Nanostructures & Self Assembling

Nanomaterials are coming into use in healthcare, electronics, cosmetics, catalysis and other areas, because they bring novel  mechanical, electrical, thermal, optical, electrochemical, catalytic properties differing markedly from that of the component materials.

Nanostructures are not simply another step in the miniaturization of materials. They often require very different production approaches. There are several processes to create nanomaterials, classified as ‘top-down’ and ‘bottom-up’., which are explored at Nanotec.

Self-Assembled Monolayers (layers that are one atom or molecule deep) are also routinely made and used in chemistry. The formation and properties of these layers need to be understood from the atomic level upwards, even in quite complex layers (such as lubricants). Advances are being made in the control of the composition and smoothness of surfaces, and the growth of films.

Furthermore, engineered surfaces with tailored properties such as large surface area or specific reactivity are used routinely in a range of applications such as in fuel cells, sensing and catalysts. The large surface area provided by nanoparticles, together with their ability to self assemble on a support surface, could be of use in all of these applications. Main topics in the focus are:

  1. Metallic Plasmonic Nanosystems
  2. Molecular Architectures at Interfaces
  3. High Charge Mobility Columnar Mesophases
  4. Organic/inorganic Nanocomposites
  5. Nanotextured Materials

Metallic Plasmonic Nanosystems

Research topics:

  1. Design, growth and investigation of plasmonic nanostructures coupled to semiconductors, ceramics, glass and plastics by MBE, thermal evaporation and plasma sputtering
  2. Synthesis of plasmonic systems alternative to nobel metals
  3. Design and synthesis of novel multifunctional multi-metallic core-shell nanoparticles supported on various substrates combining plasmonic/catalytic (e.g. Ag/Pd) and plasmonic/magnetic (e.g Au/Co) functionalities
  4. Development of Biochemical sensing exploting SERS mechanism
  5. Design of Enhanced light-matter interaction coupling semiconductors
  6. Tailoring of surface energy of support at the interface nanoparticle/substrate to tune nanoparticle shape and plasmonic response
  7. Post growth processing by annealing and plasmas to tailor optical and plasmonic properties
  8. Development of system for liquid and phase-change plasmonics
  9. Exploitation of plasmonics in localized catalysis

 

Molecular Architectures at Interfaces

The interfaces between bulk media are often site of reactions and phenomena which are distinct from the bulk substances and frequently dominate the macroscopic properties of the entire system. Understanding how molecules adsorb and react with these surfaces has potential applications in industrial processes and everyday life. Catalyses, combustions, lubrication, adhesion, wetting, electrochemical reactions are only few examples of phenomena of industrial interest which are governed by interfacial properties. Polymer surfaces and interfaces play an increasingly important role in modern electronic and optoelectronic technologies (i.e. organic transistors, OLED), as well as in biomedical applications (i.e., biocompatibility). Surface-specific IR and visible sum-frequency generation (SFG) vibrational spectroscopy is a powerful and versatile in situ surface probe which permits identification of surface molecular species and provides information about orientation of functional groups at the surface. SFG is non destructive, highly sensitive, and has good spatial, temporal, and spectral resolution. Because the technique works in real time under water and protein solutions it is also very well suited for studying biomaterials and biointerfaces.

A) In SFG experiment, pulsed VIS and IR laser beams overlapping at an interface produce a nonlinear polarization density and hence a coherent output beam at the sum frequency . B) Resonant enhancement and beams polarization dependence of the active vibrational modes of molecules provide orientation of the moieties and the molecular architecture at interface
A) In SFG experiment, pulsed VIS and IR laser beams overlapping at an interface produce a nonlinear polarization density and hence a coherent output beam at the sum frequency . B) Resonant enhancement and beams polarization dependence of the active vibrational modes of molecules provide orientation of the moieties and the molecular architecture at interface

High Charge Mobility Columnar Mesophases

Molecularly organized supramolecular materials are promising candidates for applications in organic opto-electronics since the properties of functional materials can be enhanced when they have a well-organized internal structure. Within this frame, the ability of liquid crystals to self-organize in mesophases to obtain functional architectures is frequently exploited and, in particular, the properties of columar liquid crystals are exploited since they are able to stack spontaneously into columns to give one-dimensional structures of π-conjugated organic molecules. This organization reflects in a long-range π-orbital overlap that allows, after suitable charge injection, intracolumnar charge carrier mobilities with high values comparable to those of amorphous silicon. These properties make columnar liquid crystals very attractive materials for use as organic semiconductors.

Strategies

Study and characterization of novel columnar liquid crystal based on innovative molecular and supramolecular architectures ;

Studies of discotic mesophases whit ambipolar electrical conductivity;

Development of high mobility columnar mesophases with suitable mechanical and physical properties for application in devices (OFET, Photovoltaics etc.)

Organic/inorganic  nanocomposites

Organic-inorganic nanocomposites consisting of metal or metal oxide nanoparticles embedded in an organic matrix combine unique properties offered by both organic and inorganic components on a nanoscale level and are, therefore, attractive materials for a large number of applications in the field of catalysis (e.g., Pt, ZnO, TiO2), sensing, optical filters, antibacterial metal (Ag, Cu) delivery systems, plasmonic devices.

Strategies

  1. One-step simultaneous metal sputtering and plasma polymerization from a suitable monomer forming the embedding matrix. This approach, carried out in reactor as TRIMAG is particularly appealing since it is possible to independently change the precursor of the matrix (CFx, CHx, SiOx,…) and the metal target (Au, Pt, Ag, …) producing different nano-composite coatings with tunable metal content.
  2. Nanocomposite coatings containing Metal oxide nanoparticles can be prepared in low pressure reactors as TRIMAG (link a TRIMAG in URT Facilities) using the oxide target or the metal one, in a O2 containing plasma.
  3. Inorganic nanoparticles/polymer nanocomposite coatings are prepared by an atmospheric pressure dielectric barrier discharge fed with the aerosol of a dispersion containing preformed NPs and the  precursor of the organic matrix.

Nanotextured materials

Plasma nanotexturing is a quite fast method to address biomimetic properties to simple raw materials such as polymer or glass.  It can be driven via bottom up approach or a top down one: in the first case the adsorbed precursors can organize in a hierarchical way leading to  a micro/nanotextured coating, in the latter subtractive etching, assisted by the random arrival of inhibitors,  leads to the formation of pillars. After nanotexturing, the chemistry of the surface can be tuned by a suitable plasma deposited coatings, to become more hydrophobic or hydrophilic or functionalized. Nanotextured surfaces give access to unique properties such as water and oil repellency, antireflectivity (moth eye effect), superhydrophilicity and anti-fog.

Strategies

  1. Nanotexturing of surfaces can be obtained by plasma rough etching of polymers with O2 fed plasma or in the case of silicon based materials (Si, SiO2 but even silicone) with fluorine producing plasmas
  2. transfer of a pattern produced by exposing a micro-featured (i.e. TEM copper grid) or nano-featured mask (i.e. colloidal lithography)
  3. deposition of teflon-like coatings in soft plasma conditions (i.e. modulated/pulsed discharges)
  4. aerosol-assited cold plasma deposition of nanocomposite coatings consisting of inorganic nanoparticles embedded in an organic matrix and showing hierarchical multiscale surface texture.

Facilities & Labs

NanoChem @ URT Bari

LyCril @ Rende (CS)

P.LAS.M.I. Lab @ Bari

People

Maria_LosurdoMaria

Losurdo

Director of Research CNR

Giovanni_BrunoGiovanni

Bruno

Associate Director of Research CNR

mariamichelgiangregorio_researcherMaria Michela

Giangregorio

CNR Researcher

giuseppevalerioBianco_researcherGiuseppe Valerio

Bianco

CNR Researcher

Fiorenza_FanelliFiorenza

Fanelli

CNR Researcher

Francesco FracassiFrancesco

Fracassi

Associate Professor

Eloisa_SardellaEloisa

Sardella

CNR Researcher

Federica_ciuchiFederica

Chiuchi

CNR Researcher

Pasquale_PagliusiPasquale

Pagliusi

Associate Professor

termineRoberto

Termine

CNR Research

fabio_palumbor150Fabio

Palumbo

CNR Researcher

Pietro-FaviaPietro

Favia

Associate Professor

Antonella MilellaAntonella

Milella

Associate Professor

Attilio_GolemmeAttilio

Golemme

Associate Professor

Viso_UomoAlessandro

Servidio

Associate PHD Student

Publications

  1. A. Aprile, F. Ciuchi, R. Pinalli, E. Dalcanale, P. Pagliusi, Probing Molecular Recognition at the Solid-Gas Interface by Sum-Frequency Vibrational Spectroscopy, Journal of Physical Chemistry Letters, 7, 3022-3026, (2016) DOI10.1021/acs.jpclett.6b01300
  2. Feringan, P. Romero, J. L. Serrano, C. L. Folcia, J. Etxebarria, J. Ortega, R. Termine, A. Golemme, R Gimenez, T Sierra, “H-Bonded Donor-Acceptor Units Segregated in Coaxial Columnar Assemblies: Toward High Mobility Ambipolar Organic SemiconductorsJournal of the American Chemical Society, 138, 12511-8, (2016) DOI:10.1021/jacs.6b06792
  3. Gracia, B. Fering_n, J. L. Serrano, R. Termine, A. Golemme, A. Omenat, J. Barberà, “Functional Carbazole Liquid-Crystal Block Codendrimers with Optical and Electronic PropertiesChemistry – a European Journal, 21, 1359-1369, (2015) DOI:10.1002/chem.201404555
  4. M. W. Knight, T. Coenen, Y. Yang, B. J.M. Brenny, M. Losurdo, A. S. Brown, H. O. Everitt, A. Polman, “Gallium Plasmonics: Deep Subwavelength Spectroscopic Imaging of Single and Interacting Gallium Nanoparticles” ACS Nano 9, 2049–2060 (2015) Doi:1021/nn5072254

Other selected publications:

  1. M. Losurdo, C. Yi, A. Suvorova, S. Rubanov, T.-H. Kim, M M Giangregorio, W Jiao, I. Bergmair, G. Bruno, A. S Brown, Demonstrating the Capability of the High-Performance Plasmonic Gallium-Graphene Couple, ACS Nano 02/2014; 8(3). DOI:10.1021/nn500472r
  2. Y. Yang, N. Akozbek, T.-H Kim, J. Marcos Sanz, F. Moreno, M. Losurdo, A. S. Brown, H. O. Everitt, “Ultraviolet-visible plasmonic properties of gallium nanoparticles investigated by variable angle spectroscopic and Mueller matrix ellipsometry”, ACS Photonics, 1, 582 (2014) DOI: 10.1021/ph500042v
  3. M. M.Giangregorio, B. Dastmalchi, A. Suvorova, G.V. Bianco, K. Hingerll, G. Bruno, M. Losurdo,Effect of Interface Energy and Electron Transfer on Shape, Plasmon resonance and SERS activity of Supported Surfactant-free Gold NanoparticlesRSC Adv., 4, 29660-29667 (2014) DOI: 10.1039/c4ra03749a
  4. M.M. Giangregorio, G.V. Bianco, P. Capezzuto, G. Bruno and M. Losurdo, “Surface plasmon resonance combined with spectroscopic ellipsometry read-out for probing surface–biomolecule interaction” Thin Solid Films, 571, 478-483 (2014) DOI: 10.1016/j.tsf.2013.11.143
  5. F. Fanelli, F. Fracassi Aerosol-Assisted Atmospheric Pressure Cold Plasma Deposition of Organic–Inorganic Nanocomposite Coatings, Plasma Chemistry and Plasma Processing, 34,  473-487 (2014) DOI: 10.1007/s11090-013-9518-9
  6. F. Fanelli, A. M. Mastrangelo, F. Fracassi, Aerosol-Assisted Atmospheric Cold Plasma Deposition and Characterization of Superhydrophobic Organic–Inorganic Nanocomposite Thin Films, Langmuir, 30, 857–865 (2014) doi: 10.1021/la404755n
  7. R. Di Mundo, R. d’Agostino, F. Palumbo, Long-Lasting Antifog Plasma Modification of Transparent Plastics, ACS Appl. Mater. Interfaces,  6, 17059–17066, (2014) doi: 10.1021/am504668s
  8. 10.A. Aprile, P. Pagliusi, F. Ciuchi, R. Pinalli, E. Dalcanale, Probing cavitand-organosilane hybrid bilayers via sum frequency vibrational spectroscopy, Langmuir 30, 12843 (2014) DOI: 10.1021/la503150z
  9. J. M. Sanz, D. Ortiz, R. Alcaraz de la Osa, J. M. Saiz, F. González, A. S. Brown, M. Losurdo, H. O. Everitt, and F. Moreno, UV Plasmonic Behavior of Various Metal Nanoparticles in the Nearand Far-Field Regimes: Geometry and Substrate Effects” J. Phys. Chem. C 117, 19606−19615 (2013). DOI: 10.1021/jp405773p
  10. T.W.H. Oates, M. Losurdo, S. Noda, K. Hinrichs, “The effect of atmospheric tarnishing on the optical and structural properties of silver nanoparticles” J. Phys. D: Appl. Phys. 46, 145308 (6pp) (2013) DOI: 10.1088/0022-3727/46/14/145308
  11. G.V. Bianco, M. Losurdo, M.M. Giangregorio, P. Capezzuto, G. Bruno, “Direct Fabrication Route to Plastic-supported Gold Nanoparticles for flexible NIR-SERS” Plasmonics 8, 159-165 (2013) DOI: 10.1007/s11468-012-9458-x
  12. Di Mundo, R.,  Palumbo, F., Barucca, G., Sabato, G., D’Agostino, R., On the “growth” of nano-structures on c-Silicon via self-masked plasma etching processes, Plasma Processes and Polymers, 10, 843-849 (2013), doi: 10.1002/ppap.201300031
  13. Sardella, E.,  Liuzzi, F.,  Comparelli, R.,  Depalo, N.,  Striccoli, M.,  Agostiano, A.,  Favia, P.,  Curri, M.L. Functionalized luminescent nanocrystals on patterned surfaces obtained by radio frequency glow discharges,   Nanotechnology ,24, 12 (2013) DOI:10.1002/ppap.200900112
  14. Bucos, T. Sierra, A. Golemme, R. Termine, J. Barbera, R. Gimenez, J. Luis Serrano, P. Romero, M. Marcos, “Multifunctional Supramolecular Dendrimers with an s-Triazine Ring as the Central Core: Liquid Crystalline, Fluorescence and Photoconductive Properties” Chemistry – a European Journal, 20, 10027-10037 (2014).
  15. Benito-Hernandez, U.K. Pandey, E. Cavero, R. Termine, E. M. Garcia-Frutos, J. L. Serrano, A. Golemme, B. Gomez-Lor, “High Hole Mobility in Triindole-Based Columnar phases: Removing the Bottleneck of Homogeneous Macroscopic Orientation”Chemistry of Material, 25, 117-121 (2013).
  16. Pérez, J. L. Serrano, T. Sierra, A. Ballesteros, D. de Saá, R. Termine, U. Kumar Pandey, A. Golemne,A Linear Conjugated Core for Multifunctional Columnar Liquid CrystalsNew Journal of Chemistry, 36, 830-842 (2012).
  17. C.Y. Chen, Wei-Tao Liu, P. Pagliusi, Y.R. Shen Sum-frequency vibrational spectroscopy study of photo-irradiated polymer surfaces Macromolecules 42, 2122-2126 (2009)
  18. P. Pagliusi, F. Lagugné-Labarthet, D.K. Shenoy, E. Dalcanale, Y.R. Shen Sensing vase-to-kite switching of cavitands by Sum-Frequency Vibrational Spectroscopy, Journal of the American Chemical Society 128, 12610-12611 (2006)
  19. P. Pagliusi, C.Y. Chen, Y.R. Shen, Molecular orientation and alignment of rubbed poly(vinyl cinnamate) surfaces, Journal of Chemical Physics 125, 201104 (2006)

Patents

Projects

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