsorption configuration and a better passivation effect for the iodine-vacant FAPbI 3 surface. In summary, this work provides useful clues for the design of new D−π−A-type HTMs, and two promising helicene-based HTMs are proposed.

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“…The hole reorganization energy was calculated with the adiabatic potential energy surface approach . The crystal structure was predicted by using the polymorph module in Materials Studio, and the detailed computational procedures were reported in our previous works. ,, On the basis of the predicted structures, the hole transfer integral calculations were carried out at the PW91PW91/6-31G** level, which can give a better estimation for the electronic coupling at the density functional theory level. , …”

Section: Computational Detailsmentioning

confidence: 99%

Interfacial and Molecular Engineering of a Helicene-Based Molecular Semiconductor for Stable and Efficient Perovskite Solar Cells

Sun

Long

2023

J. Phys. Chem. C

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Due to the attractive optoelectronic properties and extensive application in solar cells, the design of new helicene-type molecular semiconductors is of remarkable importance for development of high-efficiency hole-transporting materials (HTMs). In this work, three helicene HTMs are constructed on the basis of the molecular conformation of experimentally reported T5H-OMeDPA by replacing the thia[5]helicene unit with a more curved π-linker of dithia[6]helicene and considering the effects of fluorine substitution. The electronic and optical properties, hole transport, and interfacial property are studied with quantum chemistry methods, and the results show that new tailored HTMs perform much better than T5H-OMeDPA in terms of the calculated HOMO levels, hole mobility, optical adsorption, solubility and stability, interfacial stability, and hole transfer. The more stable HOMO levels of new HTMs (SM31–SM33) will be beneficial for the regulation of interfacial energy alignment. Importantly, the hole mobilities of the designed HTMs are also distinctly improved due to the enhanced electronic coupling and lowered hole reorganization energies. The fluorine substitution can clearly heighten the orbital overlapping via compact molecule packing. In the meantime, dithia[6]helicene can lower the reorganization energy although the more curved π-electron system often disturbs the intermolecular π–π stacking. Moreover, our results also reveal that additional Pb–S interactions can effectually promote the interface adsorption and hole extraction. In sum, our study shows the validity of fluorine substitution and introduces helicene with a more extended structure, and three potential helicene-type HTMs are proposed.

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Probing the effect of acceptor engineering in benzothiadiazole-based D-A-D-typed hole-transporting materials for perovskite solar cells

Cited by 19 publications

References 49 publications

Donor engineering of a benzothiadiazole-based D–A–D-type molecular semiconductor for perovskite solar cells: a theoretical study

Donor engineering of a benzothiadiazole-based D–A–D-type molecular semiconductor for perovskite solar cells: a theoretical study

Thia[5]helicene-Based D−π–A-type Molecular Semiconductors for Stable and Efficient Perovskite Solar Cells: A Theoretical Study

Interfacial and Molecular Engineering of a Helicene-Based Molecular Semiconductor for Stable and Efficient Perovskite Solar Cells

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