Electronic structure evolution induced by the charge redistribution during the construction of two-dimensional polymer networks from monomers to crystal frameworks

Jing, Junfeng; Chen, Weikun; Huang, Zehua; Huang, Luyan; Liang, Xuefeng; He, Yan; Li, Huifang

doi:10.1039/d2cp04196k

Cited by 3 publications

(2 citation statements)

References 57 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thereby, it is predicted that the expected charge-carrier mobility within 2D frameworks of sp 2 c-COF should be larger than that of COF366 as the more dispersive (highly curved) the band structure at the VBM/CBM, the smaller the hole/ electron effective mass, and thus the larger the expected charge-carrier mobility. 65,66 3.1. p-Type Doping Effects on the Electronic Structure of COF Monolayers. 3.1.1.…”

Section: Resultsmentioning

confidence: 99%

“…Calculated bandwidths of the top valence band and the bottom conduction band of sp 2 c-COF are about 0.15 and 0.17 eV, respectively, which are much larger than those of COF366 (bandwidth of the top valence band is 0.08 eV, and bandwidth of the bottom conduction band is 0.09 eV). Thereby, it is predicted that the expected charge-carrier mobility within 2D frameworks of sp 2 c-COF should be larger than that of COF366 as the more dispersive (highly curved) the band structure at the VBM/CBM, the smaller the hole/electron effective mass, and thus the larger the expected charge-carrier mobility. , …”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Effective Fermi-Level Modulation of Two-Dimensional Conjugated Covalent Organic Frameworks Achieved by Introducing p-Type Organic Dopants

Chen

Liang

et al. 2023

Macromolecules

Self Cite

View full text Add to dashboard Cite

Covalent organic frameworks (COFs) are a new emerging class of two-dimensional functional materials, and their unique electronic character plays a key role in practical applications. Here, to provide a useful strategy to tune the electronic character of COFs, doping effects with organic molecular acceptors, TCNQ, F4TCNQ, and TCNE, on the frontier orbital energy levels of sp2c-COF and COF366 mono- and bilayers are explored. Due to the charge transfer from COFs to dopants, the Fermi level is shifted to a lower energy and drops into the top valence band of sp2c-COF and COF366, and the VBM/CBM energy level of COFs is also decreased. Moreover, the increased electron density shifts the LUMO energy level of dopants to a higher energy. Then, two electronic states, the top valence band of COFs and the LUMO of the p-type dopants, are pinned around the Fermi level. It means that the organic molecular acceptor serves as an effective p-type dopant for COFs. In addition, it is confirmed that the stronger the electron-accepting ability of p-type dopants or the higher the surface density of the dopants, the larger the variation of the frontier energy levels of COF monolayers will be. Thereby, an overall linear correlation between the electronic property variations of COFs and the charge transfer amount from COFs to p-type dopants is observed. Our results proved that surface doping with organic molecular acceptors is a reliable approach to modulate the frontier energy level of COFs, which provides an effective strategy to optimize the performance of COF-based devices.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Effective Fermi-Level Modulation of Two-Dimensional Conjugated Covalent Organic Frameworks Achieved by Introducing p-Type Organic Dopants

Chen

Liang

et al. 2023

Macromolecules

Self Cite

View full text Add to dashboard Cite

show abstract

Improving the response of 2D COFs to the surface doping strategies through rational design of their chemical structure

Feng,

Liang,

et al. 2024

Sci. China Mater.

View full text Add to dashboard Cite

Photons, Excitons, and Electrons in Covalent Organic Frameworks

Blätte,

Ortmann,

Bein

2024

J. Am. Chem. Soc.

View full text Add to dashboard Cite

Covalent organic frameworks (COFs) are created by the condensation of molecular building blocks and nodes to form two-dimensional (2D) or three-dimensional (3D) crystalline frameworks. The diversity of molecular building blocks with different properties and functionalities and the large number of possible framework topologies open a vast space of possible welldefined porous architectures. Besides more classical applications of porous materials such as molecular absorption, separation, and catalytic conversions, interest in the optoelectronic properties of COFs has recently increased considerably. The electronic properties of both the molecular building blocks and their linkage chemistry can be controlled to tune photon absorption and emission, to create excitons and charge carriers, and to use these charge carriers in different applications such as photocatalysis, luminescence, chemical sensing, and photovoltaics. In this Perspective, we will discuss the relationship between the structural features of COFs and their optoelectronic properties, starting with the building blocks and their chemical connectivity, layer stacking in 2D COFs, control over defects and morphology including thin film synthesis, exploring the theoretical modeling of structural, electronic, and dynamic features of COFs, and discussing recent intriguing applications with a focus on photocatalysis and photoelectrochemistry. We conclude with some remarks about present challenges and future prospects of this powerful architectural paradigm.

show abstract

Electronic structure evolution induced by the charge redistribution during the construction of two-dimensional polymer networks from monomers to crystal frameworks

Abstract: Two-dimensional covalent organic frameworks (COFs) are a new type of porous crystalline materials constructed by the linkage of organic building units through covalent bonds to produce predetermined structures. Here, electronic...

Cited by 3 publications

References 57 publications

Effective Fermi-Level Modulation of Two-Dimensional Conjugated Covalent Organic Frameworks Achieved by Introducing p-Type Organic Dopants

Effective Fermi-Level Modulation of Two-Dimensional Conjugated Covalent Organic Frameworks Achieved by Introducing p-Type Organic Dopants

Improving the response of 2D COFs to the surface doping strategies through rational design of their chemical structure

Photons, Excitons, and Electrons in Covalent Organic Frameworks

Contact Info

Product

Resources

About