arXiv subjects

Dmytro F. Perepichka

Publications and source records attributed to Dmytro F. Perepichka.

4 recordsLinked to original sources

arXiv2026

Mapping the Growth of Two-Dimensional $π$-Conjugated Polymers on Au(111): Organometallic Intermediates and Edge Terminations

Kagome lattices provide an exciting space for the exploration of graphene-like $π$-conjugated molecular systems with flat bands. Using heterotriangulene-derived precursors, along with an on-surface Ullmann coupling process, makes growing polymers with Kagome lattices accessible and straightforward. Here, we use scanning tunneling microscopy alongside high-resolution atomic force microscopy to examine the evolution of tribromotrioxaazatriangulene on Au(111) into ordered, covalent films. Using density functional theory and scanning probe methods, we find previously unreported organometallic intermediate states involving Au adatoms incorporated within the growing polymer lattice. We also find that a majority of polymer edges remain brominated up to 250 $^{\circ}$C and a large number of edges bonded to Au adatoms coordinated to an adjacent bromine atom. These observations suggest that residual bromine could play a role in stabilizing the polymer edges to Au adatoms and thereby influence the growth pathways that lead to ordered Kagome polymer lattices.

cond-mat.mtrl-sci↗

arXiv2026

Revealing full molecular orientation distributions in organic thin films by nonlinear polarimetry

The performance of organic optoelectronic devices is critically dependent on how molecules orient within organic thin films. Yet, standard characterization techniques only reveal the first and second moments of the molecular orientation distribution. This limitation obscures the true molecular arrangement, as diverse distributions can yield identical low-order averages while exhibiting distinct functional properties. Here, we bridge this gap by combining multi-harmonic nonlinear polarimetry (second, third, and fourth harmonic) with the Maximum Entropy Method to reconstruct the probability distribution without any \textit{a priori} assumptions. This allows us to resolve features in the distribution such as asymmetry and bimodality, that remain invisible to conventional probes. Furthermore, we use this method to benchmark molecular dynamics simulations, revealing that these simulations often fail to capture the complex distribution despite correctly predicting the first and second moments. This work transforms molecular orientation from an inferred average into a precise observable, establishing essential validation standards for predictive material design.

physics.optics↗

arXiv2025

Molecular Engineering for Enhanced Second-Order Nonlinear Response in Spontaneously-Oriented Evaporated Organic Films

Materials with large second-order nonlinearities are crucial for next-generation integrated photonics. Spontaneously oriented organic thin films prepared by physical vapor deposition offer a promising poling-free and scalable approach. This study investigates molecular engineering strategies to enhance the second-order nonlinear response of derivatives based on the donor-acceptor molecule 2-(4'-diphenylaminobiphenyl-4-yl)quinoxaline-6,7-dicarbonitrile (TPA-QCN). Four derivatives incorporating modifications designed to increase molecular hyperpolarizability ($β$) or promote favorable orientation were synthesized and characterized. The most successful modification, intramolecular bridge-locking, simultaneously increases hyperpolarizability and enhances spontaneous orientation by reducing detrimental electrostatic interactions during deposition. It leads to a significant enhancement of the second-order nonlinear response, achieving off-resonance $χ^{(2)}_{31} \approx 16$ pm V$^{-1}$ and $χ^{(2)}_{33} \approx 18$ pm V$^{-1}$ at 1550 nm, a twofold improvement over the parent TPA-QCN. Analysis combining nonlinear optical measurements, surface potential measurement, optical anisotropy, and density functional theory calculations indicates that improved molecular orientation, rather than increased $β$ alone, is the primary driver for the enhanced performance in the leading derivatives. These findings demonstrate the effectiveness of targeting molecular orientation via structural design and position spontaneously oriented organic films as compelling poling-free candidates for integrated nonlinear photonic applications where the increased electrode-induced optical losses, fabrication complexity and footprint are a critical limitation.

physics.optics↗

arXiv2023

Synthesis of a mesoscale ordered 2D-conjugated polymer with semiconducting properties

2D materials with high charge carrier mobility and tunable electronic band gaps have attracted intense research effort for their potential use as active components in nanoelectronics. 2D-conjugated polymers (2DCP) constitute a promising sub-class due to the fact that the electronic band structure can be manipulated by varying the molecular building blocks, while at the same time preserving the key features of 2D materials such as Dirac cones and high charge mobility. The major challenge for their use in technological applications is to fabricate mesoscale ordered 2DCP networks since current synthetic routes yield only small domains with a high density of defects. Here we demonstrate the synthesis of a mesoscale ordered 2DCP with semiconducting properties and Dirac cone structures via Ullmann coupling on Au(111). This material has been obtained by combining rigid azatriangulene precursors and a hot dosing approach which favours molecular diffusion and reduces the formation of voids in the network. These results open opportunities for the synthesis of 2DCP Dirac cone materials and their integration into devices.

cond-mat.mtrl-sci↗