Designing Organic Semiconductors with Ultrasmall Reorganization Energies: Insights from Molecular Symmetry, Aromaticity and Energy Gap

Huang, Wendeng; Xie, Wen Jun; Huang, Huijuan; Zhang, Heng; Liu, Hongguang

doi:10.1021/acs.jpclett.0c01199

Cited by 34 publications

(29 citation statements)

References 67 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[ 39 ] The computed hole reorganization energy for [3]Ph is equal to 0.366 eV and is comparable to common organic semiconductors based on sp 2 ‐hybridized carbon scaffolds in organic electronics, such as oligothiophenes and acenes. [ 68,69 ] The major structural reorganization process occurring upon charging (i.e., adding a hole) involves the carbon chain, namely a variation of the bond length alternation (Figure S12b, Supporting Information). Additionally, Figure 3d depicts the HOMO orbital of dimer D1, which shows the highest hole transfer integral.…”

Section: Resultsmentioning

confidence: 99%

Stable and Solution‐Processable Cumulenic sp‐Carbon Wires: A New Paradigm for Organic Electronics

et al. 2022

View full text Add to dashboard Cite

has boosted the field of large-area flexible and printed electronics. These advances have enabled a plethora of applications such as organic light-emitting diodes, [1,2] organic photovoltaics, [3,4] organic thermoelectrics, [5,6] organic field-effect transistors (OFETs), [7][8][9][10] organic (bio)sensors, [11][12][13] and neuromorphic devices. [14,15] In this context, organic field-effect transistors (OFETs) are not only relevant for their direct technological application, but they also represent an ideal test-bed to investigate thin-film electrical properties. Organic semiconductors are typically classified in two main families, namely conjugated polymers and small molecules. The former, polymers, are particularly appealing as a result of their solution processability, and OFETs with charge mobility above the standard for hydrogenated amorphous silicon (0.5-1 cm 2 V −1 s −1 ) have been extensively reported. [16] The latter, small molecules, are prone to arrange in ordered molecular crystals, and through several years of chemical tailoring and fine tuning of the films processing, small-molecule OFETs with field-effect mobility >10 cm 2 V −1 s −1 have been achieved. [17][18][19] The chemical root of the π-conjugation of these materials is associated with the sp 2 -hybridization of carbon atoms in their backbone. This peculiar trait is also common to Solution-processed, large-area, and flexible electronics largely relies on the excellent electronic properties of sp 2 -hybridized carbon molecules, either in the form of π-conjugated small molecules and polymers or graphene and carbon nanotubes. Carbon with sp-hybridization, the foundation of the elusive allotrope carbyne, offers vast opportunities for functionalized molecules in the form of linear carbon atomic wires (CAWs), with intriguing and even superior predicted electronic properties. While CAWs represent a vibrant field of research, to date, they have only been applied sparingly to molecular devices. The recent observation of the field-effect in microcrystalline cumulenes suggests their potential applications in solution-processed thin-film transistors but concerns surrounding the stability and electronic performance have precluded developments in this direction. In the present study, ideal field-effect characteristics are demonstrated for solution-processed thin films of tetraphenyl[3]cumulene, the shortest semiconducting CAW. Films are deposited through a scalable, large-area, meniscus-coating technique, providing transistors with hole mobilities in excess of 0.1 cm 2 V −1 s −1 , as well as promising operational stability under dark conditions. These results offer a solid foundation for the exploitation of a vast class of molecular semiconductors for organic electronics based on sp-hybridized carbon systems and create a previously unexplored paradigm.

show abstract

Section: Resultsmentioning

confidence: 99%

Stable and Solution‐Processable Cumulenic sp‐Carbon Wires: A New Paradigm for Organic Electronics

et al. 2022

View full text Add to dashboard Cite

show abstract

“…The optimized structures were utilized for frequency, NMR and natural bond orbital (NBO) calculations. Specifically, the energy gap between the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) (E HL ) [ 20 ], hardness (η) [ 21 ], softness ( S ) [ 22 ], point groups [ 23 ] and geometric parameters for measuring harmonic oscillator model of aromaticity (HOMA) [ 24 ] were calculated. All detailed information for measuring HOMA is available in Section SI.1.2.…”

Section: Methodsmentioning

confidence: 99%

Elucidating the Aromatic Properties of Covalent Organic Frameworks Surface for Enhanced Polar Solvent Adsorption

et al. 2021

View full text Add to dashboard Cite

Covalent organic frameworks (COFs) have a distinguished surface as they are mostly made by boron, carbon, nitrogen and oxygen. Many applications of COFs rely on polarity, size, charge, stability and hydrophobicity/hydrophilicity of their surface. In this study, two frequently used COFs sheets, COF-1 and covalent triazine-based frameworks (CTF-1), are studied. In addition, a theoretical porous graphene (TPG) was included for comparison purposes. The three solid sheets were investigated for aromaticity and stability using quantum mechanics calculations and their ability for water and ethanol adsorption using molecular dynamics simulations. COF-1 demonstrated the poorest aromatic character due to the highest energy delocalization interaction between B–O bonding orbital of sigma type and unfilled valence-shell nonbonding of boron. CTF-1 was identified as the least kinetically stable and the most chemically reactive. Both COF-1 and CTF-1 showed good surface properties for selective adsorption of water via hydrogen bonding and electrostatic interactions. Among the three sheets, TPG’s surface was mostly affected by aromatic currents and localized π electrons on the phenyl rings which in turn made it the best platform for selective adsorption of ethanol via van der Waals interactions. These results can serve as guidelines for future studies on solvent adsorption for COFs materials.

show abstract

“…Since λ shows the extent of geometrical changes upon electron/hole transfer [34], the enhancement of λ may be attributed to the strain received from structure deplanarization [35], chemisorption induced loss of conjugation and reducing the effective intermolecular π‐orbital overlap [36]. Therefore, small λ is desirable for efficient charge transfer (electron/hole) [37, 38].…”

Section: Computational Detailsmentioning

confidence: 99%

Insight into the semiconducting performance of tetraphenyldipyranylidene derivatives in organic field‐effect transistors

Naserian

Izadyar

Arkan

2021

Int J of Quantum Chemistry

View full text Add to dashboard Cite

In this paper, tetraphenyldipyranylidene (DPPh) was considered as the primary organic molecule in organic field-effect transistors (OFETs). Electron-withdrawing atoms (F, Cl, and Br) were attached to the H-atoms of four peripheral phenyl groups of para-positions relative to the O-atoms of DPPh. The influences of different electron-withdrawing atoms on the electronic and optical properties, charge transport parameters, and charge carrier mobility were investigated at the M06-2X/6-311++G (d,p) level. The absorption and emission spectra were theoretically simulated and an intense peak in the visible region was obtained. Moreover, the charge injection energy barriers were calculated by considering Pt as the source electrode and a greater hole transport than electron transport was confirmed. Also, the obtained ratio of the hole/electron mobility shows that the insertion of the electron-withdrawing atoms in DPPh is a promising strategy to have an ambipolar or n-type semiconductor.Finally, DPPh-Br shows a greater performance in the OFETs.

show abstract

Designing Organic Semiconductors with Ultrasmall Reorganization Energies: Insights from Molecular Symmetry, Aromaticity and Energy Gap

Cited by 34 publications

References 67 publications

Stable and Solution‐Processable Cumulenic sp‐Carbon Wires: A New Paradigm for Organic Electronics

Stable and Solution‐Processable Cumulenic sp‐Carbon Wires: A New Paradigm for Organic Electronics

Elucidating the Aromatic Properties of Covalent Organic Frameworks Surface for Enhanced Polar Solvent Adsorption

Insight into the semiconducting performance of tetraphenyldipyranylidene derivatives in organic field‐effect transistors

Contact Info

Product

Resources

About