Materials Science

Contact Persons: Luigi Carbone, Vittorianna Tasco

Keywords:
NANOTEC is engaged in different fields of materials science aimed at advanced applications. Research activities are focused on the design and growth of breed-new materials via vapor- and/or solution-phase methodologies (CVD, MOCVD, MBE, PVD, PECVD, self-assembling, sol-gel, etc). Based on fundamental research, we elucidate principles underpinning processing-structure-property relationships in functional materials and nanomaterials both inorganic and organic, and their hybrids and nanocomposites, with interesting electronic, magnetic, optical, mechanical or catalytic properties. We exploit those relationships to introduce new structure-related functionalities and build a basis for “predicting” new materials. Topics covered include III-V semiconductors, Si-based alloys, organic semiconductors, dielectrics, piezoelectrics, ferroelectrics, nanomaterials, graphene, 2D-materials, nanocomposites, colloidal nanocrystals, non-crystalline solids, self-assembled monolayers and functional surfaces. Through these efforts, NANOTEC aims to create advanced materials that contribute to society functional innovations.

The research lines of the Materials Science area are listed below:

  1. Organic functional materials
  2. Graphene and 2D materials
  3. Inorganic and Hybrid Semiconductors
  4. Colloidal inorganic nanocrystals
  5. Complex fluids
  6. Sustainable chemistry

Organic functional materials
Contact Persons: Gianluca Accorsi, Agostina Lina Capodilupo, Francesca Baldassarre

Keywords: Organic Synthesis, Electrochromism, Photophysics, Photoinduced Processes, Molecular Design, Drug Delivery, Biopolymers

People: Gianluca Accorsi, Francesca Baldassarre, Agostina Lina Capodilupo, Giuseppe Ciccarella, Viviana Vergaro

The research activities in the Organic functional materials area are organized according to the research lines, hereafter listed.

Synthesis and Photophysics of π-conjugated Organic Materials. The development of advanced organic materials, based on π-conjugated functional systems, represents the starting point for several application fields. We design and synthesize new molecular building blocks and explore their opto-electronic properties, in solution and in the solid state, in order to make available new materials to be employed as optically active elements in the lighting, electrochromism, electrofluorochromism, field-effect transistor, fluorescent bioimaging, photovoltaics and advanced photonics areas. Moreover, photochemical and photophysical characterization in the UV-VIS-NIR spectral windows, at low and room temperature, are performed in order to investigate photoinduced energy- and electron-transfer processes in organic and inorganic dyes. Kinetics from pico- to second timescale, are also obtained for a full understanding of the photoinduced mechanisms in metal complexes, supramolecular systems and nanostructures. Finally, the study of artist’s pigments in terms of non-invasive recognition, colour intensity and photostability is accomplished in collaboration with international museums and art galleries.

Synthesis and Functionalization of Nanomaterials for Drug Delivery. This line of research is focused on nanomaterials synthesis and implementation which are aimed to the development of controlled release carriers for bioactive principles. The activities concern the development of: i) synthesis methods both in batch and in flow of nanostructured drug delivery systems and their characterization; ii) bioactive substances encapsulation methods of various nature and application. The Spray Dry technique was applied for the synthesis of nano-carriers based on CaCO3, carriers based on nano-cellulose fibers and chitosan micro/nanocarriers. The surfaces of these carriers have been efficiently functionalized by grafting of human albumin (HSA) and fluorophores, phospholipid, polyethylene glycol and silanes coatings in order to improve stability, bioavailability, cellular uptake and targeting. Several synthetic and natural substances, anti-cancer drugs and antimicrobial agents, have been efficiently encapsulated. The application of the Ultrasonication process has allowed the achievement of nanometric drug colloids which are stable thanks to the contribution of suitable organic coatings such as chitosan, dextran and protamine. These nano-materials and deriving systems are widely characterized by chemical, morphological / structural and biological analyses.

Figures:

  1. Photophysics of artist’s pigment (Indian Yellow) for heritage science.
  2. Vertical and horizontal electronic coupling pathways in H-shaped Mixed Valence compounds.
  3. SEM/TEM images of: spray-dried chitosan carrier (top left); cis-Pt organic complex nanocolloid obtained in chitosan solution (top right); below, native (left) and APTES/HSA functionalized (right) CaCO3 nanocrystals.
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Graphene and 2D materials
Contact Persons: Giuseppe Valerio Bianco, Giovanni Bruno

Keywords: Chemical Vapor Deposition (CVD), Graphene Growth, 2D-CVD Growth, Plasma Processing, Raman Spectroscopy, Ellipsometry, Electrical Characterization, TMD Intercalation and Exfoliation

People: Giuseppe Valerio Bianco, Giovanni Bruno, Alberto Sacchetti, Maria Losurdo, Michelaria Giangregorio, Marco Grande, Anna Di Renzo, Luisa De Marco, Aurora Rizzo

The work on Graphene and related 2D layered materials in the APULIAN GRAPHENE LAB at CNR-NANOTEC Institute is addressed mainly to the development of methodologies of Production and Material Processing. We also develop simple devices for the assessment of the potential applications and for the validation of the materials properties.

Graphene Production is performed by CVD on copper, the CVD-graphene (large area growth up to 300 cm2), and by SiC sublimation, the Epitaxial-graphene (graphene on SiC wafer up to 1” diameter) on Si-face (mono and bilayer graphene) and on C-face (few layers graphene).

2D Layered Materials Synthesis. With an expertise of decades of research in the CVD technologies, we are working on the development of efficient processes for the growth of transition metal dichalcogenides (MoS2, WS2); the goal is the growth of single- and few- layer materials on graphene as well as on other epitaxial substrates (van der Waals growth) for the optoelectronic applications. We also manipulate single- and few-layer TMDs by mechanical exfoliation or molecules intercalation for nanophotonic and electro-optical devices.

Graphene Material Processing is on methodologies for graphene transferring on different substrates (glass, silicon and plastic) and on wet and dry procedures for doping and functionalization of single and multilayer graphene. Here, our expertise is on the plasma processing of graphene for chemical functionalization to produce graphane, fluorographene and graphene oxide, thus tailoring properties to explore new applications in optoelectronic, sensors, energy and biotechnology.

Graphene Characterization. Graphene-based materials are characterized and investigated at the nanoscale by optical spectroscopy (Raman, Ellipsometry) and electrical measurements (Van der Pauw, Hall).

The research activity at the Apulian Graphene Lab, have already achieved important breakthroughs within national and international. Examples are: the production of high quality graphene layers on large area with a sheet resistance lower than 20 Ω/cm and, reliable plasma-chemical methods designed for surface functionalization of graphene.

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Inorganic and Hybrid Semiconductors
Contact Persons: Aurora Rizzo, Luisa De Marco, Silvia Colella, Vittorianna Tasco, Adriana Passaseo

Keywords: Semiconductors, Perovskites, Nitrides, Gallium Arsenide

People: Francesco Bisconti, Vitantonio Valenzano, Gianluca Bravetti, Annalisa Coriolano, Nicola Taurisano Antonella Giuri, Luisa De Marco, Silvia Colella, Aurora Rizzo, Vittorianna Tasco, Iolena Tarantini, Massimo Cuscunà, Marco Esposito, Daniela Simeone, Adriana Passaseo

The applications of these materials range from photovoltaics, to photonics, sensors, and bio-technologies.
The main lines of research in this context are:

  1. Development of III-N and III-V heterostructures with epitaxial techniques;
  2. Inorganic and hybrid halide perovskites.

1. Development of III-N and III-V heterostructures with epitaxial techniques. We study the inorganic semiconductors of the GaAs and GaN families, realized by means of epitaxial techniques, such as Molecular Beam Epitaxy and Metal Organic Chemical Vapor Deposition, analyzing their optical, structural and electronic properties in view of their application in electronic and optoelectronic devices.

2. Halide perovskites have shown remarkable opto-electronic properties in recent years: a high coefficient of light absorption, efficient ambipolar transport of charges, high tolerance to defects, simple preparation from solution. This makes them ideal materials for a series of applications, starting from photovoltaics, to light emitting diodes, or ionizing radiation detectors. We study the fundamental properties of these materials and investigate their operating mechanisms within various types of devices. We also explore material development strategies by engineering the composition, ranging from hybrid (organic-inorganic) perovskites to completely inorganic perovskites.

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Colloidal inorganic nanocrystals
Contact Persons: Luigi Carbone, Concetta Nobile, Carlo Giansante, Marcella Dell’Aglio

Keywords: Colloidal Inorganic Nanocrystals, Heterostuctured Nanocrystals, Solvothermal/Hydrothermal Synthesis, Transmission Electron Microscopy (TEM), Scanning TEM, Energy-filtered TEM, Surface Chemistry, Coordination Chemistry, Photophysics, Pulsed Laser Ablation

People: Luigi Carbone, Carlo Giansante, Marcella Dell’Aglio, Alessandro De Giacomo, Concetta Nobile, Alessandra Quarta, Danila Quarta, Riccardo Scarfiello

The research area of Colloidal inorganic nanocrystals is organized according to the research headings, hereafter listed.

Colloidal Synthesis of Inorganic Nanostructures. The research activity aims at developing advanced breeds colloidal inorganic nanocrystals, as both single material and heterostructured, made of plasmonic, magnetic or semiconductor materials, with precisely engineered compositional, structural and geometric features and predictable chemical-physical properties. It focuses on the: i) development of synthesis protocols to solution-processable organic-capped nanocrystals; ii) investigation of nanocrystal formation mechanisms; iii) atomic-level compositional characterization of the developed nanocrystals; iv) study of the correlation holding between composition, structure and geometry of the as-synthesized nanocrystals, and their optical, magnetic and (photo)catalytic properties.

Morphological, Structural and Compositional Characterization of Colloidal Nanocrystals, Single and/or Assembled in Thin Film. This research activity supports the nanocrystal synthesis research line. Understanding of the structure-property correlation and its underlying mechanism is a fundamental step in the study of chemical-physical properties associated to nanostructured materials, either individual or organized in thin films. In this sense, the characterization of nanocrystal morphology, crystallographic structure and chemical composition is performed by means of advanced high – resolution electron microscopy techniques, such as HRSEM/TEM, ADF HRSTEM, EFTEM, XEDS.

Nanoscale Surfaces and Interfaces. The research program concerns the study of surfaces and interfaces at the nanoscopic size scale. To this aim, we use colloidal inorganic semiconductor nanocrystals as (soluble) frameworks and exploit their inherently large surface-to-volume ratio. Particular emphasis is put on the surface chemistry of colloidal nanocrystals as a mean to subtly tune their optoelectronic properties and the inter-nanocrystal non-covalent bonding interactions. We ultimately pursue a thorough description towards control of the ubiquitous interfaces in nanocrystal-based solids over multiple length scales.

Pulsed Laser Ablation in Liquids (PLAL). PLAL is a relatively simple process to produce nanoparticles (NPs) and nanostructures in a “clean” way without dangerous reactants or undesired contaminants, requiring no extreme conditions of the environment synthesis. A solid target is immersed in a liquid medium and the laser beam is focused through the liquid onto the target surface. The laser induced plasma and the further cavitation bubble generation lead to NPs formation. Naked NPs produced through this approach can be successfully employed in a wide range of application fields, taking advantages of their different surface reactivity (if compared to the surface of the coated-NPs produced by chemical methods).

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Complex fluids
Contact Persons:

Keywords: Liquid Crystals, Anisotropic Fluid Dynamics, Nanoparticles Self-Assembly

People: Riccardo Barbieri, Federica Ciuchi, Michele Giocondo, Bruno Zappone, Carlo C. Versace

Liquid crystals are versatile materials, with outstanding anisotropic properties which can be a model for turbulence, a guide for the self assembling of nanoparticles or quantum dots. The guided self assembling control can be applied to the development of miniaturized devices for the optics, photonics and microfluidics. Their birefringence and their optical properties allow the LC employment in technological applications such as displays, sensors, lasers, gratings.

A special class of liquid crystal are biocompatible and then can be used in biological sensing. Our work focuses on the Nanoconfinement of liquid crystals (LC) and anisotropic fluids dynamics and Defect pattern self-assembly and guided nanoparticle (NP) assembly in thin liquid crystal films.

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Sustainable chemistry
Contact Persons: Clara Piccirillo, Cinzia Citti, Francesco Matteucci, Ornella Ursini, Ivan Colantoni

Keywords: Green Materials, Natural Template, Waste Valorization, Metabolomics, Liquid Chromatography, Mass Spectrometry, Hemp, Cannabis, Cannabinoids, Photocatalysis, Environmental Remediation

People: Clara Piccirillo, Francesca Scalera, Cinzia Citti, Giuseppe Cannazza, Francesco Matteucci, Roberto Giannanotonio, Vincenzo Maiorano, Carlo Giansante, Luigi Carbone, Barbara Cortese

The research activities in the Sustainable chemistry area are organized according to the research lines, hereafter listed.

Green Chemistry Synthesis Approaches and Sustainable Processing Methods. This research line is focused on the development of materials and scaffolds following the principles of the green chemistry, for applications in biomedicine and environment remediation.
The themes explored are:

  • Synthesis of scaffolds for tissue engineering applications using natural and sustainable templates (i.e. cork).
  • Replacement of synthetic materials (i.e. carbon nanotubes) with more sustainable and natural ones.
  • Valorisation of the by-products of the agro-food industry, extraction of high added value compounds.

Environmental Nanotechnology has been defined as “the application of nanotechnology to environmental remediation technologies” (Env. Sci. Pollut. Res (2016), 23, 13754-788). This definition includes different processes (e.g. photocatalytic degradation, adsorption, thermal decomposition of pollutants) exploiting nanomaterials to remediate contaminated air, water or soil. We are focusing on main activities: the synthesis of photocatalysts with high chemical stability and photoactivity in the visible and UV spectral range (nanoTiO2, nanoWO3/WO3-x) for application in building and automotive industries, the chemico-physical characterization and the surface functionalization of nanomaterials in order to control the dispersibility and the adhesion to the substrates in photocatalytic reactors for wastewater treatment (Advanced Oxidation Processes) and to mediate the photocatalytic activity.

Development of Qualitative, Quantitative, and Metabolomic Analysis of Extracts from Plant Matrices and Biological Fluids. Metabolomics is a new analytical approach for the study of the chemical fingerprint that specific cellular metabolic processes left behind. Metabolomics can be applied to both plant and animal biological samples. The main goal is to identify and analyze as many small molecules (metabolites) as possible present in a biological sample. To this end, techniques like ultrahigh performance liquid chromatography coupled to high-resolution mass spectrometry (UHPLC-HRMS) are applied exploiting the latest technology platforms which enable to access key information about the chemical structure of the metabolites with a high degree of accuracy and precision reaching high sensitivity levels. The metabolomics analysis is accompanied by a multivariate statistical analysis for the characterization of the analyzed samples. This research line applies such technologies to different fields spanning industrial hemp, in vitro and in vivo pharmacokinetics/pharmacodynamics studies of organic compounds, loading efficiency and release kinetics of nano-encapsulated compounds.

Figures:

  • Left: S3D calcium phosphate scaffold made from mussel shells.
  • Center: Photocatalysis for environmental applications.
  • Right: Metabolomic analysis of plant extracts and of biological fluids.
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