arXiv subjects

Lorenzo Soprani

Publications and source records attributed to Lorenzo Soprani.

3 recordsLinked to original sources

arXiv2026

A hidden bulk polymorph governs charge transport dimensionality in an organic semiconductor

Organic semiconductors (OSCs) are widely explored for flexible optoelectronic technologies, with performance governed not only by molecular design, but also by solid-state packing, which can give rise to polymorphism. Dinaphthothienothiophene (DNTT) is a benchmark OSC that has long been considered monomorphic. Here, we discover, isolate, and resolve the crystal structure of a previously unrecognised bulk polymorph of DNTT, termed blue DNTT owing to its characteristic blue emission. Coexisting with the well-known (green) DNTT in commercial powders, yet previously overlooked, blue DNTT represents the thermodynamically stable form. By combining X-ray diffraction, Raman, and THz spectroscopy with simulations, we demonstrate that polymorphism in DNTT reshapes the low-frequency phonon landscape and transfer-integral network, impacting charge transport. While green DNTT exhibits two-dimensional charge transport with holes more mobile than electrons, blue DNTT shows charge transport along all crystallographic directions enabled by a distinct herringbone packing. Electron mobility along the crystallographic a and b-axes in blue DNTT exceeds twice the hole mobility in the green phase. To our knowledge, this is the first reported acene-based semiconductor exhibiting three-dimensional charge transport. Polymorphism emerges as a key lever to tune charge transport dimensionality and carrier efficiency in organic semiconductors.

cond-mat.mtrl-sci↗

arXiv2025

Accurate and Efficient Phonon Calculations in Molecular Crystals via Minimal Molecular Displacements

Vibrational dynamics governs the fundamental properties of molecular crystals, shaping their thermodynamics, mechanics, spectroscopy, and transport phenomena. However desirable, the first-principles calculation of solid-state vibrations, i.e.\ phonons, stands as a major computational challenge in molecular crystals characterized by many atoms in the unit cell and by weak intermolecular interactions. Here we propose a formulation of the harmonic lattice dynamics based on a natural basis of molecular coordinates consisting of rigid-body displacements and intramolecular vibrations. This enables a sensible \emph{minimal molecular displacement} approximation for the calculation of the dynamical matrix, combining isolated molecule calculations with only a small number of expensive crystal supercell calculations, ultimately reducing the computational cost by up to a factor 10. The comparison with reference calculations demonstrates the quantitative accuracy of our method, especially for the challenging and dispersive low-frequency region it is designed for. Our method provides an excellent description of the thermodynamic properties and offers a privileged molecular-level insight into the complex phonons band structure of molecular materials.

cond-mat.mtrl-sci↗

arXiv2022

Structural order promotes efficient separation of delocalized charges at molecular heterojunctions

The energetic landscape at the interface between electron donating and accepting molecular materials favors efficient conversion of intermolecular charge-transfer states (CTS) into free charge carriers in high-performance organic solar cells. Here, we elucidate how interfacial energetics, charge generation and radiative recombination are affected by structural ordering. We experimentally determine the CTS binding energy of a series of model, small molecule donor-acceptor blends, where the used acceptors (B2PYMPM, B3PYMPM and B4PYMPM) differ only in the nitrogen position of their lateral pyridine rings. We find that the formation of an ordered, face-on molecular packing in B4PYMPM is beneficial to efficient, field-independent charge separation, leading to fill factors over 70% in photovoltaic devices. This is rationalized by a comprehensive computational protocol showing that, compared to the more amorphous and isotropically oriented B2PYMPM, the higher order of the B4PYMPM molecules provides more delocalized CTS. Furthermore, we find no correlation between the quantum efficiency of radiative free charge carrier recombination and the bound or unbound nature of the CTS. This work highlights the importance of structural ordering at donor-acceptor interfaces for efficient free carrier generation and shows that more ordering and less bound CT states do not preclude efficient radiative recombination.

physics.app-ph↗