arXiv subjects

Francesco Di Stasio

Publications and source records attributed to Francesco Di Stasio.

14 recordsLinked to original sources

arXiv2026

When blinking helps: enhanced single-photon purity in the off states of perovskite quantum dots

Photoluminescence blinking typically degrades the single-photon purity of quantum dot emission. Here, we show that individual CsPbBr$_3$ perovskite quantum dots (PQDs) can exhibit the opposite behavior: low-emitting off states are dimmer and shorter-lived, yet more strongly antibunched than high-intensity on states. Using time-correlated single-photon counting combined with state-resolved second-order correlation analysis, we identify a subset of PQDs in which the zero-delay second-order correlation, $g^{(2)}_0$, decreases upon switching from the on state to the off state, indicating improved single-photon purity. In the most pronounced case, $g^{(2)}_0$ decreases from 0.23 in the on state to 0.08 in the off state. We attribute this counterintuitive behavior to self-trapped-exciton-mediated suppression of the biexciton--exciton cascade, which suppresses multiphoton emission more effectively than single-exciton emission. These findings reveal an unconventional blinking regime in PQDs and show that blinking does not necessarily degrade single-photon purity.

cond-mat.mes-hall↗

arXiv2026

Unveiling Photoluminescence Signatures of Magneto-Optical Coupling in Layered Hybrid Manganese Chloride Perovskites

Understanding the interplay between magnetic ordering and light emission is crucial for developing magneto-optical technologies. However, this phenomenon is poorly understood since observations of this coupling vary significantly across materials. In this context, hybrid organic-inorganic metal halide perovskites (HOIPs) that incorporate Mn2+ ions are a chemically and structurally tunable platform for exploring this phenomenon, since they exhibit magnetic ordering and photoluminescence (PL) emission. Here, we study two antiferromagnetic Mn-based HOIPs with different organic cations that result in distinct lattice stiffness, Mn2+-Mn2+ distance and octahedral distortion. Temperature-dependent PL excitation spectroscopy reveals changes in crystal field splitting energy and Racah parameters well above the Néel temperature (TN), indicating the emergence of Mn2+-Mn2+ magnetic interactions prior to reach long-range magnetic ordering. These variations align with the observed changes in temperature-PL evolution. The compound with a more rigid lattice shows stronger changes closer to TN, suggesting combined effects of magnetic polarons and spin-canting. In contrast, magnetic polaron-induced magnetic modifications prevail in the HOIP with a softer lattice. These results reveal the complexity of the magneto-optical coupling in Mn-based HOIPs and provide new insights into this field extensible to other 2D materials that exhibit this phenomenon with potential for advanced magneto-optical applications.

cond-mat.mtrl-sci↗

arXiv2026

Permanent Lattice Compression of Lead-Halide Perovskite for Persistently Enhanced Optoelectronic Properties

Under mild mechanical pressure, halide perovskites show enhanced optoelectronic properties. However, these improvements are reversible upon decompression, and permanent enhancements have yet to be realized. Here, we report antisolvent-assisted solvent acidolysis crystallization that enables us to prepare methylammonium lead bromide single crystals showing intense emission at all four edges under ultraviolet light excitation. We study structural variations, edge-vs-center, in these crystals using micro-X-ray diffraction and find that the enhanced emission at the edges correlates with lattice compression compared to in the central areas. Time-resolved photoluminescence measurements show much longer-lived photogenerated carriers at the compressed edges, with radiative component lifetimes of ca. 1.4 us, 10 times longer than at the central regions. The properties of the edges are exploited to fabricate planar photodetectors exhibiting detectivities of 3x10^13 Jones, compared to 5x10^12 Jones at the central regions. The enhanced lifetimes and detectivities correlate to the reduced trap state densities and the formation of shallower traps at the edges due to lattice compression.

cond-mat.mtrl-sci↗

arXiv2025

Improving the Stability of Colloidal CsPbBr3 Nanocrystals with an Alkylphosphonium Bromide as Surface Ligand Pair

In this study, we synthesised a phosphonium-based ligand, trimethyl(tetradecyl)phosphonium bromide (TTP-Br), and employed it in the post-synthesis surface treatment of Cs-oleate-capped CsPbBr3 NCs. The photoluminescence quantum yield (PLQY) of the NCs increased from 60% to more than 90%, as a consequence of replacing Cs-oleate with TTP-Br ligand pairs. Density functional theory calculations revealed that TTP+ ions bind to the NC surface by occupying Cs+ surface sites and orienting one of their P-CH3 bonds perpendicular to the surface, akin to quaternary ammonium passivation. Importantly, TTP-Br-capped NCs exhibited higher stability in air compared to didodecyldimethylammonium bromide-capped CsPbBr3 NCs (which is considered a benchmark system), retaining 90% of their PLQY after six weeks of air exposure. Light-emitting diodes fabricated with TTP-Br-capped NCs achieved a maximum external quantum efficiency of 17.2 %, demonstrating the potential of phosphonium-based molecules as surface ligands for CsPbBr3 NCs in optoelectronic applications.

cond-mat.mtrl-sci↗

arXiv2025

Near-Infrared Light Emitting Metal Halides: Materials, Mechanisms, and Applications

Near-Infrared (NIR) light emitting metal halides are emerging as a new generation of optical materials owing to their appealing features, which include low-cost synthesis, solution processability and adjustable optical properties. NIR emitting perovskite-based light-emitting diodes (LEDs) have reached an external quantum efficiency (EQE) over 20% and a device stability of over 10,000 h. Such results have sparked an interest in exploring new NIR metal halide emitters. In this review, we summarize several different types of NIR-emitting metal halides, including lead/tin bromide/iodide perovskites, lanthanide ions doped/based metal halides, double perovskites, low dimensional hybrid and Bi3+/Sb3+/Cr3+ doped metal halides, and assess their recent advancements. The characteristics and mechanisms of narrow-band or broadband NIR luminescence in all these materials are discussed in detail. We also highlight the various applications of NIR-emitting metal halides and provide an outlook for the field.

cond-mat.mtrl-sci↗

arXiv2025

Enhanced vibrational optical activity by near-zero index chiral effective media

The enhancement of the inherently weak optical activity of solvated molecules by superchiral fields, crucial for detecting their chirality, is a research frontier of photonics and the basis of novel chiroptical detection schemes. Here, we show that an effective medium consisting of randomly dispersed metal-based nanoparticles embedded within an optically active solvated drug (aqueous reparixin) can enhance vibrational optical rotation and circular dichroism thanks to superchirality produced by slow light in near-zero index conditions. We evaluate from first principles the effective bianisotropic response of the bulk chiral effective medium, showing that, by adjusting the nanoparticles filling fraction, vibrational optical activity is greatly enhanced by a factor $\simeq 10^2-10^3$ at the near-zero index resonance. Our results are relevant for the development of innovative devices capable of detecting the chirality of low-volume samples, with applications in quantum chemistry and nanomedicine.

physics.optics↗

arXiv2023

Plasmon-enhanced circular dichroism spectroscopy of chiral drug solutions

We investigate the potential of surface plasmon polaritons at noble metal interfaces for surface-enhanced chiroptical sensing of dilute chiral drug solutions. The high quality factor of surface plasmon resonances in both Otto and Kretschmann configurations enables the enhancement of circular dichroism differenatial absorption thanks to the large near-field intensity of such plasmonic excitations. Furthermore, the subwavelength confinement of surface plasmon polaritons is key to attain chiroptical sensitivity to small amounts of drug volumes placed around $\simeq 100$ nm by the metal surface. Our calculations focus on reparixin, a pharmaceutical molecule currently used in clinical studies for patients with community-acquired pneumonia, including COVID-19 and acute respiratory distress syndrome. Considering realistic dilute solutions of reparixin dissolved in water with concentration $\leq 5$ mg$/$ml, we find a circular-dichroism differential absorption enhancement factor of the order $\simeq 20$ and chirality-induced polarization distortion upon surface plasmon polariton excitation.

physics.optics↗

arXiv2020

Enhancing the Performance of CdSe/CdS Dot-in- Rod Light Emitting Diodes via Surface Ligand Modification

The surface ligands on colloidal nanocrystals (NCs) play an important role in the performance of NCs based optoelectronic devices such as photovoltaic cells, photodetectors and light emitting diodes (LEDs). On one hand, the NC emission depends critically on the passivation of the surface to minimize trap states that can provide non-radiative recombination channels. On the other hand, the electrical properties of NC films are dominated by the ligands that constitute the barriers for charge transport from one NC to its neighbor. Therefore, surface modifications via ligandexchange have been employed to improve the conductance of NC films. However, in light emitting devices, such surface modifications are more critical due to their possible detrimental effects on the emission properties. In this work, we study the role of surface ligand modifications on the optical and electrical properties of CdSe/CdS dot-in-rods (DiRs) in films, and investigate their performance in all-solution processed LEDs. The DiR films maintain high PLQY, around 40-50%, and their electroluminescence in the LED preserves the excellent color purity of the PL. In the LEDs, the ligand-exchange boosted the luminance, reaching a four-fold increase from 2200 cd/m2 for native surfactants to 8500 cd/m2 for the exchanged aminoethanethiol ligands. Moreover, the efficiency roll-off, operational stability, and shelf life are significantly improved, and the external quantum efficiency is modestly increased from 5.1 % to 5.4 %. We relate these improvements to the increased conductivity of the emissive layer, and to the better charge balance of the electrically injected carriers. In this respect, we performed ultraviolet photoelectron spectroscopy (UPS) to obtain deeper insight in the band alignment of the LED structure.

physics.chem-ph↗

arXiv2020

Core/Shell CdSe/CdS Bone-Shaped Nanocrystals with a Thick and Anisotropic Shell as Optical Emitters

Colloidal core/shell nanocrystals are key materials for optoelectronics, enabling control over essential properties via precise engineering of the shape, thickness, and crystal lattice structure of their shell. Here, we apply the growth protocol for CdS branched nanocrystals on CdSe nanoplatelet seeds and obtain bone-shaped heterostructures with a highly anisotropic shell. Surprisingly, the nanoplatelets withstand the high growth temperature of 350 °C and we obtain structures with a CdSe nanoplatelet core that is overcoated by a shell of cubic CdS, on top of which tetrahedral CdS structures with hexagonal lattice are formed. These complex core/shell nanocrystals show a bandedge emission around 657 nm with a photoluminescence quantum yield of ca. 42 % in solution, which is also retained in thin films. Interestingly, the nanocrystals manifest simultaneous red and green emission, and the relatively long wavelength of the green emission indicates charge recombination at the cubic/hexagonal interface of the CdS shell. The nanocrystal films show amplified spontaneous emission, random lasing, and distributed feedback lasing when the material is deposited on suitable gratings. Our work stimulates the design and fabrication of more exotic core/shell heterostructures where charge carrier delocalization, dipole moment, and other optical and electrical properties can be engineered.

physics.chem-ph↗

arXiv2019

High-Efficiency Light-Emitting Diodes based on Formamidinium lead bromide nanocrystals and solution processed transport layers

Perovskite nanocrystal light-emitting diodes (LEDs) employing architecture comprising a ZnO nanoparticles electron-transport layer and a conjugated polymer hole-transport layer have been fabricated. The obtained LEDs demonstrate a maximum external-quantum-efficiency of 6.04%, luminance of 12998 Cd/m2 and stable electroluminescence at 519 nm. Importantly, such high efficiency and brightness have been achieved by employing solution processed transport layers, formamidinium lead bromide nanocrystals (CH(NH2)2PbBr3 NCs) synthesized at room-temperature and in air without the use of a Schlenk line, and a procedure based on atomic layer deposition to insolubilize the NC film. The obtained NCs show a photoluminescence quantum yield of 90% that is retained upon film fabrica-tion. The results show that perovskite NC LEDs can achieve high-performance without the use of transport layers deposited through evapo-ration in ultra-high-vacuum.

physics.app-ph↗

arXiv2019

High Open Circuit voltage solar cells based on bright mixed halide CsPbBrI2 perovskite nanocrystals synthesized under ambient air conditions

Lead halide perovskite nanocrystals (NCs) are currently emerging as one of the most interesting solution processed semiconductors since they possess high photoluminescence quantum yield (PLQY), and colour tunability through anion exchange reactions or quantum confinement. Here, we show efficient solar cells based on mixed halide (CsPbBrI2) NCs obtained via anion exchange reactions in ambient conditions. We performed anion exchange reactions in concentrated NC solutions with I-, thus inducing a PL red-shift up to 676 nm, and obtaining a high PLQY in film (65%). Solar cell devices operating in the wavelength range 350-660 nm were fabricated in air with two different deposition methods. The solar cells display a photo-conversion efficiency of 5.3% and open circuit voltage (Voc) up to 1.31V, among the highest reported for perovskite based solar cells with band gap below 2eV, clearly demonstrating the potential of this material.

physics.app-ph↗

arXiv2018

Multirate 5G Downlink Performance Comparison for f-OFDM and w-OFDM Schemes with Different Numerologies

One of the main open problems for next generation wireless networks, is to find the new OFDM-based waveform to be used in 5G. The new modulation scheme must primarily be able to achieve higher spectral efficiency than its predecessor. The main 3GPP's candidate is a new version of OFDM, called Filtered Orthogonal Frequency-Division Multiplexing (f-OFDM), which is similar to OFDM but with additional filtering in order to reduce Out-Of-Band (OOB) emissions and to obtain a better spectral-localization. Another option is windowed-OFDM (w-OFDM), which is basically a classical OFDM scheme where each symbol is windowed and overlapped in the time domain. In this paper we compare classic OFDM signals using Cyclic Prefix (CP-OFDM) with f-OFDM and w-OFDM, each one with multiple parametric options and numerologies. A multirate transmitter simultaneously operating with multiple numerologies is considered, where the transmitted sub-bands must be up-sampled and interpolated in order to generate the composite numerical signal fed to the Digital to Analog Converter (DAC). Finally, we discuss advantages and disadvantages of the various schemes.

eess.SP↗

arXiv2018

Single-mode lasing from colloidal water-soluble CdSe/CdS quantum dot-in-rods

Core-shell CdSe/CdS nanocrystals are a very promising material for light emitting applications. Their solution-phase synthesis is based on surface-stabilizing ligands that makes them soluble in organic solvents, like toluene or chloroform. However, solubility of these materials in water provides many advantages, such as additional process routes and easier handling. So far, solubilization of CdSe/CdS nanocrystals in water that avoids detrimental effects on the luminescent properties, poses a major challenge. This work demonstrates how core-shell CdSe/CdS quantum dot-in-rods can be transferred into water using a ligand exchange method employing mercaptopropionic acid (MPA). Key to maintaining the light-emitting properties is an enlarged CdS rod diameter, which prevents potential surface defects formed during the ligand exchange from affecting the photophysics of the dot-in-rods. Films made from water-soluble dot-in-rods show amplified spontaneous emission (ASE) with a similar threshold (130 microJ/cm2) as the pristine material (115 microJ/cm2). To demonstrate feasibility for lasing applications, self-assembled micro lasers are fabricated via the coffee-ring effect that display single-mode operation and a very low threshold of around 10 microJ/cm2. The performance of these micro lasers is enhanced by the small size of MPA ligands, enabling a high packing density of the dot-in-rods.

physics.app-ph↗

arXiv2016

Colloidal Synthesis of Strongly Fluorescent CsPbBr3 Nanowires with Width Tunable down to the Quantum Confinement Regime

We report the colloidal synthesis of strongly fluorescent CsPbBr3 perovskite nanowires (NWs) with rectangular section and with tuneable width, from 20 nm (exhibiting no quantum confinement, hence emitting in the green) down to around 3 nm (in the strong quan-tum-confinement regime, emitting in the blue), by introducing in the synthesis a short acid (octanoic acid or hexanoic acid) together with alkyl amines (octylamine and oleylamine). Temperatures below 70 °C promoted the formation of monodisperse, few unit cell thick NWs that were free from byproducts. The photoluminescence quantum yield of the NW samples went from 12% for non-confined NWs emitting at 524 nm to a maximum of 77% for the 5 nm diameter NWs emitting at 497 nm, down to 30% for the thinnest NWs (diameter ~ 3nm), in the latter sample most likely due to aggregation occurring in solution.

physics.chem-ph↗