Theoretical insights on morphology and charge transport properties of two-dimensional N,N′-ditridecylperylene-3,4,9,10-tetra carboxylic diimide aggregates

Lorenzoni, Andrea; Gallino, Federico; Muccini, Michele; Mercuri, Francesco

doi:10.1039/c6ra06784k

Cited by 11 publications

(37 citation statements)

References 54 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Simulation models were prepared basing on the configurations of the perylene diimide cores taken from equilibrated 2D (monolayer) CF and ST layer phases, as described in ref. 23. Initially, the flexible C13 alkyl chains of PTCDI-C13 were arranged to form, in the direction orthogonal to that of π-stacking, a fully-interdigitated 3D bulk crystal.…”

Section: Resultsmentioning

confidence: 99%

“…In bilayers, however, the topmost and bottommost alkyl chains of PTCDI-C13 lean towards the π-cores, in analogy to what is observed in monolayers. 23 The tilted configuration of the C13 chains can thus be considered a structural feature of the topmost layers in ordered PTCDI-C13 aggregates, corresponding to the surfaces exposed to scanning-probe techniques, or at heterointerfaces. Notably, the computed inter-layer distance for the CF lay-on bulk configurations (25.2 Å) agrees remarkably well with the height of the PTCDI-C13 unit cell (25.3 Å) obtained by XRD experiments.…”

Section: Resultsmentioning

confidence: 99%

“…20,21 Nevertheless, the intrinsic polycrystalline nature of aggregates and the alterations of morphology with film thickness prevent a precise determination of the packing of PTCDI-C13 in devices at the molecular level. 22,23 In this work, we investigate the structural properties of bulk and bilayer ordered aggregates of PTCDI-C13 by molecular dynamics (MD) simulations. The relationship between morphology and charge transport is evaluated by computing electron transfer integrals at the density functional theory (DFT) level.…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, calculations were also performed on the 3D aggregation of PTCDI-C13 in the ST configuration, which is likely to occur in kinetically-controlled growth conditions. 23 The integration between atomistic MD, metadynamics simulations, DFT total energy calculations, evaluation of electronic transfer integrals and the comparison with available experimental data, guides us in assessing the structure of PTCDI-C13 in nanoaggregates as a function of growing conditions, correlating molecular structure to potential performances in devices.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

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

2017

Self Cite

View full text Add to dashboard Cite

The morphology of layered aggregates of N,N'-ditridecylperylene-3,4,9,10-tetracarboxylic diimide (PTCDI-C13), a prototypical n-type semiconductor for organic electronic devices, was investigated by molecular dynamics (MD) and corroborated by metadynamics simulations. Calculations were targeted to ordered three-dimensional aggregates, differing in the relative orientation of the perylene π-cores and on the degree of interdigitation among contiguous planar layers. Our simulations indicated the non-interdigitated cofacial structure as the thermodynamically most stable form of ordered PTCDI-C13 aggregates, both in bulk crystals and bilayers. Other structures, however, may occur in the growth of PTCDI-C13 in kinetic conditions. Density functional theory (DFT) calculations were also performed to evaluate the relative total electronic energy of 3D crystals of PTCDI-C13 and related transfer integrals, correlating structure with potential charge transport properties in devices. The most stable ordered aggregated form of PTCDI-C13 exhibits significant transfer integrals for electrons, and accounts for the remarkable n-type charge transport properties observed in thin-films grown in thermodynamic conditions. The effect of structural disorder on charge transport properties was also assessed by computing transfer integrals in PTCDI-C13 layers at the interface with model surfaces. Targeting a strategic material for organic electronics, this work also highlights an integrated computational approach to simulate the structure and energetics of competing 3D morphologies in thin-films, and to shed light on the details of ordered structures that are responsible for the charge transport in small-molecule organic semiconductors.

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

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

2017

Self Cite

View full text Add to dashboard Cite

show abstract

“…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

Self Cite

View full text Add to dashboard Cite

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.

show abstract

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

Lorenzoni

Muccini

Mercuri

2019

Advcd Theory and Sims

Self Cite

View full text Add to dashboard Cite

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.

show abstract

Theoretical insights on morphology and charge transport properties of two-dimensional N,N′-ditridecylperylene-3,4,9,10-tetra carboxylic diimide aggregates

Abstract: An integrated computational approach, based on molecular dynamics and density functional theory, reveals an interplay between morphology, processing and charge transport properties in layered aggregates of PTCDI-C13.

Cited by 11 publications

References 54 publications

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

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

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

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

Contact Info

Product

Resources

About