
Liberato MannaIstituto Italiano di Tecnologia | IIT · Dipartimento di Nanochimica
Liberato Manna
Phd
About
771
Publications
182,202
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Introduction
EN. My research interests include the synthesis of colloidal nanocrystals, the study of structural, chemical and surface transformations in nanoscale materials, and their applications in energy, photonics, and electronics.
IT. I miei interessi di ricerca includono la sintesi di nanocristalli colloidali, lo studio delle proprietà strutturali, delle trasformazioni chimiche e di superficie di materiali alla nanoscala, e le loro applicazioni nei settori dell’energia, fotonica ed elettronica.
Additional affiliations
April 2009 - March 2020
Education
November 1990 - March 2001
Publications
Publications (771)
Light‐emitting diodes (LEDs) based on halide perovskite nanocrystals have attracted extensive attention due to their considerable luminescence efficiency, wide color gamut, high color purity, and facile material synthesis. Since the first demonstration of LEDs based on MAPbBr3 nanocrystals was reported in 2014, the community has witnessed a rapid d...
We report the synthesis of ethylammonium lead iodide (EAPbI3) colloidal nanocrystals as another member of the lead halide perovskites family. The insertion of an unusually large A-cation (274 pm in diameter) in the perovskite structure, hitherto considered unlikely due to the unfavorable Goldschmidt tolerance factor, results in a significantly larg...
The recent emergence of quantum‐confined nanomaterials in the field of radiation detection, in particular lead halide perovskite nanocrystals, offers scalability and performance advantages over conventional materials. This development raises fundamental questions about the mechanism of scintillation itself at the nanoscale and the role of particle...
Efficiency and emission rate are two traditionally conflicting parameters in radiation detection, and achieving their simultaneous maximization could significantly advance ultrafast time-of-flight (ToF) technologies. In this study, we demonstrate that this goal is attainable by harnessing the giant oscillator strength (GOS) inherent to weakly confi...
Perovskite nanocrystal superlattices are being actively studied after reports have emerged on collective excitonic properties at cryogenic temperatures, where energetic disorder is minimized due to the frozen lattice vibrations. However, an important issue related to structural disorder of superlattices at low temperatures has received little atten...
We report the synthesis of nanocrystal heterostructures composed of CsPbCl3 and PbS domains sharing an epitaxial interface. We were able to promote the growth of a PbS domain (in competition with the more commonly observed Pb4S3Cl2 one) on top of the CsPbCl3 domain by employing Mn²⁺ ions, the latter most likely acting as scavengers of Cl– ions. Com...
The recent emergence of quantum confined nanomaterials in the field of radiation detection, in particular lead halide perovskite nanocrystals, offers potentially revolutionary scalability and performance advantages over conventional materials. This development raises fundamental questions about the mechanism of scintillation itself at the nanoscale...
A colloidal synthesis protocol is demonstrated for InAs@InP core@shell quantum dots (QDs) with a tunable InP shell thickness (ranging from 3 to 8 monolayers), utilizing tris(diethylamino)‐arsine and ‐phosphine. Structural analysis reveals that the InP shell preferentially grows onto the tetrahedral InAs cores along the <‐1‐1‐1> directions, forming...
Absorbing near‐infrared (NIR) photons, with longer wavelengths, in atomically thin monolayer MoS2 presents a significant challenge due to its weak optical absorption and narrow absorption bands. Consequently, MoS2‐based photodetector devices often experience low responsivity and a limited detection window. Herein, a novel InAs@ZnSe core@shell/1L‐Mo...
Colloidal epitaxial heterostructures are nanoparticles composed of two different materials connected at an interface, which can exhibit properties different from those of their individual components. The ability to combine dissimilar materials offers wide opportunities to create functional heterostructures. However, the design stage often focuses o...
Perovskite nanocrystal superlattices are being actively studied after reports have emerged on collective excitonic properties at cryogenic temperatures, where energetic disorder is minimized due to the frozen lattice vibrations. However, an important issue related to structural disorder of superlattices at low temperatures has received little atten...
Understanding and mimicking the processes of life has been an endeavour for generations of scientists across all the fields of science and technology. Artificially designing the complexity of living cells from purely synthetic materials poses a significant challenge due to their complex bottom-up assembly. We show that a solvothermal reaction of pr...
We report a colloidal synthesis of blue emissive, stable cube-shaped CsPbBr3 quantum dots (QDs) in the strong quantum confinement regime via a dissolution-recrystallization starting from pre-synthesized (KxCs1-x)4PbBr6 nanocrystals which are then reacted with PbBr2. This is markedly different from the known case of Cs4PbBr6 nanocrystals that react...
Lead halide perovskite nanocrystals (LHP NCs) are generally prone to surface defect formation during the purification process, resulting in a reduced photoluminescence (PL) quantum yield. The purification of LHP NCs using antisolvents leads to the detachment of surface atoms and ligandsin the form of alkylammonium‐halides or A‐carboxylates (A: Cs,...
We report a colloidal synthesis of blue emissive, stable cube-shaped CsPbBr3 quantum dots (QDs) in the strong quantum confinement regime via dissolution–recrystallization starting from pre-syntesized (KxCs1–x)4PbBr6 nanocrystals which are then reacted with PbBr2. This is markedly different from the known case of Cs4PbBr6 nanocrystals that react wit...
Heavy‐metal‐free III–V colloidal quantum dots (QDs) exhibit promising attributes for application in optoelectronics. Among them, InAs QDs are demonstrating excellent optical performance with respect to absorption and emission in the near‐infrared spectral domain. Recently, InAs QDs attained a substantial improvement in photoluminescence quantum yie...
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) of over 2...
Designing robust and cost‐effective electrocatalysts for efficient alkaline oxygen evolution reaction (OER) is of great significance in the field of water electrolysis. In this study, an electrochemical strategy to activate stainless steel (SS) electrodes for efficient OER is introduced. By cycling the SS electrode within a potential window that en...
The development of quantum simulators, artificial platforms where the predictions of many-body theories of correlated quantum materials can be tested in a controllable and tunable way, is one of the main challenges of condensed matter physics. Here we introduce artificial lattices made of lead halide perovskite nanocubes as a new platform to simula...
Halide perovskites, in the form of thin films and colloidal nanocrystals, have recently taken semiconductor optoelectronics research by storm, and have emerged as promising candidates for high‐performance solar cells, light‐emitting diodes (LEDs), lasers, photodetectors, and radiation detectors. The impressive optical and optoelectronic properties,...
Combining multiple species working in tandem for different hydrogen evolution reaction (HER) steps is an effective strategy to design HER electrocatalysts. Here, we engineered a hierarchical electrode for the HER composed of amorphous-TiO2/Cu nanorods (NRs) decorated with cost-effective Ru–Cu nanoheterostructures (Ru mass loading = 52 μg/cm²). Such...
Halide exchange is a popular strategy to tune the properties of CsPbX3 nanocrystals after synthesis. However, while Cl → Br and Br → I exchanges proceed through the formation of stable mixed-halide nanocrystals, the Cl ⇌ I exchange is more elusive. Indeed, the large size difference between chloride and iodide ions causes a miscibility gap in the Cs...
We have approached the synthesis of colloidal InAs nanocrystals (NCs) using amino-As and ligands that are different from the commonly employed oleylamine (OA). We found that carboxylic and phosphonic acids led only to oxides, whereas tri-n-octylphosphine, dioctylamine, or trioctylamine (TOA), when employed as the sole ligands, yielded InAs NCs with...
The seeded growth method offers an efficient way to design core–shell semiconductor nanocrystals in the liquid phase. The combination of seed and shell materials offers wide tunability of morphologies and photophysical properties. Also, semiconductor nanorods (NRs) exhibit unique polarized luminescence which can potentially break the theoretical li...
Alkaline electrolyzers generally produce hydrogen at current densities below 0.5 A/cm². Here, we design a cost-effective and robust cathode, consisting of electrodeposited Ru nanoparticles (mass loading ~ 53 µg/cm²) on vertically oriented Cu nanoplatelet arrays grown on metallic meshes. Such cathode is coupled with an anode based on stacked stainle...
The search for efficient, re‐absorption‐free scintillators has recently focused the attention on antimony‐based halides, which exhibit largely Stokes shifted luminescence due to radiative recombination of excitons self‐trapped (STE) in strongly Jahn–Teller distorted Sb³⁺ color centers. Here, the synthesis of a hybrid structure is reported with chem...
The manipulation of nano-objects through heating is an effective strategy for inducing structural modifications and therefore changing the optoelectronic properties of semiconducting materials. Despite its potential, the underlying mechanism of the structural transformations remains elusive, largely due to the challenges associated with their in si...
Quantum dot (QD) based light-emitting diodes (QLEDs) hold great promise for next-generation lighting and displays. In order to reach a wide color gamut, deep red QLEDs emitting at wavelengths beyond 630 nm are highly desirable but have rarely been reported. Here, we synthesized deep red emitting ZnCdSe/ZnSeS QDs (diameter ∼16 nm) with a continuous...
Lanthanide-doped LiYF4 (Ln:YLF) is commonly used for a broad variety of optical applications, such as lasing, photon upconversion and optical refrigeration. When synthesized as nanocrystals (NCs), this material is also of interest for biological applications and fundamental physical studies. Until now, it was unclear how Ln:YLF NCs grow from their...
InAs-based nanocrystals can enable RoHS-compliant optoelectronic devices, but their photoluminescence efficiency needs improvement for practical applications. We report an optimized synthesis of InAs@ZnSe core@shell nanocrystals that allows to finely tune the ZnSe shell thickness up to 7 mono-layers (MLs) and to boost the emission, reaching a quant...
Conspectus
The surface chemistry of lead halide perovskite nanocrystals (NCs) plays a major role in dictating their colloidal and structural stability as well as governing their optical properties. A deep understanding of the nature of the ligand shell, ligand–NC, and ligand–solvent interactions is therefore of utmost importance. Our recent studie...
One major concern toward the performance and stability of halide perovskite-based optoelectronic devices is the formation of metallic lead that promotes nonradiative recombination of charge carriers. The origin of metallic lead formation is being disputed whether it occurs during the perovskite synthesis or only after light, electron, or X-ray beam...
We illustrate here the high photocatalytic activity of sustainable lead-free metal halide nanocrystals (NCs), namely, Cs3Sb2Br9 NCs, in the reduction of p-substituted benzyl bromides in the absence of a cocatalyst. The electronic properties of the benzyl bromide substituents and the substrate affinity to the NC surface determine the selectivity in...
Organic-inorganic Pb-free layered perovskites are efficient broadband emitters and thus are promising materials for lighting applications. However, their synthetic protocols require a controlled atmosphere, high temperature, and long preparation time. This hinders the potential tunability of their emission through organic cations, as is instead com...
CuFeS2 chalcopyrite nanoparticles (NPs) can generate heat under exposure to near-infrared laser irradiation. Here, we develop a protocol to decorate the surface of CuFeS2 NPs (13 nm) with a thermoresponsive (TR) polymer based on poly(ethylene glycol methacrylate) to combine heat-mediated drug delivery and photothermal heat damage. The resulting TR-...
Synthesis protocols of colloidal semiconductor nanocrystals (NCs) comprise the coordination of the semiconductive inorganic core by a layer of organic ligands, which play a crucial role in stabilizing the NCs in organic solvents. Understanding the distribution, binding and mobility of ligands on the different NC facets is key to prevent the formati...
The development of Quantum Simulators, artificial platforms where the predictions of many-body theories of correlated quantum materials can be tested in a controllable and tunable way, is one of the main challenges of condensed matter physics. Here we introduce artificial lattices made of lead halide perovskite nanocubes as a new platform to simula...
Ytterbium-doped LiYF4 (Yb:YLF) is a commonly used material for laser applications, as a photon upconversion medium, and for optical refrigeration. As nanocrystals (NCs), the material is also of interest for biological and physical applications. Unfortunately, as with most phosphors, with the reduction in size comes a large reduction of the photolum...
We report a detailed study on the first colloidal synthesis of NiAs nanocrystals. By optimizing the synthesis parameters, we were able to obtain trioctylphosphine-capped NiAs nanoplatelets with an average diameter of ∼10 nm and a thickness of ca. 4 nm. We then studied the performance of such NiAs nanocrystals as electrocatalysts for electrochemical...
ConspectusFor almost a decade now, lead halide perovskite nanocrystals have been the subject of a steadily growing number of publications, most of them regarding CsPbBr3 nanocubes. Many of these works report X-ray diffraction patterns where the first Bragg peak has an unusual shape, as if it was composed of two or more overlapping peaks. However, t...
In recent years remarkable progress has been made on developing low‐dimensional perovskite‐related materials. In particular, with the aim of going toward compounds with low toxicity, various low‐dimensional metal halide nanocrystals have been synthesized and investigated. These nanocrystalline compounds crystallize in a plethora of structures and d...
Colloidal quantum dots (QDs) emitting in the infrared (IR) are promising building blocks for numerous photonic, optoelectronic and biomedical applications owing to their low-cost solution-processability and tunable emission. Among them, lead- and mercury-based QDs are currently the most developed materials. Yet, due to toxicity issues, the scientif...
Mixing bromine and iodine within lead halide perovskites is a common strategy to tune their optical properties. This comes at the cost of instability, as illumination induces halide segregation and degrades device performances. Hence, understanding the behavior of mixed-halide perovskites is crucial for applications. In 3D perovskites such as MAPb(...