Rational Design of Low-Dimensional Hybrid Organic/Inorganic Interfaces for Enhanced Second-Harmonic Generation
Abstract
Hybrid interfaces formed by push-pull organic molecules physisorbed on two-dimensional (2D) semiconductors provide a structurally tunable platform for engineering second-harmonic generation (SHG). However, predicting and optimizing their macroscopic response remains a formidable challenge due to the phase-sensitive interference between the nonlinear responses of the adlayer and substrate. Here, we develop a physics-informed computational screening framework that decomposes the effective second-order susceptibility into its constituent substrate, molecular, and electric-field-induced SHG channels. Validated by fully atomistic first-principles calculations across representative interface structures, this model maps the complete orientation-resolved tensor landscape of chemically modulated carbon-conjugated polar molecules on 2D substrates with distinct symmetry. Crucially, our findings dismantle the conventional reliance on static polar descriptors, demonstrating that the ground-state permanent dipole magnitude is a fundamentally unreliable proxy for macroscopic nonlinear response. Instead, we show that the ultimate criterion for SHG maximization is encoded in the phase-resolved projection of the full anisotropic molecular hyperpolarizability tensor. On non-centrosymmetric substrates, the coherent interference between the physisorbed adlayer and the underlying 2D matrix induces a characteristic Fano-like asymmetry and ranking reversals that are entirely absent on centrosymmetric platforms. By establishing that functionalization topology, dynamic spatial orientation, and substrate point-group symmetry constitute a single, non-separable parameter space, this work provides a systematic blueprint for the rational assembly, predictive discovery, and non-invasive characterization of next-generation low-dimensional hybrid materials for nonlinear optoelectronics.
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BibTeX
@misc{guerrini2026rational,
title = {{Rational Design of Low-Dimensional Hybrid Organic/Inorganic Interfaces for Enhanced Second-Harmonic Generation}},
author = {Michele Guerrini and Muhammad Sufyan Ramzan and Caterina Cocchi},
howpublished = {arXiv},
year = {2026},
month = sep,
doi = {10.48550/arxiv.2609.29255},
eprint = {2609.29255},
archivePrefix = {arXiv},
url = {https://arxiv.org/abs/2609.29255},
}
RIS
TY - UNPB
TI - Rational Design of Low-Dimensional Hybrid Organic/Inorganic Interfaces for Enhanced Second-Harmonic Generation
AU - Michele Guerrini
AU - Muhammad Sufyan Ramzan
AU - Caterina Cocchi
PY - 2026
DA - 2026/09/24
PB - arXiv
DO - 10.48550/arxiv.2609.29255
UR - https://arxiv.org/abs/2609.29255
AB - Hybrid interfaces formed by push-pull organic molecules physisorbed on two-dimensional (2D) semiconductors provide a structurally tunable platform for engineering second-harmonic generation (SHG). However, predicting and optimizing their macroscopic response remains a formidable challenge due to the phase-sensitive interference between the nonlinear responses of the adlayer and substrate. Here, we develop a physics-informed computational screening framework that decomposes the effective second-order susceptibility into its constituent substrate, molecular, and electric-field-induced SHG channels. Validated by fully atomistic first-principles calculations across representative interface structures, this model maps the complete orientation-resolved tensor landscape of chemically modulated carbon-conjugated polar molecules on 2D substrates with distinct symmetry. Crucially, our findings dismantle the conventional reliance on static polar descriptors, demonstrating that the ground-state permanent dipole magnitude is a fundamentally unreliable proxy for macroscopic nonlinear response. Instead, we show that the ultimate criterion for SHG maximization is encoded in the phase-resolved projection of the full anisotropic molecular hyperpolarizability tensor. On non-centrosymmetric substrates, the coherent interference between the physisorbed adlayer and the underlying 2D matrix induces a characteristic Fano-like asymmetry and ranking reversals that are entirely absent on centrosymmetric platforms. By establishing that functionalization topology, dynamic spatial orientation, and substrate point-group symmetry constitute a single, non-separable parameter space, this work provides a systematic blueprint for the rational assembly, predictive discovery, and non-invasive characterization of next-generation low-dimensional hybrid materials for nonlinear optoelectronics.
ER -