Rencontres Jeunes du C'Nano GSO - à l'occasion de la remise du Prix de thèse du C'Nano Grand-Sud-Ouest
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Rencontres Jeunes du
C’Nano GSO
à l’occasion de la remise du
Prix de thèse du C’Nano Grand-Sud-Ouest
Lundi 21 juin 2021
Programme & Abstracts
C’Nano National Bureau C’Nano Grand-Sud-Ouest
Contact : cnano_com@cnrs.fr Contact : cnano_gso@cnrs.fr
Page internet : cnano.fr Page internet : cnano.fr/grand-sud-ouest
Twitter : @CNano_national Twitter : @CNano_gso
Date : lundi 21 juin (14h – 17h)
Format : visioconférence
PROGRAMME
Accueil et présentation du C’Nano
Conférence de Miguel MONGE-OROZ (Universidad de la Rioja)
« Gold-based nanostructures: nanoplasmonics for chemistry and (photo)catalysis »
Remise du Prix de thèse C’Nano Grand-Sud-Ouest 2020 à la lauréate :
Maria Letizia DE MARCO (Institut de Chimie de la Matière Condensée de Bordeaux, CNRS /
Université de Bordeaux) : « Supercritical Synthesis of Silicon Particles for Optical Metamaterials »
Présentations des jeunes du C’Nano Grand-Sud-Ouest
Haitham HRICH (L2C, Montpellier)
Basile BOUVET (ICGM, Montpellier)
Miquel CARDONA FARRENY (LCC, Toulouse)
Jordan GARO (IPREM-ICGM, Pau-Montpellier)
Diana KAZARYAN (LCPO, Bordeaux)
David TILVE MARTINEZ (CRPP, Bordeaux)
Domitille BAUX (L2C, Montpellier)
Sara AMAR (CRPP, Bordeaux)
Abstracts disponibles ci-dessous.
Abstract de
Maria Letizia DE MARCO
(Institut de Chimie de la Matière Condensée de Bordeaux,
CNRS / Université de Bordeaux)
Lauréate Prix de thèse C’Nano
Grand-Sud-Ouest 2020
First Name, Family Name: Maria Letizia DE MARCO
Employer, Laboratory: Université de Bordeaux, Institut de la Matière Condensée de Bordeaux
Thesis supervisor(s): Cyril AYMONIER & Glenna L. DRISKO
City: Bordeaux
Supercritical Synthesis of Silicon Particles for Optical Metamaterials
Optical Metamaterials are a class of artificial materials with unique optical properties, such as light cloaking,
total transmittivity and negative refraction. These extraordinary optical properties, which are not found in
natural materials, are obtained in metamaterials by a collection of resonant units -called meta-atoms- disposed
within a matrix. The meta-atoms are required to be small with respect the incident wavelength, and to have
strong scattering efficiency. Silicon spherical particles are the best candidate as meta-atoms in the visible range,
thanks to their intense scattering resonances stemming from their high refractive index. However, the lack of
efficient synthetic methods for monodisperse silicon spheres has hindered the realization of silicon-based
optical metamaterials. In my work, I developed a novel synthetic strategy for the realization of monodisperse
core-shell Si@SiOxNy, with controlled core size and shell thickness. The synthesis is carried out in supercritical
medium, which ensures the high temperature required for the nucleation and growth of Si particles. The shell
thickness and core size are varied by varying the relative concentration of two Si molecular precursors, the
trisilane and the silicon bis-amidinate. The optical properties of these core-shell particles were studied by
combining optical characterization and simulations of the scattering properties. We discovered that, thanks to
the presence of the SiOxNy shell, the two stronger scattering resonances -the magnetic and electric dipole
resonance- are coalesced, leading to total forward light scattering from the core-shell particles. This discovery
opens a feasible route for the fabrication silicon-based optical metamaterials characterized by a negative
refractive index, and metasurfaces having properties such as broadband total transmission in the visible
spectrum.
Keywords: Supercritical fluids, silicon, metamaterials
Abstracts des jeunes du C’Nano
Grand-Sud-Ouest
First Name, Family Name: Haitham HRICH
Title: PhD student 2nd year
Employer, Laboratory: Laboratoire Charles Coulomb (L2C-UMR 5221)
Thesis supervisor(s): Sylvie CONTRERAS and Périne LANDOIS
City: Montpellier
Toward monolayer graphene grown by sublimation on 4h-sic (0001) large terraces
It is well known that, at high temperature, silicon carbide (SiC) undergo a surface reconstruction. During this
phenomenon steps with different surface energies tend to be bunched together in order to minimize the total
surface energy i.e., step bunching. During epitaxial growth of graphene on 4H-SiC (0001), step bunching occurs,
until the buffer layer (BL) is formed. The influence of several factors on the width and height of steps have been
investigated. First, the miscut angle on steps formation have been studied by a combined optical alignment and
X-ray diffraction method. This method, which is unusual for SiC substrates, allowed us to reveal cut-off angles
inferior to 0.07° for our SiC wafers. Then, the effect of dihydrogen etching, on the width of steps formed during
graphene growth on 4H-SiC (0001) have been revealed. Large steps up to 20 μm have been observed using both
optical microscopy (MO) and atomic force microscopy (AFM). However, the Raman maps showed only BL on
our samples. In order to achieve the growth of monolayer graphene (1LG) an isotherm coupled with stopping
H2 right after have been used. A reproducible and controlled process, in Ar-H2 mix gases system, allowing a
homogeneous distribution of well-aligned steps up to 15 μm, has been achieved. Raman map in figure1 shows
that our samples are mostly covered with 1LG (up to 70% of the surface). The number of graphene layers were
estimated using the ratio of the integrated intensity of the G band of graphene on the integrated intensity of
the G band of a highly oriented pyrolytic graphite used as reference (AG-Gr/AG-HOPG).
Fig. 1. Raman analyses of a sample grown under Ar-H2 mix environment until 1500°C and then under full Ar environment. (a) 45 μm x
21 μm Raman map of the ratio of integrated intensity of the G-peak + Buffer Layer, in graphene from 1540 to 1640 cm-1, on the G peak
of a reference HOPG. (b) Average Raman spectra of more than 7000 (≈70% of the map) spectra corresponding to a ratio around 3.7%,
i.e., monolayer graphene.
Keywords: Graphene, Hydrogen Etching, Miscut Angle, Silicon Carbide, Step Bunching
First Name, Family Name: Basile BOUVET Title: PhD Student 1st year Employer, Laboratory: Département 1 – Institut Charles Gerhardt de Montpellier Thesis supervisor(s): Pr. Joulia LARIONOVA, Dr. Gautier FÉLIX City: Montpellier We design a core-shell nanostructure presenting a multifunctional system combining heating and thermometer functions. The heater consists in a magnetic core made of Fe3O4@SiO2 core@shell nanoparticles, able to generate an important temperature rise (up to 70 °C) under an applied alternating current magnetic field. A silica coating optimized method leads to obtain an uniform silica shell, which serves for a covalent anchoring of acetylacetonate groups. Those latter are able to chelate lanthanide (Ln3+) ions. This Ln3+complex (Ln3+ = Tb3+/Eu3+), works as a luminescent thermometer based on the luminescence intensity ratio (LIR) between Tb3+ green and Eu3+ red emissions. Temperature-dependence of the lanthanide emission presents an excellent linearity in the operating temperature range (25─70 °C) with a maximum relative thermal sensitivity. The luminescent nanothermometer offers in the same time a thermal- and a photo-stability and also presents reproducibility after several heating cycles. Therefore, this new multifunctional nanosystem has a potential for becoming a local thermometer of magnetic liquid induced hyperthermia. Keywords: Thermometry, Hyperthermia, Nanoplatforms, Multifunctional, Iron Oxide
First name, Family name: Miquel CARDONA FARRENY
Title: PhD student, 2nd year
Employer, Laboratory: Université Paul Sabatier, Laboratoire de Chimie de Coordination
Thesis supervisors: Rosa AXET and Karine PHILIPPOT
City: Toulouse
Biomass valorisation by bimetallic catalysts
Lignocellulosic biomass has appeared to be a promising feedstock for the production of sustainable chemicals
and fuels which may be compatible with the current combustion engines and chemically identical to the ones
obtained from petroleum. This biomass, containing cellulose, hemicelluloses and lignin, can be found in
agricultural residues, waste streams, wood and energy crops. From hemicelluloses and cellulose, furfural and
hydroxymethylfurfural (HMF), two platform molecules, can respectively be produced. Its hydrogenation
provides a plethora of interesting compounds such as methylfuran and 2,5-dimethylfuran, two potential
biofuels.1-3 Selective, efficient and cheap catalysts are needed for a future industrial implementation. Here, we
propose a family of bimetallic materials constituted by Ni or Cu, two earth-abundant metals, nanoalloyed with
Ru, a well-known metal for hydrogenations which increases their activity, selectivity and stability.4-5 Ultra-small
(First name, Family name: Jordan, Garo
Title: PhD student 2nd year
Employer, Laboratory: IPREM Pau and ICGM Montpellier
Thesis supervisors: Dr JM. SOTIROPOULOS and Dr K. MIQUEU (IPREM Pau ) / Pr F. SEREIN-SPIRAU (ICGM
Montpellier)
City: Montpellier
π-conjugated materials from biosourced precursors
for opto-electronic applications
Biomass origin molecules are potentially appropriate starting materials to achieve rapid multifunctional organic
targets that can be valued in several crucial and societal fields such as energy, people health and safety. Plants
resources provide suitable multifunctional and complex substructures that can be implemented in materials in
a wide range of low cost and weak carbon fingerprint devices like organic light emitting diode (OLEDs), field
effect transistors (OFETs), organic photovoltaic cells (OPVs), analytes ultra-traces sensors and thermo- and
electrochromic devices[1–3].
For these applications, suitable materials will be designed by organic π-conjugated sequences resulting
from electrons acceptor units (A) characterized by a low LUMO level linked to electrons donor units (D)
associated to a high HOMO level. Among easily available and suitable raw materials vanillin derivatives can be
used as the donor subunit and in order to elaborate more extended conjugation systems the intramolecular
Diels-Alder reaction will be investigated in the presence of an acceptor unit (A) (Figure).
In this work, first DFT calculations were performed to determine the relative levels of the frontier
orbitals of the donor and of the acceptor building blocks and the impact of the substituents of the A/D units on
the feasibility of the Diels-Alder reaction (activation barriers). Secondly, in the most favorable cases this [4+2]
cycloaddition will be investigated to synthesize new and original π-conjugated compounds up to 80%.
References:
1. F. B. Dias, K. N. Bourdakos, V. Jankus, Adv. Mater. 2013, 25, 3707–3714.
2. Z. Su, W. Li, B. Chu, J. Phys. D: Appl. Phys. 2008, 41, 085103.
3. O. Ostroverkhova, Chemical Reviews. 2016, 116, 13279–13412.
Mots-clefs : Energy, biosourced raw materials, DFT, organic synthesisFirst Name, Family Name: Diana KAZARYAN
Title: 2nd year PhD student
Employer, Laboratory: CNRS, LCPO
Thesis supervisor(s): Dr. Olivier SANDRE, Dr. Frédéric PERUCH
City: Bordeaux
Biological cell killing induced by anisotropic magnetic polymersome rotation under
low frequency alternating magnetic field
This project aims at combining the properties of polymersomes as drug delivery systems as well as the magnetic
properties of superparamagnetic iron oxide nanoparticles (SPIONS) in order to force mechanical disruption of
cell membranes, under the application of a low frequency magnetic field (LF), inducing cell death. Amphiphilic
diblock copolymers and SPIONS are utilized for the synthesis of anisotropic magnetic polymersomes. The
SPIONS are embedded in the hydrophobic membrane and are capable of inducing morphological changes of
the polymersomes, under the application of a static magnetic field, by aggregating in a straight line and forcing
a deformation which results in anisotropic nanoparticles. Permanent deformation will be induced by UV cross-
linking of the hydrophobic membrane while under the magnetic field. Such “ellipsoid” like polymersomes will
be introduced into cells at a higher rate than isotropic polymersomes. Finally cell death will be accomplished by
application of a LF magnetic field, forcing the polymersomes to rotate with a magnetic torque and distort cell
membranes, resulting in cell death. This presentation will cover the physicochemical study that was necessary
to prepare the “bricks” of the designed nanocomposite system, together with preliminary results of cell
internalization and toxicity. The latest developments of the project are showcased on its website:
www.lcpo.fr/anr-maverick.
Keywords: amphiphilic diblock copolymer synthesis; poly(isoprene); poly(trimethylene carbonate); poly (ethylene oxide);
cross-linking; iron oxide nanoparticles; polymer grafting onto nanoparticles; transmission electron microscopy.First Name, Family Name: David TILVE MARTINEZ
Title: PhD 1st
Employer, Laboratory: Centre de recherche Paul Pascal – CNRS Univ. Bordeaux
Thesis supervisor(s): Philippe POULIN
City: Bordeaux
3D printing of conductive nanocarbon based composites
3D Printing offers new opportunities for the manufacturing of objects in a variety of fields. In the so-called
Digital Light Processing technology (DLP), the object is printed layer-by-layer via the projection of 2D light
patterns onto a photocurable resin. Generally, such resins are transparent and electrically insulating. Printing
conductive materials loaded with nanocarbon particles, including nanotubes or graphene, would significantly
broaden the spectrum of applications of the DLP technology. However, several challenges are faced towards
this objective. First of all, a special attention has to be paid to the dispersion and stabilization of nanoparticles
in the resin materials. Second, it becomes critical to understand and control how the presence of the particles
affect the rheological and optical properties of the photocurable inks. We will present in this work first
attempts for the realization of 3D printed materials made of nanocarbon based composites. We will show the
efficient dispersion of nanoparticles and their DLP printing in different conditions. The electrical properties of
the composites will also be shown and discussed.
Keywords: 3D printing, nanocarbon, nanotubes, graphenePrénom, NOM : Domitille BAUX
Statut : Doctorante en 1ère année
Employeur, Laboratoire : Université de Montpellier, Laboratoire Charles Coulomb
Encadrant.e.s de thèse : Nicolas IZARD, Emmanuel ROUSSEAU
Ville : Montpellier
Nanotubes de carbone métalliques pour des applications en plasmonique
Les nanotubes de carbone sont des objets nanométriques unidimensionnels qui peuvent présenter un caractère
métallique ou semi-conducteur selon leur géométrie. A l’échelle nanométrique, les nanotubes de carbone ont
une conductivité électrique comparable à celle de métaux macroscopiques.[1,2] Les nanotubes métalliques
apparaissent alors comme des candidats idéaux pour des applications en plasmonique (effet d’antenne
plasmonique, exaltation de la luminescence d’un émetteur).
Leurs propriétés optiques sont connues pour des mélanges de nanotubes de carbone métalliques et semi-
conducteurs. Néanmoins, il n’existe ni mesures expérimentales des constantes diélectriques aux fréquences
optiques (et/ou proche infrarouge) de nanotubes de carbone métalliques ni calculs numériques de DFT incluant
les transitions intra-bandes dans la littérature.
Nos mesures des propriétés optiques de nanotubes de carbone triés métalliques et semi-conducteurs reposent
sur des expériences de réflectance/transmittance (dans le proche et moyen infrarouge) de films de nanotubes
de carbone métalliques déposés sur substrat. Je présenterai une procédure permettant de remonter à l’indice
de réfraction de nanotubes de carbone métalliques à partir de données expérimentales via l’exploitation de
relations de Kramers-Kronig.
Références
1. Seunghun Hong and Sung Myung. A flexible approach to mobility. Nature Nanotechno-logy, 2(4) :207–208, April 2007
2. HONGJIEDAI, ALIJAVEY, ERICPOP, DAVIDMANN, WOONGKIM, and YUERUI LU. Electrical transport properties and field effect
transistors of carbon nanotubes. Nano, 01(01) :1–13, July 2006
Mots-clefs : nanotubes de carbone métalliques, plasmonique, indice de réfraction, relations de Kramers-KronigFirst Name, Family Name: Sara AMAR
Title: PhD student
Employer, Laboratory: Centre de recherche Paul Pascal – CNRS Univ. Bordeaux
Thesis supervisor(s): Alain PENICAUD and Alain DERRÉ
City: Pessac
Zeolite-Templated Carbon: a Promising Material for Supercapacitors
Chemical vapor infiltration (CVI) of a hydrocarbon in a molecular sieve is a synthesis technique used to generate
a crystalline structure of carbon that remains up to now purely theoretical: Schwarzite [1-2]. This structure has
indeed been foreseen as a promising material to manufacture electrodes for supercapacitors. Nonetheless,
many technological challenges still have to be overcome in order to make this synthesis technique more
accessible [1].
The molecular sieve that was selected for this study is zeolite, for its extraordinary adsoption properties. Zeolite
is used as a template: the aim is to replicate its structure by infiltrating carbon atoms inside the nanopores [3].
The idea is to obtain, after zeolite dissolution by means of hydrofluoric acid treatment, a material that is
exclusively composed of carbon, with a 3D porosity network consisting of nano-sized pores and thus displaying
a high specific surface (see figure1).
SEM observation shows that the obtained material has a very similar structure to that of the initial zeolite (see
figure 2) which augurs well for the successful replication of the zeolite structure.
Therefore, the presentation will focus on the synthesis and characterization of these materials, using
thermogravimetric analysis, X-Ray diffraction, Raman, etc.
Fig. 1 : Schematic Zeolite-Templated Carbon (ZTC) Synthesis [3] Fig. 2 : SEM image of carbon material obtained after zeolite
dissolution with hydrofluoric acid
References
[1] : E. Braun, Y. Leeb, S. M. Moosavib, S. Barthelb, R. Mercadod, I. A. Baburine, D. M. Proserpiof,g, and B. Smit, Generating carbon
schwarzites via zeolite-templating, E8116–E8124 | PNAS | vol. 115 | no. 35
[2] : M. Tagami, Y. Liang, H. Naito, Y. Kawazoe, M. Kotani, Negatively curved cubic carbon crystals with octahedral symmetry, Carbon 76,
2014, 266-27
[3]: H. Nishihara and T. Kyotani, Zeolite-templated carbons – three-dimensional microporous graphene frameworks, Chem. Commun.,
2018, 54, 5648
Keywords: Zeolite-Templated Carbon, Supercapacitor, Chemical Vapor Infiltration, porous materialsAbstract de Miguel MONGE-OROZ
Universidad de la RiojaFirst Name, Family Name: Miguel MONGE
Title: Associate Professor
Employer, Laboratory: University of La Rioja (SPAIN)
City: Logroño
Gold-based nanostructures: nanoplasmonics for chemistry and (photo)catalysis
Well-defined nanostructures with controlled size, shape, composition and surface state are needed for
an in-depth study of their properties and the development of applications. The combination of organometallic
chemistry with soft chemistry or materials chemistry constitute interesting approaches for the design of
nanohybrid systems. In such cases, the presence of gold and silver nanostructures provides interesting
plasmonic properties as, for instance, photothermal heating, optical near field effect or hot-electron injection.[1]
When plasmonic nanostructures form heterojunctions with semiconductors, novel and efficient photocatalysts
can be designed. In addition, when gold and silver nanoparticles are purposefully aggregated at the surface of
nanodroplets or within a polymeric matrix, a plasmonic coupling takes place leading to broadband absorbance
materials with very efficient light-to-thermal energy conversion abilities that, in some cases, promote
interesting chemical reactions like H2 evolution from NH3-BH3 complex.
In this communication some novel gold-based plasmonic nanohybrids are shown, namely: (i) bimetallic
Au-Ag nanorods that can be heated up to 130 ºC by low power NIR LED light irradiation;[2] (ii) Au colloidosomes
formed at the surface of oleic acid nanodroplets that display stimuli-responsive properties;[3] (iii) polymer
stabilized Au-Ag nanoparticles grafted on TiO2 nanoparticles and reduced graphene-oxide nanosheets for
photocatalytic removal of pollutants[4] and (iv) Au-Ag NPs grafted on carbon nitride nanosheets for
photocatalytic depletion of persistent antibiotic ciprofloxacin.
Figure 1. Au-Ag nanorods stabilized with glutathione (left); Au colloidosome with an urchin-like shape (middle) and Au-Ag nanoparticle
at the surface of a TiO2 nanoparticle.
[1] I. F. Teixeira, E. C. M. Barbosa, S. C. E. Tsang, P. H. C. Camargo, Chem. Soc. Rev., 2018, 47, 7783-7817.
[2] J. Crespo, J. M. López-de-Luzuriaga, M. Monge, M. Elena Olmos, M. Rodríguez-Castillo, B. Cormary, K. Soulantica, M. Sestu and A.
Falqui, Chem. Commun., 2015, 51, 16691–16694.
[3] J. M. López-de-Luzuriaga, M. Monge, J. Quintana, M. Rodríguez-Castillo, Nanoscale Adv., 2021, 3, 198-205.
[4] H. Atout, A. Bouguettoucha, D. Chebli, J. Crespo, J.-C. Dupin, J. M. López-de-Luzuriaga, H. Martínez, M. Monge, M. E. Olmos, M.
Rodríguez-Castillo, New J. Chem., 2021. DOI: 10.1039/D1NJ01879E.
Keywords: gold; silver; nanostrcutures; plasmonics, photothermal effectYou can also read
