Crossover from Hopping to Band-Like Charge Transport in an Organic Semiconductor Model: Atomistic Nonadiabatic Molecular Dynamics Simulation

Giannini, Samuele; Carof, Antoine; Blumberger, Jochen

doi:10.1021/acs.jpclett.8b01112

Cited by 80 publications

(156 citation statements)

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“…46,47 Through direct propagation of the hole wavefunction, critical quantities are evaluated, such as the hole drift mobility, and a detailed picture of polaron dynamics is promptly sketched, hence allowing the differentiation between hopping and band-like conductivity mechanisms. 48 Our basic findings indicate that the peripheral substitution has a staggering effect on charge transfer. The differences in the side chain length and the morphology lead to variations in the solid state packing that directly alter the intracolumnar stacking patterns and the associated hole charge transfer integrals.…”

Section: Introductionmentioning

confidence: 69%

“…The key assumptions of the FOB-SH methodology are that the full many-body electronic wavefunction can be replaced by a one-particle wavefunction for the excess charge carrier, with the latter expressed in a quasi-diabatic basis made up of orthogonalized fragment molecular orbitals (FMO), and that electronnuclei dynamics are approximated by a mixed quantum-classical scheme, with explicit treatment of diagonal and off-diagonal electron-phonon coupling. [46][47][48] In the FOB-SH method, an excess charge carrier is treated by a time-dependent one-particle wavefunction C(t) which is expanded on a basis of orthogonalized FMOs:…”

Section: Methodsmentioning

confidence: 99%

“…Although SH is an intuitively derived algorithm, it has been shown to provide fair approximate quantum dynamics, especially when coupled with appropriate decoherence corrections, for a large number of systems and still remains the best compromise between accuracy and computational efficiency. [46][47][48][49] In order to explore the suitability of alkyl-substituted tetracenes as hole conducting media, mixed quantum-classical non-adiabatic molecular dynamics simulations are employed by means of the fragment orbital-based surface hopping methodology. 46,47 Through direct propagation of the hole wavefunction, critical quantities are evaluated, such as the hole drift mobility, and a detailed picture of polaron dynamics is promptly sketched, hence allowing the differentiation between hopping and band-like conductivity mechanisms.…”

Section: Introductionmentioning

confidence: 99%

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Identifying high-mobility tetracene derivatives using a non-adiabatic molecular dynamics approach

et al. 2020

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The search for conductive soft matter materials with significant charge mobility under ambient conditions has been a major priority in organic electronics (OE) research. Alkylated tetracenes are promising cost-effective candidate molecules that can be synthesized using wet chemistry methods, resulting in columnar single crystals with pronounced structural stability at and above room temperature. A remarkable characteristic of these materials is the capability of tuning the tetracene core intracolumnar stacking pattern and the crystal melting point via the side chain length and type modifications. In this study, we examine the performance of a series of alkylated tetracenes as hole conducting materials using a novel atomistic simulation technique that allows us to predict both the charge transport mechanism and mobilities. Our simulations demonstrate that molecular wires of alkylated tetracenes are capable of polaronic hole conduction at room temperature, with mobility values ranging up to 21 cm 2 V À1 s À1 , thus rendering such materials a highly promising choice for flexible OE applications. As regards the charge transfer robustness, two promising tetracene derivatives are identified with the capability of seamless inter-wire polaron delocalization, alleviating possible transfer bottlenecks due to local molecular defects. Our findings suggest that alkylated tetracenes offer an attractive route towards flexible columnar OE materials with unprecedented hole mobilities. † Electronic supplementary information (ESI) available: Description of the FOBSH methodology; systems under study; utilized force field and molecular dynamics simulations details; reorganization energy and charge transfer integral calculations details; classical force field validation results; inverse participation ratio time series for the TMT molecular crystal. See

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Section: Introductionmentioning

confidence: 69%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Identifying high-mobility tetracene derivatives using a non-adiabatic molecular dynamics approach

et al. 2020

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“…When disorder is so strong that the carriers become localized on a single molecular site, Eq. (1) ceases to be valid and a transition to a thermally activated hopping regime is expected [34][35][36][37] . The breakdown of the TL regime can be estimated by setting L ≈ a in Eq.…”

Section: In Inorganic Semiconductors Including the Observation Of Anmentioning

confidence: 99%

Charge transport in high-mobility conjugated polymers and molecular semiconductors

et al. 2020

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Conjugated polymers and molecular semiconductors are emerging as a viable semiconductor technology in industries such as displays, electronics, renewable energy, sensing and healthcare. A key enabling factor has been significant scientific progress in improving their charge transport properties and carrier mobilities, which has been made possible by a better understanding of the molecular structure-property relationships and the underpinning charge transport physics. Here we aim to present a coherent review of how we understand charge transport in these high-mobility van der Waals bonded semiconductors. Specific questions of interest include estimates for intrinsic limits to the carrier mobilities that might ultimately be achievable; a discussion of the coupling between charge and structural dynamics; the importance of molecular conformations and mesoscale structural features; how the transport physics of conjugated polymers and small molecule semiconductors are related; and how the incorporation of counterions in doped films-as used, for example, in bioelectronics and thermoelectric devices-affects the electronic structure and charge transport properties.

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“…Using Marcus theory in this manner is similar to other recent high throughput methods which have evaluated structures using these types of properties. 11 As an assessment of its predictive power against a more complete description of charge transport, we carried out comparisons of Marcus theory against mobilities from non-adiabatic molecular dynamics [36][37][38][39][40][41] (see Table S2 and Fig. S4, ESI † for details) for a series of functionalised tetracenes.…”

Section: Electron Mobility Calculationsmentioning

confidence: 99%

Evolutionary chemical space exploration for functional materials: computational organic semiconductor discovery

2020

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Computational methods, including crystal structure and property prediction, have the potential to accelerate the materials discovery process by enabling structure prediction and screening of possible molecular building blocks prior to their synthesis. However, the discovery of new functional molecular materials is still limited by the need to identify promising molecules from a vast chemical space. We describe an evolutionary method which explores a user specified region of chemical space to identify promising molecules, which are subsequently evaluated using crystal structure prediction. We demonstrate the methods for the exploration of aza-substituted pentacenes with the aim of finding small molecule organic semiconductors with high charge carrier mobilities, where the space of possible substitution patterns is too large to exhaustively search using a high throughput approach. The method efficiently explores this large space, typically requiring calculations on only $1% of molecules during a search. The results reveal two promising structural motifs: aza-substituted naphtho[1,2-a]anthracenes with reorganisation energies as low as pentacene and a series of pyridazine-based molecules having both low reorganisation energies and high electron affinities. † Electronic supplementary information (ESI) available: Full details of computational methods, tting of molecular to solid-state electron affinities, ESF maps of all molecules, low energy predicted crystal structures and calculated properties. See

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Crossover from Hopping to Band-Like Charge Transport in an Organic Semiconductor Model: Atomistic Nonadiabatic Molecular Dynamics Simulation

Cited by 80 publications

References 43 publications

Identifying high-mobility tetracene derivatives using a non-adiabatic molecular dynamics approach

Identifying high-mobility tetracene derivatives using a non-adiabatic molecular dynamics approach

Charge transport in high-mobility conjugated polymers and molecular semiconductors

Evolutionary chemical space exploration for functional materials: computational organic semiconductor discovery

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