Impact of Polarity on Anisotropic Diffusion of Conjugated Organic Molecules on the (101̅0) Zinc Oxide Surface

Miletic, Mila; Pałczynski, Karol; Jacobs, Matheus; Valencia, Ana M.; Cocchi, Caterina; Dzubiella, Joachim

doi:10.1021/acs.jpcc.8b12112

Cited by 5 publications

(3 citation statements)

References 53 publications

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“…The electronic hybridization generates new states which do not exist in the individual components and therefore uniquely define the hybrid system [6,21,[34][35][36][37]. The resulting level alignment between the constituents is very much dependent on the materials involved but also on the relative molecular concentration and orientation [22,36,[38][39][40][41][42][43]. The introduction of a dipole layer at the interface was shown to further tune the resulting lineup [44][45][46].…”

Section: Introductionmentioning

confidence: 99%

Ultrafast charge transfer and vibronic coupling in a laser-excited hybrid inorganic/organic interface

Jacobs

Krumland

Valencia

et al. 2020

Advances in Physics: X

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Hybrid interfaces formed by inorganic semiconductors and organic molecules are intriguing materials for opto-electronics. Interfacial charge transfer is primarily responsible for their peculiar electronic structure and optical response. Hence, it is essential to gain insight into this fundamental process also beyond the static picture. Ab initio methods based on real-time time-dependent density-functional theory coupled to the Ehrenfest molecular dynamics scheme are ideally suited for this problem. We investigate a laser-excited hybrid inorganic/organic interface formed by the electron acceptor molecule 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (F4TCNQ) physisorbed on a hydrogenated silicon cluster, and we discuss the fundamental mechanisms of charge transfer in the ultrashort time window following the impulsive excitation. The considered interface is p-doped and exhibits charge transfer in the ground state. When it is excited by a resonant laser pulse, the charge transfer across the interface is additionally increased, but contrary to previous observations in allorganic donor/acceptor complexes, it is not further promoted by vibronic coupling. In the considered time window of 100 fs, the molecular vibrations are coupled to the electron dynamics and enhance intramolecular charge transfer. Our results highlight the complexity of the physics involved and demonstrate the ability of the adopted formalism to achieve a comprehensive understanding of ultrafast charge transfer in hybrid materials.

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Section: Introductionmentioning

confidence: 99%

Ultrafast charge transfer and vibronic coupling in a laser-excited hybrid inorganic/organic interface

Jacobs

Krumland

Valencia

et al. 2020

Advances in Physics: X

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“…This value lies in the range of diffusion coefficients previously determined for systems comprising organic molecules on oxide surfaces. Computation study of para -hexaphenyl on zinc oxide surface determined the value of 5 μm 2 s −1 at room temperature; the fluorination of the molecule with 2 of 4F atoms decreased the diffusion coefficient value to 1 μm 2 s −1 or 0.1 μm 2 s −1 , respectively 51 . In another computational study, the diffusion coefficient decreased from 190–0.02 μm 2 s −1 with increasing chain size from benzene to para -hexaphenyl on silica surface 43 .…”

Section: Resultsmentioning

confidence: 98%

Superflux of an organic adlayer towards its local reactive immobilization

Salamon,

Bukvišová,

Jan

et al. 2023

Commun Chem

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On-surface mass transport is the key process determining the kinetics and dynamics of on-surface reactions, including the formation of nanostructures, catalysis, or surface cleaning. Volatile organic compounds (VOC) localized on a majority of surfaces dramatically change their properties and act as reactants in many surface reactions. However, the fundamental question “How far and how fast can the molecules travel on the surface to react?” remains open. Here we show that isoprene, the natural VOC, can travel ~1 μm s−1, i.e., centimeters per day, quickly filling low-concentration areas if they become locally depleted. We show that VOC have high surface adhesion on ceramic surfaces and simultaneously high mobility providing a steady flow of resource material for focused electron beam synthesis, which is applicable also on rough or porous surfaces. Our work established the mass transport of reactants on solid surfaces and explored a route for nanofabrication using the natural VOC layer.

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“…For instance,the hydrogens in the meta positions of both terminal phenyl groups of the prototypical organic para-Sexiphenyl (p-6P) molecule can be substituted by fluor atoms to introduce two local dipole moments at both terminal groups [4,5]. This, in turn, changes the degree of diffusion-anisotropy of the molecule on the inorganic zinc oxide 1010 surface which leads to differences in the growth morphology [6].…”

Section: Introductionmentioning

confidence: 99%

Growth modes of partially fluorinated organic molecules on amorphous silicon dioxide

Miletic,

Palczynski,

Dzubiella

2021

Preprint

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We study the influence of fluorination on nucleation and growth of the organic para-sexiphenyl molecule (p-6P) on amorphous silicon dioxide (a-SiO2) by means of atomistically resolved classical molecular dynamics computer simulations. We use a simulation model that mimics the experimental deposition from the vapor and subsequent self-assembly onto the underlying surface. Our model reproduces the experimentally observed orientational changes from lying to upright standing configurations of the grown layers. We demonstrate that the increase in the number of fluorinated groups inside the p-6P leads to a smoother, layer-by-layer growth on the a-SiO2 surface: We observe that in the first layers, due to strong molecule-substrate interactions the molecules first grow in chiral (fan-like) structures, where each consecutive molecule has a higher angle, supported by molecules lying underneath. Subsequently deposited molecules bind to the already standing molecules of the chiral structures until all molecules are standing. The growth of chiral islands is the main mechanism for growth of the fluorinated p-6P derivative, while the p-6P, due to the lower interaction with the underlying substrate, forms less chiral structures. This leads to a lower energy barrier for step-edge crossing for the fluorinated molecules. We find that partial fluorination of the p-6P molecule can in this way significantly alter its growth behaviour by modifying the rough, 3D growth into a smooth, layer-by-layer growth. This has implications for the rational design of molecules and their functionalized forms which could be tailored for a desired growth behavior and structure formation.

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Impact of Polarity on Anisotropic Diffusion of Conjugated Organic Molecules on the (101̅0) Zinc Oxide Surface

Cited by 5 publications

References 53 publications

Ultrafast charge transfer and vibronic coupling in a laser-excited hybrid inorganic/organic interface

Ultrafast charge transfer and vibronic coupling in a laser-excited hybrid inorganic/organic interface

Superflux of an organic adlayer towards its local reactive immobilization

Growth modes of partially fluorinated organic molecules on amorphous silicon dioxide

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