Liberato Manna

Liberato Manna
Istituto Italiano di Tecnologia | IIT · Dipartimento di Nanochimica

Phd

About

661
Publications
125,932
Reads
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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
Istituto Italiano di Tecnologia
Position
  • Direttore
Education
November 1990 - March 2001

Publications

Publications (661)
Article
The most developed approaches for the synthesis of InAs nanocrystals (NCs) rely on pyrophoric, toxic, and not readily available tris-trimethylsilyl (or tris-trimethylgermil) arsine precursors. Less toxic and commercially available chemicals, such as tris(dimethylamino)arsine, have recently emerged as alternative As precursors. Nevertheless, InAs NC...
Article
Full-text available
Simultaneously achieving both broad absorption and sharp emission in the near-infrared (NIR) is challenging. Coupling of an efficient absorber such as lead halide perovskites to lanthanide emissive species is a promising way to meet the demands for visible-to-NIR spectral conversion. However, lead-based perovskite sensitizers suffer from relatively...
Article
Radiation detectors are widely used in physics, materials science, chemistry, and biology. Halide perovskites are known for their superior properties including tunable bandgaps and chemical compositions, high defect tolerance, solution-processable synthesis of films and crystals, and high carrier diffusion length. Recently, halide perovskites have...
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The development of earth‐abundant electrocatalysts (ECs) operating at high current densities in water splitting electrolyzers is pivotal for the widespread use of the current green hydrogen production plants. Transition metal dichalcogenides (TMDs) have emerged as promising alternatives to the most efficient noble metal ECs, leading to a wealth of...
Article
Here we present a colloidal approach to synthesize bismuth chalcohalide nanocrystals (BiEX NCs, in which E = S, Se and X = Cl, Br, I). Our method yields orthorhombic elongated BiEX NCs, with BiSCl crystallizing in a previously unknown polymorph. The BiEX NCs display composition dependent band gap spanning the visible spectral range and absorption c...
Article
Full-text available
Metal halide perovskite nanocrystals, an emerging class of materials for advanced photonic and optoelectronic applications, are mainly fabricated with colloidal chemistry routes. On the quest for new properties according to application needs, new perovskite systems of various morphologies and levels of doping and alloying have been developed, often...
Article
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We utilize the solvent acidolysis crystallization technique to grow mixed dimethylammonium/methylammonium lead tribromide (DMA/MAPbBr3) crystals reaching the highest dimethylammonium incorporation of 44% while maintaining the 3D cubic perovskite phase. These mixed perovskite crystals show suppression of the orthorhombic phase and a lower tetragonal...
Article
Here we present a colloidal approach to synthesize bismuth chalcohalide nanocrystals (BiEX NCs, in which E = S, Se and X = Cl, Br, I). Our method yields orthorhombic elongated BiEX NCs, with BiSCl crystallizing in a previously unknown polymorph. The BiEX NCs display composition dependent band gap spanning the visible spectral range and absorption c...
Article
Full-text available
Fermi level pinning in doped metal oxide (MO) nanocrystals (NCs) results in the formation of depletion layers, which affect their optical and electronic properties, and ultimately their application in smart optoelectronics, photocatalysis, or energy storage. For a precise control over functionality, it is important to understand and control their e...
Article
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The interaction of lead bromide perovskite nanocrystals with charged ligands, such as salts, zwitterions, or acid–base pairs, has been extensively documented over the past few years. On the other hand, little is known about the reactivity of perovskite nanocrystals toward neutral ligands. To fill this gap, in this work we study the interaction of C...
Chapter
In this chapter we provide an overview of the fundamental thermodynamic and kinetic parameters governing the growth of colloidal nanoparticles. We also give a phenomenological description of shape control of nanostructures, along with several examples drawn from the literature.
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The encapsulation of colloidal lead halide perovskite nanocrystals within silica (SiO2) is one of the strategies to protect them from polar solvents and other external factors. Here, we demonstrate the overcoating of CsPbBr3 perovskite nanocrystals with silica by exploiting the anhydride-induced transformation of Cs4PbBr6 nanocrystals. CsPbBr3@SiO2...
Article
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The engineering of the structural and morphological properties of nanomaterials is a fundamental aspect to attain desired performance in energy storage/conversion systems and multifunctional composites. We report the synthesis of room temperature-stable metallic rutile VO2 (VO2 (R)) nanosheets by topochemically transforming liquid-phase exfoliated...
Article
Layered double perovskites are currently being investigated as emerging halide-based materials for optoelectronic applications. Herein, we present the synthesis of Cs4MnxCd1-xSb2Cl12 (0 ≤ x ≤ 1) nanocrystals (NCs). X-ray powder diffraction evidences the retention of the same crystal structure for all the inspected compositions; transmission electro...
Article
Full-text available
The research on two-dimensional colloidal semiconductors has received a boost from the emergence of ultrathin lead halide perovskite nanoplatelets. While the optical properties of these materials have been widely investigated, their accurate structural and compositional characterization is still challenging. Here, we exploited the natural tendency...
Article
We have realized a Lithium Iron Phosphate (LFP)-graphene nanohybrid obtained by a direct LFP crystal colloidal synthesis on few-layer graphene (FLG) flakes produced by the liquid phase exfoliation (LPE) of pristine graphite. This hybrid material has been tested as a cathode in Li-ion batteries, achieving fast charge/discharge responses to high spec...
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We have investigated the transformations of colloidal Pd-Cu and Pt-Cu bimetallic alloy nanocrystals (NCs) supported on γ-Al2O3 when exposed to a sequence of oxidizing and then reducing atmospheres, in both cases at high temperature (350 °C). A combination of in situ diffuse reflectance infrared Fourier transform spectroscopy and X-ray absorption sp...
Article
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Lead halide perovskites (LHP) are rapidly emerging as efficient, low-cost, solution-processable scintillators for radiation detection. Carrier trapping is arguably the most critical limitation to the scintillation performance. Nonetheless, no clear picture of the trapping and detrapping mechanisms to/from shallow and deep trap states involved in th...
Article
Full-text available
Cs4PbBr6 (0D) nanocrystals at room temperature have both been reported as nonemissive and green-emissive systems in conflicting reports, with no consensus regarding both the origin of the green emission and the emission quenching mechanism. Here, via ab initio molecular dynamics (AIMD) simulations and temperature-dependent photoluminescence (PL) sp...
Preprint
Full-text available
Layered double perovskite are currently investigated as emerging halide-based materials for optoelectronic applications. Herein, we present the synthesis of Cs4MnxCd1-xSb2Cl12 (0 ≤ x ≤ 1) nanocrystals (NCs). X-ray powder diffraction evidences the retaining of the same crystal structure for all the inspected composition; transmission electron micros...
Preprint
Layered double perovskite are currently investigated as emerging halide-based materials for optoelectronic applications. Herein, we present the synthesis of Cs4MnxCd1-xSb2Cl12 (0 ≤ x ≤ 1) nanocrystals (NCs). X-ray powder diffraction evidences the retaining of the same crystal structure for all the inspected composition; transmission electron micros...
Preprint
Full-text available
The research on bidimensional colloidal semiconductors has received a boost from the emergence of ultrathin lead-halide perovskite nanoplatelets. While the optical properties of these materials have been widely investigated, their accurate structural and compositional characterization is still challenging. Here, we exploited the natural tendency of...
Preprint
The research on bidimensional colloidal semiconductors has received a boost from the emergence of ultrathin lead-halide perovskite nanoplatelets. While the optical properties of these materials have been widely investigated, their accurate structural and compositional characterization is still challenging. Here, we exploited the natural tendency of...
Preprint
Full-text available
The understanding of depletion layers is of major importance to control the optical and electronic properties of metal oxide (MO) nanocrystals (NCs). Here, we show that depletion layer engineering is the main mechanism of photodoping of MO NCs. We show that the introduction of different electronic interfaces induces a double-bending of the electron...
Article
Full-text available
We report a one-step synthesis of halide perovskite nanocrystals embedded in amphiphilic polymer (poly(acrylic acid)-block-poly(styrene), PAA-b-PS) micelles, based on injecting a dimethyl-formamide solution of PAA-b-PS, PbBr 2 , ABr (A = Cs, formamidinium, or both) and "additive" molecules in toluene. These bifunctional or trifunctional short chain...
Article
Full-text available
Lead halide perovskite nanocrystals have drawn attention as active light-absorbing or -emitting materials for opto-electronic applications due to their facile synthesis, intrinsic defect tolerance, and color-pure emission ranging over the entire visible spectrum. To optimize their application in, e.g., solar cells and light-emitting diodes, it is d...
Article
Full-text available
Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent c...
Article
The family of metal halide (MH) nanocrystal materials is still vastly unexplored and unlocking their full potential is just at the beginning. The understanding and, therefore, the optimization of the properties of these nanoscale systems passes through a series of experimental characterization techniques that span compositional analysis, resolution...
Article
Full-text available
We synthesize colloidal nanocrystals (NCs) of Rb3InCl6, composed of isolated metal halide octahedra (“0D”), and of Cs2NaInCl6 and Cs2KInCl6 double perovskites, where all octahedra share corners and are interconnected (“3D”), with the aim to elucidate and compare their optical features once doped with Sb³⁺ ions. Our optical and computational analyse...
Article
Hollow structures made of nanoscale building blocks are of great interest as catalysts for electrochemical water splitting. Here we report a solution-phase synthesis of yolk-shell Co3O4/Co1−xRuxO2microspheres (MSs) having a shell made of Co1−xRuxO2nanorods and the core of Co3O4. Benefiting from the peculiar morphology and the synergy between the di...
Article
Ternary I-III-VI 2 nanocrystals (NCs), such as AgInS 2 and CuInS 2 , are garnering interest as heavy-metal-free materials for photovoltaics, luminescent solar concentrators, LEDs, and bioimaging. The origin of the emission and absorption properties in this class of NCs is still a subject of debate. Recent theoretical and experimental studies reveal...
Article
Full-text available
The unique combination of organic and inorganic layers in 2D layered perovskites offers promise for the design of a variety of materials for mechatronics, flexoelectrics, energy conversion, and lighting. However, the potential tailoring of their properties through the organic building blocks is not yet well understood. Here, different classes of or...
Article
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The structural flexibility of 2D layered halide perovskites provides unprecedented opportunities for tuning their optical properties. For example, lattice distortions facilitate white emission that stems from self‐trapped excitons or defects, and organic cations and halides determine structural stability and emission range. Here, we investigate the...
Article
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The synergy between the organic component of two-dimensional (2D) metal halide layered perovskites and flexible polymers offers an unexplored window to tune their optical properties at low mechanical stress. Thus, there is a significant interest in exploiting their PL anisotropy by controlling their orientation and elucidating their interactions. H...
Article
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Using mesoporous SiO2 to encapsulate CsPbBr3 nanocrystals is one of the best strategies to exploit such materials in devices. However, the CsPbBr3/SiO2 composites produced so far do not exhibit strong photoluminescence emission and, simultaneously, high stability against heat and water. We demonstrate a molten-salts-based approach delivering CsPbBr...
Article
Full-text available
Colloidal superlattices are fascinating materials made of ordered nanocrystals, yet they are rarely called “atomically precise”. That is unsurprising, given how challenging it is to quantify the degree of structural order in these materials. However, once that order crosses a certain threshold, the constructive interference of X-rays diffracted by...
Article
The Cs4PbBr6 nanocrystals are often used as a starting material for the preparation of green-emitting CsPbBr3 perovskite nanocrystals by means of chemical and physical transformations. Herein, we probe the Cs4PbBr6 nanocrystals dispersed in a solvent by liquid cell transmission electron microscopy (LCTEM). The nanocrystal dispersion in toluene is p...
Article
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We report the synthesis of colloidal CsPbX3–Pb4S3Br2 (X = Cl, Br, I) nanocrystal heterostructures, providing an example of a sharp and atomically resolved epitaxial interface between a metal halide perovskite and a non-perovskite lattice. The CsPbBr3–Pb4S3Br2 nanocrystals are prepared by a two-step direct synthesis using preformed subnanometer CsPb...
Article
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Following the impressive development of bulk lead-based perovskite photovoltaics, the “perovskite fever” did not spare nanochemistry. In just a few years, colloidal cesium lead halide perovskite nanocrystals have conquered researchers worldwide with their easy synthesis and color-pure photoluminescence. These nanomaterials promise cheap solution-pr...
Article
Full-text available
We report a contactless charge injection scheme that allows us to locally and quasi‐permanently manipulate atomically thin 2D materials, such as monolayer (1L‐)MoS2, over spatial extents of several tens of micrometers. The possibility to precisely position and localize the charge injection source to the micrometer scale post‐fabrication allowed us...
Article
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Excitonic coupling, electronic coupling, and cooperative interactions in self-assembled lead halide perovskite nanocrystals were reported to give rise to a red-shifted collective emission peak with accelerated dynamics. Here we report that similar spectroscopic features could appear as a result of the nanocrystal reactivity within the self-assemble...
Article
Even if we will not be able to find alternative materials that match all of the current performances of lead halide perovskite nanocrystals, we should not be discouraged because these alternatives can still be very useful in various light emission applications.
Article
Full-text available
We employed oleylphosphonic acid (OLPA) for the synthesis of CsPbBr3 nanocrystals (NCs). Compared to phosphonic acids with linear alkyl chains, OLPA features a higher solubility in apolar solvents, allowing us to work at lower synthesis temperatures (100 °C), which in turn offer a good control over the NCs size. This can be reduced down to 5.0 nm,...
Article
Full-text available
Various strategies have been proposed to engineer the band gap of metal halide perovskite nanocrystals (NCs) while preserving their structure and composition and thus ensuring spectral stability of the emission color. An aspect that has only been marginally investigated is how the type of surface passivation influences the structural/color stabilit...
Article
Full-text available
In this Viewpoint, we present a different way of approaching Cs-Pb-X set of compounds. Instead of [PbX6]4– octahedra, we take the arrangement of Cs+ cations as the leading structural motif. From such a perspective, the parent structure of the group is CsX, where the Cs+ ions form a substructure of cubic cages, each enclosing a single halide ion. Su...
Article
Full-text available
The nanoengineering of the structure of transition metal dichalcogenides (TMDs) is widely pursued to develop viable catalysts for the hydrogen evolution reaction (HER) alternative to the precious metallic ones. Metallic group‐5 TMDs have been demonstrated to be effective catalysts for the HER in acidic media, making affordable real proton exchange...
Preprint
Full-text available
Metal halide perovskites represent a flourishing area of research, driven by both their potential application in photo-voltaics and optoelectronics, and for the fundamental science underpinning their unique optoelectronic properties. The advent of colloidal methods for the synthesis of halide perovskite nanocrystals has brought to the attention int...
Article
Lead‐free halide perovskites such as the easily synthesized double perovskite Cs2AgInCl6 have generated great attention as promising alternatives to lead‐based counterparts. This Minireview takes a close look at Cs2AgInCl6 materials in the form of bulk crystals as well as nanocrystals in terms of doping engineering, photoluminescence modification,...
Article
Inorganic lead halide perovskites are promising candidates for optoelectronic applications, due to their high photoluminescence quantum yield and narrow emission line widths. Particularly attractive is the possibility to vary the bandgap as a function of the halide composition and the size or shape of the crystals at the nanoscale. Here we present...
Preprint
Colloidal superlattices are fascinating materials made of ordered nanocrystals, yet they are rarely called “atomically precise.” That is unsurprising, given how challenging it is to quantify the degree of structural order in these materials. However, once that order crosses a certain threshold, constructive interference of X-rays diffracted by the...
Article
Lead‐free halide perovskites have drawn wide attention for the recent attempts to find alternative solutions to the toxic and poorly stable lead‐based counterparts. Among them, double perovskites with Cs 2 AgInCl 6 composition, often doped with various elements, have been under the spotlight for their intriguing optical properties, viz., self‐trapp...