arXiv subjects

Emanuele Orgiu

Publications and source records attributed to Emanuele Orgiu.

8 recordsLinked to original sources

arXiv2026

Operando Raman probing of mode selective electron phonon coupling in two dimensional halide perovskites

Electron phonon coupling governs charge transport, carrier relaxation, and polaron formation in halide perovskites, yet its microscopic origin in low dimensional systems remains poorly understood. Here, we combine operando, bias dependent Raman spectroscopy with density functional theory (DFT) calculations to directly probe carrier lattice interactions in two-dimensional Ruddlesden Popper perovskites,(PEA)$_2$PbI$_4$ and its fluorinated analogue, (PEA-F)$_2$PbI$_4$. Under applied electric fields, both systems exhibit mode-selective Raman linewidth broadening predominantly near 100 cm$^{-1}$, whereas other phonon modes remain largely unaffected, revealing highly selective coupling between injected carriers and specific lattice vibrations. DFT calculations identify these modes as hybrid organic inorganic vibrations involving coupled motion of the organic spacer and symmetric Pb I equatorial stretching, rather than purely inorganic phonons. Fluorination fundamentally reconstructs the vibrational landscape by modifying molecular packing, crystal symmetry, and organic inorganic coupling, resulting in changes to the phonon density of states, longer phonon lifetimes, and an enhanced carrier mediated lattice response. Notably, electrical bias produces opposite phonon lifetime evolution in thin films and single crystals: the phonon lifetime decreases by approximately 17 to 22% in thin films but increases 20 to 26% in single crystals. These contrasting responses demonstrate that structural order plays a fundamental role in determining carrier phonon interactions and phonon relaxation pathways in two-dimensional halide perovskites.

cond-mat.mtrl-sci↗

arXiv2026

Role of structure and charge trapping on the bipolaron formation and magnetic-field response of gated conjugated polymers

Conjugated polymers exhibit unique spin-dependent phenomena arising from weak yet critical hyperfine interactions. Understanding these spin effects, particularly the spin-dependent formation and decay of correlated spin pairs, is important for advancing both organic electronics and polymer-based spintronics. Intrinsic magnetic-field responses such as magnetoresistance have primarily been investigated in diode architectures, where electrons and holes coexist. However, such systems are less suitable for probing bipolaron formation in unipolar transport, and the relationship between polymer structure and bipolaron formation in lightly doped polymers remains unclear. Here, we systematically investigate intrinsic magnetoresistance in representative conjugated polymers using field-effect transistors and observe a generally positive magnetoresistance. First-principles simulations reveal that bipolarons preferentially form on short conjugated segments associated with amorphous regions. Moreover, comparisons across these polymers show that enhanced charge trapping correlates with stronger magnetoresistance, implying promoted bipolaron formation. Bipolaron-incorporated energylevel-alignment modeling near metal/polymer interfaces suggests that charge traps can increase the bipolaron density.

cond-mat.mtrl-sci↗

arXiv2024

Enhanced Terahertz Spectroscopy of a Monolayer Transition Metal Dichalcogenide

Two-dimensional materials, including transition metal dichalcogenides, are attractive for a variety of applications in electronics as well as photonics and have recently been envisioned as an appealing platform for phonon polaritonics. However, their direct characterization in the terahertz spectral region, of interest for retrieving, e.g., their phonon response, represents a major challenge, due to the limited sensitivity of typical terahertz spectroscopic tools and the weak interaction of such long-wavelength radiation with sub-nanometer systems. In this work, by exploiting an ad-hoc engineered metallic surface enabling a ten-thousand-fold local absorption boost, we perform enhanced terahertz spectroscopy of a monolayer transition metal dichalcogenide (tungsten diselenide) and extract its dipole-active phonon resonance features. In addition, we use these data to obtain the monolayer effective permittivity around its phonon resonance. Via the direct terahertz characterization of the phonon response of such two-dimensional systems, this method opens the path to the rational design of phonon polariton devices exploiting monolayer transition metal dichalcogenides.

physics.optics↗

arXiv2023

Non-invasive digital etching of van der Waals semiconductors

The capability to finely tailor material thickness with simultaneous atomic precision and non-invasivity would be useful for constructing quantum platforms and post-Moore microelectronics. However, it remains challenging to attain synchronized controls over tailoring selectivity and precision. Here we report a protocol that allows for non-invasive and atomically digital etching of van der Waals transition-metal dichalcogenides through selective alloying via low-temperature thermal diffusion and subsequent wet etching. The mechanism of selective alloying between sacrifice metal atoms and defective or pristine dichalcogenides is analyzed with high-resolution scanning transmission electron microscopy. Also, the non-invasive nature and atomic level precision of our etching technique are corroborated by consistent spectral, crystallographic and electrical characterization measurements. The low-temperature charge mobility of as-etched MoS$_2$ reaches up to $1200\,$cm$^{2}\cdot$V$^{-1}\cdot$s$^{-1}$, comparable to that of exfoliated pristine counterparts. The entire protocol represents a highly precise and non-invasive tailoring route for material manipulation.

cond-mat.mtrl-sci↗

arXiv2023

Nano-Subsidence Assisted Precise Integration of Patterned Two-Dimensional Materials for High-Performance Photodetector Arrays

The spatially precise integration of arrays of micro-patterned two-dimensional (2D) crystals onto three-dimensionally structured Si/SiO$_2$ substrates represents an attractive strategy towards the low-cost system-on-chip integration of extended functions in silicon microelectronics. However, the reliable integration of the arrays of 2D materials on non-flat surfaces has thus far proved extremely challenging due to their poor adhesion to underlying substrates as ruled by weak van der Waals interactions. Here we report on a novel fabrication method based on nano-subsidence which enables the precise and reliable integration of the micro-patterned 2D materials/silicon photodiode arrays exhibiting high uniformity. Our devices display peak sensitivity as high as 0.35 A/W and external quantum efficiency (EQE) of ca. 90%, outperforming most commercial photodiodes. The nano-subsidence technique opens a viable path to on-chip integrate 2D crystals onto silicon for beyond-silicon microelectronics.

physics.app-ph↗

arXiv2021

Analysis of external and internal disorder to understand band-like transport in n-type organic semiconductors

Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both internal and external (i.e. related to the interactions with the dielectric layer), especially for n-type materials. Internal dynamic disorder stems from large thermal fluctuations both in intermolecular transfer integrals and (molecular) site energies in weakly interacting van der Waals solids and sources transient localization of the charge carriers. The molecular vibrations that drive transient localization typically operate at low-frequency (< a-few-hundred cm-1), which renders it difficult to assess them experimentally. Hitherto, this has prevented the identification of clear molecular design rules to control and reduce dynamic disorder. In addition, the disorder can also be external, being controlled by the gate insulator dielectric properties. Here we report on a comprehensive study of charge transport in two closely related n-type molecular organic semiconductors using a combination of temperature-dependent inelastic neutron scattering and photoelectron spectroscopy corroborated by electrical measurements, theory and simulations. We provide unambiguous evidence that ad hoc molecular design enables to free the electron charge carriers from both internal and external disorder to ultimately reach band-like electron transport.

cond-mat.mtrl-sci↗

arXiv2019

Freeing electrons from extrinsic and intrinsic disorder yields band-like transport in n-type organic semiconductors

Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both intrinsic and extrinsic, especially for n-type materials. Intrinsic dynamic disorder stems from large thermal fluctuations both in intermolecular transfer integrals and (molecular) site energies in weakly interacting van der Waals solids and sources transient localization of the charge carriers. The molecular vibrations that drive transient localization typically operate at low-frequency (< a-few-hundred cm-1), which renders it difficult to assess them experimentally. Hitherto, this has prevented the identification of clear molecular design rules to control and reduce dynamic disorder. In addition, the disorder can also be extrinsic, being controlled by the gate insulator dielectric properties. Here we report on a comprehensive study of charge transport in two closely related n-type molecular organic semiconductors using a combination of temperature-dependent inelastic neutron scattering and photoelectron spectroscopy corroborated by electrical measurements, theory and simulations. We provide unambiguous evidence that ad hoc molecular design enables to free the electron charge carriers from both intrinsic and extrinsic disorder to ultimately reach band-like electron transport.

cond-mat.mtrl-sci↗

arXiv2016

Charge transport and mobility engineering in two-dimensional transition metal chalcogenide semiconductors

Two-dimensional (2D) van der Waals semiconductors represent the thinnest, air stable semiconducting materials known. Their unique optical, electronic and mechanical properties hold great potential for harnessing them as key components in novel applications for electronics and optoelectronics. However, the charge transport behavior in 2D semiconductors is more susceptible to external surroundings (e.g. gaseous adsorbates from air and trapped charges in substrates) and their electronic performance is generally lower than corresponding bulk materials due to the fact that surface and bulk coincide. In this article, we review recent progress on the charge transport properties and carrier mobility engineering of 2D transition metal chalcogenides, with a particular focus on the markedly high dependence of carrier mobility on thickness. We unveil the origin of this unique thickness dependence and elaborate the devised strategies to master it for carrier mobility optimization. Specifically, physical and chemical methods towards the optimization of the major factors influencing the extrinsic transport such as electrode/semiconductor contacts, interfacial Coulomb impurities and atomic defects are discussed. In particular, the use of \textit{ad-hoc} molecules makes it possible to engineer the interface with the dielectric and heal the vacancies in such materials. By casting fresh light onto the theoretical and experimental works, we provide a guide for improving the electronic performance of the 2D semiconductors, with the ultimate goal of achieving technologically viable atomically thin (opto)electronics.

cond-mat.mes-hall↗