Morphology and Electronic Properties of <i>N</i>,<i>N</i>′-Ditridecylperylene-3,4,9,10-tetracarboxylic Diimide Layered Aggregates: From Structural Predictions to Charge Transport

Lorenzoni, Andrea; Muccini, Michele; Mercuri, Francesco

doi:10.1021/acs.jpcc.7b05365

Cited by 16 publications

(21 citation statements)

References 46 publications

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“…The formation of unstructured aggregates of PTCDI‐C13 at the interface with graphene in simulated kinetically controlled conditions agrees with experimental characterization of as‐cast samples, as shown in Figure j. The distribution of the intermolecular orientation angles reveals the formation of small molecular clusters with short‐range crystalline 1D ordering, corresponding mainly to the staggered (ST) phase of PTCDI‐C13 and is related to the strong π–π intermolecular interactions. The local orientational ordering, however, decays rapidly with the distance, converging at long distances to the value expected for fully isotropic systems (see Figure S3, Supporting Information).…”

Section: Resultssupporting

confidence: 82%

“…In our simulations, the intermolecular π–π stacking arises from the interplay between van der Waals (LJ terms) and Coulomb terms of the interaction potential. The force‐field parameters used lead to a remarkable accuracy in the description of the π–π stacking interaction in PTCDI‐C13 aggregates, as shown in previous work . The stability of the CF configuration, however, can be altered by the interaction with the substrate, as will be shown below.…”

Section: Resultsmentioning

confidence: 53%

“…Molecular dynamics calculations were performed by applying the all‐atom OPLS force field for both graphene and PTCDI‐C13. The force field for PTCDI‐C13 was successfully applied in previous works . The interaction between PTCDI‐C13 and graphene was described as mixed Lennard–Jones (LJ) terms.…”

Section: Methodsmentioning

confidence: 99%

“…The role of molecular structure and morphology at the nanoscale is particularly relevant in the formation of aggregates at the interface with a substrate, where the interplay between the emerging polymorphism of perylene diimide derivatives and the effect of processing has strong consequences on charge transport properties in devices. In particular, PTCDI‐C13 constitutes a suitable benchmark to assess the predictive power of our approach, as it is known to form different aggregated structures at the nanoscale depending on fabrication conditions and on the nature of the underlying substrate . Graphene, on the other hand, besides being a material of paramount technological relevance, can also be considered as an ideal 2D substrate for the formation of heterojunctions with molecular systems .…”

Section: Introductionmentioning

confidence: 99%

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A Computational Predictive Approach for Controlling the Morphology of Functional Molecular Aggregates on Substrates

Lorenzoni

Muccini

Mercuri

2019

Advcd Theory and Sims

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Full control of the growth dynamics and morphology of nanoscale molecular aggregates on substrates is a crucial factor for the development of novel materials and devices for technological applications. A novel computational approach based on molecular dynamics, which is able to predict the structure of nanoscale aggregates of organic small molecules on substrates as a function of growth and processing conditions, is presented. In the simulation protocol proposed, molecules are progressively added to the substrate, one by one, reproducing vacuum thermal deposition processes. The simulation parameters affect the structure of the configuration, and formation of molecular aggregates is spontaneously observed upon reaching a critical molecular density at the interface. Suitable simulation parameters allow to access different molecular aggregation morphologies on substrates, including crystalline phases, matching the structural variability observed in real fabrication conditions. This approach is benchmarked by simulating the morphology of aggregates of N,N′-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (PTCDI-C13), a prototypical n-type semiconductor for organic electronics, on graphene, in different growth conditions. Simulations predict structural features of aggregates of PTCDI-C13 on graphene that are in excellent agreement with experiments and, at the same time, provide a rationale and quantitative relationship between molecular structure and observed aggregation morphologies.

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Section: Resultssupporting

confidence: 82%

Section: Resultsmentioning

confidence: 53%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

A Computational Predictive Approach for Controlling the Morphology of Functional Molecular Aggregates on Substrates

Lorenzoni

Muccini

Mercuri

2019

Advcd Theory and Sims

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“…The interface morphology can be predicted by molecular dynamics simulations, typically parameterized using density-functional calculations on small subsystems. [12][13][14][15][16][17][18][19] Yet, the accurate description of the electronic coupling between organic and inorganic materials requires highly demanding ab-initio methods, including electronic correlation. 20, 21 Finally, the calculation of charge injection deep inside the organic material requires the simulation of the charge dynamics that could be tackled with a kinetic Monte Carlo approach.…”

Section: Introductionmentioning

confidence: 99%

Nanoscale morphology and electronic coupling at the interface between indium tin oxide and organic molecular materials

2018

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The correlation between nanoscale morphology and charge injection rates at the interface between an organic semiconductor layer and a transparent metal oxide electrode was investigated by integrating molecular dynamics simulations with electronic structure calculations. The simulation approach proposed has been applied to the analysis of the hole injection mechanism at the interface between an amorphous layer of tris[(3-phenyl-1H-benzimidazol-1-yl-2(3H)-ylidene)-1,2-phenylene]Ir (DPBIC), a hole transport and emitter molecule, and the surface of indium tin oxide (ITO), a material commonly used as anode in OLEDs. The link between interface morphology and charge injection was investigated by implementing a two-step, top-down simulation approach. Namely, nanoscale molecular aggregation phenomena at the organic/electrode interface were first assessed by molecular dynamics simulations, mimicking different processing conditions, and followed by density functional theory calculations of the electronic coupling between molecular levels and the manifold of electrode states involved in the charge injection process. The correlation between structural parameters and electronic coupling suggests a significant role of specific molecule/electrode configurations on charge transport processes at the interface, resulting in a broad distribution of charge injection rates, and highlights the link between molecular structure, nanoscale aggregation and processing in the realization of heterointerfaces for efficient charge injection in organic electronic devices.

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3D versus 2D Electrolyte–Semiconductor Interfaces in Rylenediimide‐Based Electron‐Transporting Water‐Gated Organic Field‐Effect Transistors

Prescimone

Benvenuti

Natali

et al. 2020

Adv Elect Materials

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aqueous electrolyte solution acting as the gate dielectric in contact with the organic semiconductor (OS). [1,2] This kind of architecture enables the WGOFET to transduce bioelectrical signals and to detect molecular analytes, ions, and biomarkers. [1,3,4] In WGOFETs the charge accumulation in the OS is caused by the electrolyte ions migrating close to the OS interface and to the gate interface when a gate potential is applied. [5,6] Thus, charge accumulation in the OS film and charge transport occur close to OS/electrolyte interface. In this scenario, the structural organization and the morphological features of the OS/ electrolyte interface play a crucial role in the device performance, as expected in any class of field-effect transistors based on thin films. The growth mechanism of the active layer as the thin-film layer thickness is increased typically controls the film morphology and molecular organization of the interface that is finally exposed to water, as it is in the case of standard OFET devices with a top-gate configuration. [6-8] Among the plethora of organic semiconductors with different molecular structures and tailored electrical properties, thin films comprised by linear molecular systems, like pentacene and α-sexithiophene, are subjected to a transition from a layer-by-layer to island growth upon completion of a few molecular monolayers (5-6 nm). [9-12] This growth mechanism Water-gated organic field-effect transistors (WGOFETs) are relevant devices for use in the fields of biosensors and biosystems. However, real applications require very stringent performance in terms of electrochemical stability and charge mobility to the organic semiconductor in contact with an aqueous environment. Here, a comparative study of two small-molecule electrontransporting perylenediimide semiconductors, which differ only in the N-substituents named PDIF-CN 2 and PDI8-CN 2 is reported. The two materials present similar solid-state arrangements but, while the PDI8-CN 2 shows a more 3D growth modality and electron mobility independent of the semiconductor layer thickness (≈10 −4 cm 2 V −1 s −1), the PDIF-CN 2 has an almost-2D growth modality and the mobility increases with the semiconductor film thickness, reaching a maximum value of ≈5 × 10 −3 cm 2 V −1 s −1 at 30 nm. Above this thickness, the PDIF-CN 2 switches to a more 3D growth modality, and the mobility drops by one order of magnitude. XRR analysis indicates that a PDIF-CN 2 film can be modeled as a dense layered structure in which each layer is decoupled from the others due to the presence of fluorocarbonchains. The availability of additional pathways for charge transport from buried layers and the 2D versus 3D growth can explain the mobility dependence on the film thickness.

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Morphology and Electronic Properties of N,N′-Ditridecylperylene-3,4,9,10-tetracarboxylic Diimide Layered Aggregates: From Structural Predictions to Charge Transport

Cited by 16 publications

References 46 publications

A Computational Predictive Approach for Controlling the Morphology of Functional Molecular Aggregates on Substrates

A Computational Predictive Approach for Controlling the Morphology of Functional Molecular Aggregates on Substrates

Nanoscale morphology and electronic coupling at the interface between indium tin oxide and organic molecular materials

3D versus 2D Electrolyte–Semiconductor Interfaces in Rylenediimide‐Based Electron‐Transporting Water‐Gated Organic Field‐Effect Transistors

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