Porphyrin Supramolecule as Surface Carrier Modulator Imparts Hole Transporter with Enhanced Mobility for Perovskite Photovoltaics

Mu, Xijiao; Li, Yajun; Xiao, Guo‐Bin; Xu, Cheng; Gao, Xingbang

doi:10.1002/anie.202307152

Cited by 6 publications

(2 citation statements)

References 44 publications

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“…In more recent work, Cao and collaborators also reported the remarkable increase in the hole mobility of a spiro-OMeTAD film (8-fold higher) after doping with oxygen-bridged dimer Fe-50 (Figure ). This improvement was ascribed to the formation of a one-dimensional supramolecular structure via π–π interactions of adjacent dimers to reach large polarons on their oxygen bridges providing a sequential charge transfer on the HTM interface . The synthesis of oxygen-bridged porphyrin dimer Fe-50 was based on the treatment of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin 40 with FeCl 3 .…”

Section: Porphyrins As Defect Passivator Improving Charge Transport I...mentioning

confidence: 99%

“…This improvement was ascribed to the formation of a one-dimensional supramolecular structure via π–π interactions of adjacent dimers to reach large polarons on their oxygen bridges providing a sequential charge transfer on the HTM interface. 58 The synthesis of oxygen-bridged porphyrin dimer Fe-50 was based on the treatment of 5-(4-aminophenyl)-10,15,20-triphenylporphyrin 40 with FeCl 3 .…”

Section: Porphyrins As Defect Passivator Improving Charge Transport I...mentioning

confidence: 99%

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Porphyrin-Based Hole-Transporting Materials for Perovskite Solar Cells: Boosting Performance with Smart Synthesis

Reis,

Pereira,

Moura

et al. 2024

ACS Omega

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Perovskite solar cells (PSCs) are becoming a promising and revolutionary advancement within the photovoltaic field globally. Continuous improvement in efficiency, straightforward processing methods, and use of lightweight and cost-effective materials represent superior features, among other notable aspects. Still, long-term stability and durability are issues to address to facilitate widespread commercial adoption and practical application prospects. Research has focused on overcoming these challenges, and charge transport materials play a critical role in determining charge dynamics, photovoltaic performance, and device stability. Conventional hole-transporting materials (HTMs), spiro-OMe-TAD and PTAA, contribute to remarkable power conversion efficiencies owing to high thin-film quality and matched energy alignment. However, they often show a high material cost, low carrier mobility, and poor stability, which greatly limit their practical applications. Now, this review outlines recent advances in synthetic approaches to porphyrin-based HTMs to tune the charge dynamics by optimizing their molecular structures and properties. The main structural features comprise porphyrins of A 4 -type, trans A 2 B 2 -type, and photosynthetic pigment analogues. Strategies include well-established routes to provide the required macrocycles, such as condensation of pyrrole or dipyrromethanes with suitable aldehydes, metalation of the porphyrin inner core, and postfunctionalization of peripheral positions. These functionalizations involve conventional procedures (e.g., halogenation, esterification, transesterification, nucleophilic oxidation, reduction, and nucleophilic substitution) as well as metal-catalyzed ones such as Suzuki−Miyaura, Sonogashira, Buchwald−Hartwig, and Ullmann cross-coupling reactions. As HTMs can also protect the perovskite layer from the external environment, porphyrin structures play a pivotal role in chemical, mechanical, and environmental stability, with their high hydrophobicity ability as the most significant parameter. The impact of porphyrins on the hole hopping of other HTMs while acting as an additive or an interlayer, passivating defects, and improving charge transport is also highlighted to provide real insights into ways to develop efficient and stable porphyrin-based materials for PSCs. This perspective aims to guide the scientific community in the design of new porphyrin molecules to place PSCs as an outperformer in photovoltaic technologies.

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Section: Porphyrins As Defect Passivator Improving Charge Transport I...mentioning

confidence: 99%

Section: Porphyrins As Defect Passivator Improving Charge Transport I...mentioning

confidence: 99%

Porphyrin-Based Hole-Transporting Materials for Perovskite Solar Cells: Boosting Performance with Smart Synthesis

Reis,

Pereira,

Moura

et al. 2024

ACS Omega

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Direction Modulation of Intramolecular Electric Field Boosts Hole Transport in Phthalocyanines for Perovskite Solar Cells

Xiao,

Mu,

Suo

et al. 2024

Angewandte Chemie

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Tuning the strength of intramolecular electric field (IEF) in conjugated molecules has emerged as an effective approach to boost charge transfer. While direction manipulation of IEF would be a potential way that is still unclear. Here, we leverage the control of peripheral substituents of conjugated phthalocyanines to chemically tune the spatial orientation of IEF. By analyzing the spatial swing of side chains using the Kolmogorov‐Arnold representation and least squares algorithm, a comprehensive mathematical‐physical model has been established. This model enables rapid evaluation of the IEF and maximum hole transport performance induced by spatial swings. The champion phthalocyanine as dopant‐free hole transport material in perovskite solar cell realizes a record performance of 23.41 %. Greatly device stability is also exhibited. This work affords a new way to enhance hole transport capabilities of conjugated molecules by optimizing their IEF vector for photovoltaic devices.

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Direction Modulation of Intramolecular Electric Field Boosts Hole Transport in Phthalocyanines for Perovskite Solar Cells

Xiao,

Mu,

Suo

et al. 2024

Angew Chem Int Ed

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Porphyrin Supramolecule as Surface Carrier Modulator Imparts Hole Transporter with Enhanced Mobility for Perovskite Photovoltaics

Cited by 6 publications

References 44 publications

Porphyrin-Based Hole-Transporting Materials for Perovskite Solar Cells: Boosting Performance with Smart Synthesis

Porphyrin-Based Hole-Transporting Materials for Perovskite Solar Cells: Boosting Performance with Smart Synthesis

Direction Modulation of Intramolecular Electric Field Boosts Hole Transport in Phthalocyanines for Perovskite Solar Cells

Direction Modulation of Intramolecular Electric Field Boosts Hole Transport in Phthalocyanines for Perovskite Solar Cells

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