Nanostructures 2015-2018

Scientific report 2015-2018

PSC : Physics and Confined System

In this document, you will find some short summary of the different achievements and up-going research developed within the following axes :

Sub-axes :

- Nanostructures - Surfaces, Interfaces - Ultrafast Phenomena

These researches are conducted within the three teams NNM (NanoMagnetism and Modeling), PIMS (Physics of Interfaces and Structured Materials), NOVA (NanoOptics, Vibrations, and Acoustics).

Nanostructures 2015-2018

1-Nanostructure influence on magnetic properties PSC group axes: Nanostructures

Researchers: N.Yaacoub, J-M. Grenèche, Y.Labaye, F.Calvayrac, R.Busselez

❖ Exploring the Magnetic Disorder in Ultrathin Iron Oxide Hollow Nanoparticles

Abstract: Magnetic nanoparticles are of special interest in the field of storage information and nanomedicine (hyperthermia, medical imagery, …). Due to the nanometric size of the particles they can be guided using a magnetic field. Unfortunately, reducing the size of the nanomagnets leads to magnetic instability incompatible to technological applications. Modifying the shape of the nanoparticles (core-shell particles, Hollow particles, …) lead to an exaltation of surface/interface effects and an

Figure 1: Properties of Hollow magnetic nanoparticle.

enhancement of the magnetic anisotropy and the apparition of dynamical effect (superparamagnetic). As an example, by use of in-field Mössbauer spectrometry, we have shown the existence of complex non-collinear magnetic structure in iron oxide hollow nanoparticles. Indeed, this structure consists in a ferrimagnetic layer of few atomic planes confined between two layers with canted structure resulting from two antiferromagnetic coupled speromagnetic structures. Such a magnetic structure leads to an increase of the magnetic coupling between the interfacial moments of the magnetic phases. The exchange bias coupling finally tends to increase the magnetic anisotropy of the nanoparticles and in definitive the magnetic stability of the nanostructure.

Projects: ANR Obnarem, Pics France-Italie

Related papers:

● F. Sayed, N. Yaacoub, Y. Labaye, R. S. Hassan, G. Singh, P. A. Kumar, J. M. Greneche, R. Mathieu, G. C. Hadjipanayis, E. Agostinelli and D. Peddis, Surface Effects in Ultrathin Iron Oxide Hollow Nanoparticles: Exploring Magnetic Disorder at the Nanoscale, J. Phys. Chem. C, 2018, 122, 7516–7524.

● G. Muscas, N. Yaacoub, G. Concas, F. Sayed, R. Sayed Hassan, J. M. Greneche, C. Cannas, A.

Musinu, V. Foglietti, S. Casciardi, C. Sangregorio and D. Peddis, Evolution of the magnetic structure with chemical composition in spinel iron oxide nanoparticles, Nanoscale, 2015, 7, 13576–13585.

● T. Gaudisson, R. Sayed-Hassan, N. Yaacoub, G. Franceschin, S. Nowak, J.-M. Grenèche, N.

Menguy, P. Sainctavit and S. Ammar, On the exact crystal structure of exchange-biased Fe 3 O 4 –CoO nanoaggregates produced by seed-mediated growth in polyol, CrystEngComm, 2016, 18, 3799–3807.

● F. Sayed, Y. Labaye, R. Sayed Hassan, F. El Haj Hassan, N. Yaacoub and J. M. Greneche, Size and thickness effect on magnetic structures of maghemite hollow magnetic nanoparticles, Journal of Nanoparticle Research, 2016, 18, 279.

● Y. Prado, N. Daffé, A. Michel, T. Georgelin, N. Yaacoub, J.-M. Grenèche, F. Choueikani, E. Otero, P. Ohresser, M.-A. Arrio, C. Cartier-dit-Moulin, P. Sainctavit, B. Fleury, V. Dupuis, L. Lisnard and J. Fresnais, Enhancing the magnetic anisotropy of maghemite nanoparticles via the surface coordination of molecular complexes, Nature Communications, 2015, 6, 10139.

❖ Spin disorder versus Exchange bias coupling in magnetic nanoparticles with complex architecture (Hollow, shell/shell, …)

Abstract: An important relevant features of the size effect in magnetic nanoparticles

(NPs) is the occurrence of non-collinear spin structures (spin canting, magnetic

frustration, spin disorder). Indeed, the non-collinear spin structures could strongly

modify the magnetic properties of the magnetic NPs, for example as it was shown

recently by us which found a strong correlation between complex spin disorder and

exchange bias (EB) features in iron oxide hollow NPs. Although the macroscopic model

of EB effect existed for nearly six decades, the microscopic origin of this phenomenon is

still requiring further investigation in some specific systems at nanoscales. Even in the

case of very well-studied and investigated nanomaterials such as spinel ferrites, a full

understanding of the correlation between spin structure, surface/interface effect and EB

coupling is still lacking. In this context, we propose to investigate this phenomenon in

systems presenting high spin disorder like Hollow NPs with different sizes and shell thickness and extended this study to a system of shell/shell that consists of two magnetic phases: a ferrimagnetic phase and an antiferromagnetic one. The idea is to discriminate the EB resulting from surface spin disorder from that resulting from spins interface coupling between two different magnetic phases. Figure below show the Mössbauer spectra for hollow (g-Fe2O4) and shell/shell (g-Fe2O4/NiO) NPs with same external diameter and thickness (15 nm and 7.5 nm). As a preliminary result, we observe that the spin disorder is bigger in the shell/shell than in the hollow one. On the other hand the EB observed in shell/shell NPs is bigger than that observed in hollow NPs. This raises the question about the effect of the antiferromagnetic phase on the spin disorder and the EB coupling in this kind of nanoscale systems ? Finally, In order to avoid the effect of dipolar interaction and study its effects on spin disorder and EB we propose to disperse these systems in non magnetic matrix.

-12 -6 0 6 12

0.92 0.97

1.01 measured at 11 K, 8 T

Hollow γ-Fe2O3

relative transmission

V [mm/s] 0.95-12 -6 0 6 12

0.97 0.99

1.01 measured at 11 K, 8 T

Hollow γ-Fe2O3/NiO

relative transmission

V [mm/s]

Figure 2: In-field Mössbauer spectra of magnetic NPs with different architectures: γ-Fe2O3, (hollow) and γ- Fe2O3/NiO (Shell/shell)

❖ Classical Magnetic models: towards a multi-scale approach

Abstract: Phenomenological magnetic models are able to bridge a gap between the microscopic magnetic properties and local organization of magnetic sites from a first part and the overall magnetic properties of bulk or nanosized materials from a second part.

Figure 3: Left: Influence of dopamine functionalization on magnetic properties. Right:

Influence of structure relaxation on magnetic properties

In the case of Heisenberg model, the magnetic Hamiltonian is governed by few critical parameters, namely the magnetic moments of sites, the exchange energy between neighbors, the volume anisotropy constant and for finite size objects, the surface anisotropy constant and interface anisotropy constants.

Accuracy of the results emerging from the classical model is then intimately related to the theoretical or experimental determination of the underlying magnetic parameters and microscopic site organization of the system. This level of knowledge is not necessarily fulfilled in the case of complex structures or unusual compounds. Using a numeric multi-scale approach coupling ab-initio, molecular dynamics and Heisenberg simulations, access to a finer level of description. From one part the use of molecular dynamics simulation, permits to relax the structure of nano-sized or bulk systems and then to reproduce the magnetic sites position and distribution in a more realistic way.

From another side, adjustments of ab-initio calculations and Heisenberg model on a large statistical sample of representative local environments allow us to determine the microscopic magnetic parameters.

Project: ANR Obnarem Related Papers:

● K. Brymora and F. Calvayrac, Surface anisotropy of iron oxide nanoparticles and slabs from first principles: Influence of coatings and ligands as a test of the Heisenberg model, Journal of Magnetism and Magnetic Materials, 2017, 434, 14–22.

● F. Sayed, Y. Labaye, R. Sayed Hassan, F. El Haj Hassan, N. Yaacoub and J. M. Greneche, Size and thickness effect on magnetic structures of maghemite hollow magnetic nanoparticles, Journal of Nanoparticle Research, 2016, 18, 279.

● Z. Nehme, Y. Labaye, R. Sayed Hassan, N. Yaacoub and J. M. Greneche, Modeling of hysteresis loops by Monte Carlo simulation, AIP Advances, 2015, 5, 127124.

2- Tayloring of magnetic and multiferroic phases PSC group axes: Nanostructures

Researchers: N.Randriantonandro, F.Calvayrac

❖ Rare Earth free permanent magnets

Abstract: Among currently investigated rare-earth-free magnets, ferromagnetic τ-MnAl is a potential candidate having promising intrinsic magnetic properties. Mn(Fe)AlC was synthesized by mechanical alloying method. Effects of carbon on microstructure and magnetic properties were systematically investigated. It was found that high purity of τ- MnAl(C) could be obtained at 2 at.% C doping, showing clearly stabilizing effect of carbon. Mn

Al

C

has the best magnetic properties: magnetization at 2T M2T = 414 kA.m

, remanent magnetization M

= 237 kA.m

, coercivity H

= 229 k.Am

, and |BH|

= 11.2 kJ.m

. HC increased inversely with the crystallite size of τ phase and proportionally with C content. Moreover, first principle calculation showed both stabilizing effect and preferable interstitial positions of carbon in tetragonal τ-MnAl.

Mn

Fe

Al

C

(x= 0.25, 0.5, 1, 2, 4, 6) alloys were also synthesized by mechanical

alloying method, showing the high purity of τ phase up to 2 at.% Fe doping. Adding of Fe

on MnAl(C) reduced both magnetization and T

but likely increased slightly H

. 57Fe

Mössbauer spectrometry at 300K was used to probe local environment in ε-, τ-, β-, and

γ

-MnFeAl(C). In which, γ

-, ε-, and β-MnFeAl(C) exhibited a quadrupolar structure

while τ -Mn

Fe

Al

C

spectrum showed a rather complex magnetic hyperfine splitting. The interaction between Fe and Mn examined by in-field Mössbauer measurement at 10 K and 8 T showed a non-collinear magnetic structure between Fe and Mn with different canting angles at different sites. Hyperfine field of MnFeAl alloy calculated by Wien2k supported both magnetic properties and Mössbauer results.

Figure 4: Changes in magnetic moment with substitution. Mössbauer spectra showing ferrimagnetic order.

Magnetization curve of substituted phases

Related paper:

● V. Tang Nguyen, F. Calvayrac, A. Bajorek and N. Randrianantoandro, Mechanical alloying and theoretical studies of MnAl(C) magnets, Journal of Magnetism and Magnetic Materials, 2018, 462, 96–104

❖ Multiferroic Materials

Abstract: Multiferroic materials constitute a class of multifunctional materials presenting in the same time coupled properties in terms of ferromagnetic-ferroelectric and ferroelastic order. On a fundamental scale, the nature of the interactions and in particular the magnetoelastic coupling mechanism is not fully understood despite the amount of experiments. On a technological level, this class of material is interesting in the field of information storage or for microelectromechanical systems development.

Among multiferroic materials, BiFeO

is one is one of the few which presents in the same time both ferroelectric and magnetic order above 300K. However despite this unique property, BiFeO

also presents a magnetic helicoïdal structure of Fe

magnetic moments, this magnetic structure leads to weak magnetoelectric coupling. A drastic increase of magnetoelectric coupling can be obtained through the breakdown of helicoïdal spirale and the formation of an antiferromagnetic linear structure of type G leading to a non-zero mean magnetization.

Multiples ways can be followed to breakdown this helicoidal structure among them:

1. Reducing the size of the material dimension to a value lower than the cycloid period (~64 nm). This can be obtained by a polyol method for synthetizing BiFeO

nanoparticles.

2. Substituting Bi

and Fe

by Ti

and Zr

using a ceramic synthesis in order to partially break helicoïdal structure of Fe

magnetic moments

Equi-atomic -MnAl

-Mn1+xAl1-x

Fe doped Mn1+xAl1-x

Figure 5: Left: MEB picture of BiFeO3 particles obtained with polyol process. Right: Modification of helicoïdal magnetic order and apparition of ferromagnetic order

Surfaces, Interfaces

1. Plasmonics and Enhanced Vibrational Spectroscopies PSC axe: Surfaces et Interfaces Fonctionnelles

Researchers: Jean-François Bardeau, Alain Bulou, Philippe Daniel, Nicolas Delorme, Mathieu Edely, Nicolas Errien, Alain Gibaud, Fabienne Lagarde, Marc Lamy de La Chapelle.

Abstract:

The metallic nanoparticles or nanostructures can strongly interact with light.

They can provide some huge enhancement of the near field at the vicinity of the metallic surface due to the excitation of the localised surface plasmon (LSP). The plasmonic properties depend on geometrical parameters (size, shape, coupling...) of the nanopatterned metals and can be finely controlled and tuned on a wide range of wavelength.

v Field enhacement and SERS optimization

We work on the relation between the LSP and the enhancement efficiency depending on

the geometrical parameters of the dedicated nanostructures. We notably determine the

influence of the LSP on the surface enhanced Raman scattering (SERS).

Moreover, in the team, we developed strong skills in the structuration of metallic surfaces at micro/nanoscales to create nanostructured substrates for highly sensitive SERS applications.

Projets: ANR NanoBiosensor, ANR Louise, ANR Piranex Publication(s), book chapter(s), patent(s):

•

Technol. 2018, 1800134 - DOI: 10.1002/admt.201800134

• N. Quilis, M. Lequeux, P. Venugopalan, I. Khan, W. Knoll, S. Boujday, M. Lamy de la Chapelle, J. Dostalek, Tunable laser interference lithography preparation of plasmonic nanoparticle arrays tailored for SERS, Nanoscale, 10, 10268, 2018

• R. Gillibert, F. Colas, R. Yasukuni, G. Picardi, M. Lamy de la Chapelle, Plasmonic Properties of Aluminium Nanocylinders in the Visible Range, J. Phys. Chem. C 121(4), 2402, 2017

• R. Gillibert, T. Tafer, M. Lamy de la Chapelle, Strong coupling between localized surface plasmon and Bragg mode on aluminium nanocylinders grating deposited on aluminium film, Physica Status Solidi a, 214(8), 1600793, 2017

• F. Colas, M. Cottat, R. Gillibert, N. Guillot, N. Djaker, N. Lidgi-Guigui, T. Toury, D. Barchiesi, A.

Toma, E. Di Fabrizio, P. G. Gucciardi, M. Lamy de la Chapelle, Red-Shift Effects in Surface Enhanced Raman Spectroscopy: Spectral or Intensity Dependence of the Near-Field?, J. Phys.

Chem. C120 (25), 13675, 2016

• R. Gillibert, M. Sarkar, J. F. Bryche, R. Yasukuni, J. Moreau, M. Besbes, G. Barbillon, P. Gogol, B, Bartenlian, M. Canva, M. Lamy de la Chapelle, Directional Surface Enhanced Raman Scattering on gold nano-gratings, Nanotechnology 27/11, 115202, 2016

• R. Gillibert, M. Sarkar, J. Moreau, M. Besbes, M. Canva, M. Lamy de la Chapelle, Near Field Enhancement Localization on Plasmonic Gratings, J. Phys. Chem. C 120 (48), 27562, 2016

• J. F. Bryche, R. Gillibert, G. Barbillon, P. Gogol, J. Moreau, M. Lamy de la Chapelle, B.

Bartenlian, M. Canva, Plasmonic enhancement by a continuous gold underlayer: application to SERS sensing, Plasmonics, 11/2, 601, 2016

• J. F. Bryche, A. Tsigara, B. Bélier, M. Lamy de la Chapelle, M. Canva, B. Bartenlian, G.

Barbillon, Surface enhanced Raman scattering improvement of gold triangular nanoprisms by a gold reflective underlayer for chemical sensing, Sensor and actuator B, 228, 31, 2016

• Patent: Procédé de Fabrication d’un motif métallique nanostructuré et motif métallique- Inventeurs : M. Edely, N. Delorme, J.-F. Bardeau (2014 - N° de dépôt : 1461880)

v Molecular plasmonics and thermoplasmonics

The plasmonic properties of metallic nanostructures can induced side effects such as local increase of the temperature, known as thermoplasmonics effect, or the formation of hot electrons that can react with molecules. We study and exploit such properties. For instance, we demonstrated that some chemical reaction, such as the click chemistry, can be initiated and mediated by the plasmon or that large temperatures can be reached at the nanostructure surface to heat the local medium.

Projets: X-TREM

Publication(s), book chapter(s), patent(s):

• Tijunelyte, E. Guenin, N. Lidgi-Guigui, F. Colas, J. Ibrahim, T. Toury, M. Lamy de la Chapelle, Nanoplasmonics tuned “click chemistry”, Nanoscale, 7/13, 7105, 2016

• S. Betelu, I. Tijunelyte, L. Boubekeur-Lecaque, I. Ignatiadis, J. Ibrahim, S. Gaboreau, C. Berho, T.

Toury, E. Guenin, N. Lidgi-Guigui, N. Félidj, E. Rinnert, Marc Lamy de la Chapelle, Evidence of the Grafting Mechanisms of Diazonium Salts on Gold Nanostructures, J. Phys. Chem. C, 120 (32), 18158, 2016

• G. Picardi, F. Colas, R. Gillibert, M. Lamy de la Chapelle, Spectral Shift of the Plasmon Resonance between the Optical Extinction and Absorption of Gold and Aluminum Nanodisks, J. Phys. Chem. C, 120 (45), 26025, 2016

• Tijunelyte, I. Kherbouche, S. Gam-Derouich, M. Nguyen, N. Lidgi-Guigui, M. Lamy de la Chapelle, A. Lamouri, G. Levi, J. Aubard, A. Chevillot-Biraud, C. Mangeney, N. Felidj, Multi- functionalization of lithographically designed gold nanodisks by plasmon-mediated reduction of aryl diazonium salts, Nanoscale Horizon, 3, 53, 2018

v Plasmonic applications in sensing

The field enhancement can be exploited for large enhancement of the spectroscopical signal of any molecules located at the vicinity of the nanoparticle surface. It is then possible to detect molecular species at low concentration and provide high sensitivity to the detection. Thus, several projects were devoted to the enhancement of Raman signal (SERS) allowing the detection and analysis of molecules in very small concentrations.

Most applications are turned towards the detection of biomolecules in medecine,

pollutants in environment, contaminants and micro-organisms in food.

Projets:

Publication(s), book chapter(s), patent(s):

• R. Gillibert, M. Triba, Marc Lamy de la Chapelle, Surface Enhanced Raman Scattering Sensor for Highly Sensitive and Selective Detection of Ochratoxin A, Analyst, 143, 339, 2018.

• R. Gillibert, J. Q. Huang, Y. Zhang, W. L. Fu, M. Lamy de la Chapelle Explosive detection by Surface Enhanced Raman Scattering, Trend in Analytical Chemistry, 105, 166, 2018

• R. Gillibert, J. Q. Huang, Y. Zhang, W. L. Fu, M. Lamy de la Chapelle Food quality control by Surface Enhanced Raman Scattering, Trend in Analytical Chemistry, 105, 185, 2018

• M. Cottat, R. Yasukuni, Y. Homma, N. Lidgi-Guigui, N. Varin-Blank, M. Lamy de la Chapelle, C.

Le Roy, Phosphorylation impact on Spleen Tyrosine kinase conformation by Surface Enhanced Raman Spectroscopy, Scientific Reports 7, 39766, 2017.

• Chauvet, R., F. Lagarde, T. Charrier, A. Assaf, G. Thouand, and P. Daniel. “Microbiological Identification by Surface-Enhanced Raman Spectroscopy.” Applied Spectroscopy Reviews 52, no. 2 (2017). https://doi.org/10.1080/05704928.2016.1209760

• I. Tijunelyte, S. Betelu, J. Moreau, I. Ignatiadis, C. Berho, N. Lidgi-Guigui, E. Guenin, C. David, S.

Vergnole, E. Rinnert, Marc Lamy de la Chapelle, Diazonium Salt-Based Surface-Enhanced Raman Spectroscopy Nanosensor: Detection and Quantitation of Aromatic Hydrocarbons in Water Sample, Sensors, 17(6), 1198, 2017

• M. Dribek, E. Rinnert, F. Colas, M.-P. Crassous, N. Thioune, C. David, M. Lamy de la Chapelle, C. Compère, Organometallic nanoprobe to enhance optical response on the polycyclic aromatic hydrocarbon benzo[a]pyrene immunoassay using SERS technology, Environmental Science and Pollution Research, 24(35), 27070, 2017

• Alami, A. El, F. Lagarde, U. Tamer, M. Baitoul, and P. Daniel. “Enhanced Raman Spectroscopy Coupled to Chemometrics for Identification and Quantification of Acetylcholinesterase

Inhibitors.” Vibrational Spectroscopy 87 (2016).

https://doi.org/10.1016/j.vibspec.2016.09.005.

• Enhanced Vibrational Spectroscopies as Tools for Small Molecule Biosensing, S. Boujday, M.

Lamy de la Chapelle, J. Srajer, W. Knoll, Sensors, 15, 21239, 2015

• M. Cottat, C. D’Andrea, R.Yasukuni, N. Malashikhina, R. Grinyte, N. Lidgi-Guigui, B. Fazio, A.

Sutton, O. Oudar, N. Charnaux, V. Pavlov, A. Toma, E. Di Fabrizio, P. G. Gucciardi M. Lamy de la

Chapelle , High Sensitivity, High Selectivity SERS Detection of MnSOD Using Optical Nanoantennas Functionalized with Aptamers,J. Phys. Chem. C 119 15532, 2015.

2. Physics and structural properties of soft matter

PSC axe: Surfaces et Interfaces Fonctionnelles

Researchers: Jean-François Bardeau, Guillaume Brotons, Philippe Daniel, Nicolas Delorme, Mathieu Edely, Nicolas Errien, Alain Gibaud, Fabienne Lagarde, Olivier Noel.

Several projects of our team are devoted to the study of soft matter physical properties as their mechanical, thermal or structural properties under different environments.

v Nano-mechanics of soft matter

Projets: Mecacell

Publication(s), book chapter(s), patent(s):

0 40 80 120 160 200

-2 0 2 4 6 8 10 12 14 16 18 20

x

Normal Force (nN)

Separation (nm) y

X:#Membrane#thickness#

Y:#Penetra3on#Force#

Fit with the Hertzian model to get the Young modulus

0 5 10 15 20 25

0 2 4 6 8 10

Friction Force (nN)

Normal Force (nN) Δ Friction Ofset Amontons’(law:(

FF(=(ξFN#

-50 0 50 100 150 200 250 300 350

0 1 2 3 4 5

Δ Friction offset (nN)

Sliding Speed (µm/s) Y = 0,0119x R2 = 0,9894 Viscosity="(12"±"1")"µN.s/m"

Nano%mechanics,on,cell,membranes,

Circular,AFM,mode,

Lateral,interac8ons, Normal,

interac8ons,

Viscoelas8city, Complex,biological,object,

• Et-Thakafy, O., N. Delorme, F. Guyomarc’h, and C. Lopez, Mechanical properties of milk sphingomyelin bilayer membranes in the gel phase: Effects of naturally complex heterogeneity, saturation and acyl chain length investigated on liposomes using AFM. Chemistry and Physics of Lipids, 2018. 210: p. 47-59, DOI: https://doi.org/10.1016/j.chemphyslip.2017.11.014.

• Et-Thakafy, O., N. Delorme, C. Gaillard, C. Mériadec, F. Artzner, C. Lopez, and F. Guyomarc’h, Mechanical Properties of Membranes Composed of Gel-Phase or Fluid-Phase Phospholipids Probed on Liposomes by Atomic Force Spectroscopy. Langmuir, 2017. 33(21): p. 5117-5126, DOI:

10.1021/acs.langmuir.7b00363.

• Ayche, K., A. Ventura, J.F. Bardeau, B. Minisini, J.F. Pilard, and N. Delorme, Natural rubber based thin coating for MEMS encapsulation. Progress in Organic Coatings, 2016. 99: p. 308-313, DOI:

http://dx.doi.org/10.1016/j.porgcoat.2016.06.010.

v Structural properties of polymers and complex composites films

Several techniques mastered in the team allow deep polymer characterization providing structural and physical information.

Since both infrared and Raman spectroscopies give complementary information, we use these techniques as effective tools to monitor the molecular structure and properties of polymers. Coupled with chemometrics, vibrational spectroscopies are used in the team to control polymer structure under different environments (thermal degradation, UV ageing, mechanical deformation, very thin films behaviors); to develop new bio-based polymers (cellulose, natural rubber) and to assess the distribution of fillers in composite polymers.

We have also developed a strong expertise in X-ray reflectivity....

Projets:

Publication(s), book chapter(s), patent(s):

• Anisotropic One-Dimensional Aqueous Polymer Gel Electrolyte for Photoelectrochemical Devices:

Improvement in Hydrophobic TiO2–Dye/Electrolyte InterfaceKK Sonigara, JV Vaghasiya, HK Machhi, J Prasad, A Gibaud, SS Soni. ACS Applied Energy Materials, 2018

• New proton conducting membrane based on bacterial cellulose/polyaniline nanocomposite film impregnated with guanidinium-based ionic liquid, S. Rogalsky, J.-F. Bardeau, S. Makhno, N.

Babkina, O. Tarasyuk, T. Cherniavska, I. Orlovska, N. Kozyrovska, O. Brovko, Polymer 142, 183- 195 (2018)

• 81. K. Taksapattanakul, T. Tulyapitak, P. Phinyocheep, P. Ruamcharoen, J. Ruamcharoen , F.

Lagarde, M. Edely, P. Daniel. Raman investigation of thermoplastic vulcanizates based on hydrogenated natural rubber/polypropylene blends. Polymer Testing. 57 107-114 (2017)

• S. Ghamrawi, J.-P. Bouchara, O. Tarasyuk, S. Rogalsky, L. Lyoshina, O. Bulko, J.-F. Bardeau, Promising silicones modified with cationic biocides for the development of antimicrobial medical devices, Materials Science and Engineering C 75, 969–979 (2017)

• Taksapattanakul, T.Tulyapitak, P. Phinyocheep, P. Ruamcharoen, J. Ruamcharoen, F. Lagarde, P.

Daniel The Effect of Percent Hydrogenation and Vulcanization System on Ozone Stability of Hydrogenated Natural Rubber Vulcanizates using Raman Spectroscopy. Polymer Degradation and Stability, 141 58-68 (2017)

• JV Vaghasiya, KK Sonigara, T Beuvier, A Gibaud, SS Soni, Iodine induced 1-D lamellar self assembly in organic ionic crystals for solid state dye sensitized solar cells, Nanoscale 9 (41), 15949-15957, 2017

• Chebil, M.S., G. Vignaud, J.K. Bal, T. Beuvier, N. Delorme, Y. Grohens, and A. Gibaud, Reversibility in glass transition behavior after erasing stress induced by spin coating process. Polymer, 2017.

122: p. 45-51, DOI: https://doi.org/10.1016/j.polymer.2017.06.044.

• JV Vaghasiya, KK Sonigara, J Prasad, T Beuvier, A Gibaud, SS Soni, Role of a phenothiazine/phenoxazine donor in solid ionic conductors for efficient solid state dye sensitized solar cells, Journal of Materials Chemistry A 5 (11), 5373-5382, 2017

• Unni, A.B., G. Vignaud, J.P. Chapel, J. Giermanska, J.K. Bal, N. Delorme, T. Beuvier, S. Thomas, Y.

Grohens, and A. Gibaud, Probing the Density Variation of Confined Polymer Thin Films via Simple Model-Independent Nanoparticle Adsorption. Macromolecules, 2017. 50(3): p. 1027-1036, DOI:

10.1021/acs.macromol.6b02617.

• Beena Unni, A., G. Vignaud, J.K. Bal, N. Delorme, T. Beuvier, S. Thomas, Y. Grohens, and A. Gibaud, Solvent Assisted Rinsing: Stability/Instability of Ultrathin Polymer Residual Layer. Macromolecules, 2016. 49(5): p. 1807-1815, DOI: 10.1021/acs.macromol.5b02435.

0.1 0.2 0.3 0.4 0.5 0.6

10^-12 10^-7 10^-2 10³

PS_130K_1.5g/L_Pressurization

Reflectivity

q_z (Å^-1)

0bar 15bars 30bars 50bars 65bars

• K. Ayche, A. Ventura, J.-F. Bardeau, B. Minisini, J.-F. Pilard, N. Delorme, Natural rubber based thin coating for MEMS encapsulation, Progress in Organic Coating 99, 308-3013 (2016)

• S. Rogalsky, J.-F. Bardeau, H. Wu, L. Lyoshina, O. Bulko, O. Tarasyuk, S. Makhno, T. Cherniavska, Y.

Kyselov, J. H. Koo, Structural, thermal and antibacterial properties of polyamide 11/polymeric biocide polyhexamethylene guanidine dodecylbenzenesulfonate composites, Journal of Materials Science 51, 7716-7730 (2016)

• D. Hodyna, J.-F. Bardeau, L. Metelytsia, S. Riabov, L. Kobrina, S. Laptiy, L. Kalashnikova, V.

Parkhomenko, O. Tarasyuk, S. Rogalsky, Efficient antimicrobial activity and reduced toxicity of 1- dodecy1-3-methylimidazolium tetrafluoroborate ionic liquid/beta-cyclodextrin complex, Chemical Engineering Journal 284, 1136-1145 (2016)

• A . Gibaud, J.K. Bal, E.M. Gullikson, C. Wang and G. Vignaud, AIP Advances, 6 (9), 095016, 2016

• J.K. Bal, T. Beuvier, A.B. Unni,E. Chavez, G. Vignaud, N. Delorme, M. Chebil,. Grohens, A. Gibaud, ACS Nano, 9, 8184, 2015

• Delorme, N., M.S. Chebil, G. Vignaud, V. Le Houerou, J.F. Bardeau, R. Busselez, A. Gibaud, and Y.

Grohens, Experimental evidence of ultrathin polymer film stratification by AFM force spectroscopy.

Eur. Phys. J. E, 2015. 38: p. 56.

• Bal, J.K., T. Beuvier, A.B. Unni, E.A. Chavez Panduro, G. Vignaud, N. Delorme, M.S. Chebil, Y.

Grohens, and A. Gibaud, Stability of Polymer Ultrathin Films (<7 nm) Made by a Top-Down Approach. ACS Nano, 2015. 9(8): p. 8184-8193, DOI: 10.1021/acsnano.5b02381.

3. Materials & surfaces for environment and health PSC axe: Surfaces et Interfaces Fonctionnelles

Researchers: Jean-François Bardeau, Guillaume Brotons, Alain Bulou, Philippe Daniel, Nicolas Delorme, Mathieu Edely, Nicolas Errien, Alain Gibaud, Fabienne Lagarde, Marc Lamy de La Chapelle, Olivier Noel.

Several projects of our institute are at the interface between physics, chemistry and biology. We mostly investigate the physico-chemical behavior and properties of materials and surfaces in complex environments or in interaction with cells and microorganisms. We also propose the elaboration of materials, surfaces and protocols mainly dedicated to sensing applications in medical, food and environmental fields.

v Surfaces in interaction with a complex environment

- Effect of the morphology and chemistry of TiO2 surfaces on the primary adhesion of microorganisms (i.e. bacteria and yeast). JF Bardeau

- Model bilayer lipid membranes and sensors for probing biorelevant interfaces.

G.Brotons

- Relation between physico-chemical properties of polymer microcarriers and the adhesion and differenciation of MIAMI cells in order to optimize the use of stem cells in neurodegenerative medicine. N. Delorme

- Interaction of micro and nanoplastics with marine biomolecules and microorganisms F. Lagarde, N. Errien, Ph. Daniel

- Tribology and mechanical properties modifications of biological cells in

associated pathologies (cancer, dislipidemia,...); wear mechanisms at the

nanoscale of metallic or composite materials to control emission of toxic

molecules. O. Noel

Immunofluorescence image illustrating the adhesion of MIAMI cells on

surfaces of functionalized microcarrier (PAM)

Projets: Meca-stem, Mat-Inno, Mecacell, Prompt

Publication(s), book chapter(s), patent(s):

• Vencl , P-E Mazeran , S. Bellafkih , O.Noël, Assessment of wear behaviour of copper-based nanocomposite at the nanoscale ,Wear 414–415 (2018) 212–218

• H. Fabre, D. Mercier, A. Galtayries, D. Portet, N. Delorme, and J.-F. Bardeau, Applied Surface Science 432, 15 (2018).

• Ariunzaya. Ts, Solongo. B, Rentsenmyadag. D, Erdene-Ochir. G, Ninjbadgar. Ts, P. Daniel, A.

Gibaud. Comparison Study on Antimicrobial and Photocatalytic Activity of Different Shaped ZnO Nanoparticles, accepted for publication in Solid state phenomena – October 2018

• G. Ragchaa, B. Mongol, S. Munkhsaikhan, N. Tuvjargal1, J. Davaasambuu, S. Enkhtor, L. Enkhtor1, O. Tegus, P. Daniel, Carbon Nanotube Fabrication Based on Animal Red Blood Cells. Solid State Phenomena, ISSN: 1662-9779, 271 64-69 (2018).

• Squillace O, Esnault C, Pilard JF and Brotons G. Grafting Commercial Surfactants (Brij, CiEj) and PEG to Electrodes via Aryldiazonium Salts. ACS Appl Mater Interfaces. 2017 Dec 6;9(48):42313- 42326.

• I. Paul-pont et al. (incl. G. Brotons, F. Lagarde) (2018), constraints and priorities for conducting experimental exposures of marine organisms to microplastics, frontiers in marine science 5, DOI:

10.3389/fmars.2018.00252.

• Noël, O., Vencl, A., Mazeran, P.-E., Exploring wear at the nano-scale with the circular mode AFM, Belstein Journal of Nanotechnology (2017)

• Lagarde F, Olivier O, Zanella M, Daniel P, Hiard S, Caruso A. Microplastic interactions with freshwater microalgae: Hetero-aggregation and changes in plastic density appear strongly dependent on polymer type. Environ Pollut. 2016;215.

v Detection, analysis and sensing for environment and health

Vibrational spectroscopies allow the fast and reliable identification and detection of molecules in any sample (liquid, solid, gaz, complex matrix…) with the possibility to strongly enhance the signal (SERS) allowing the detection of very small concentrations.

Our group developed strong skills in elaborating strategies for the immobilization, fast detection and analysis of organic molecules or microorganisms for environmental and health applications: organic pollutants in wood recycling industry, microorganisms and antibioresistance, food contaminants, pesticides in waters, micro and nanoplastics in aquatic compartments and biota, biomarkers in body fluids….

Projets: SeaBioPack, Agrifood, ANR Louise, ANR Nanoplastics, Miplaqua, Projet ANSES JFB, BASEMAN, MATIERES

Publication(s), book chapter(s), patent(s):

• N. T. X. Nguyen, S. Sarter, N. Hai Nguyen, P. Daniel. Detection of molecular changes induced by antibiotics in Escherichia coli using Raman and IR spectroscopies. Spectrochimica Part A:

Molecular and Biomolecular Spectroscopy. 183 395-401(2017).

• N. N. Phuong; L. Poirier; F. Lagarde; A. Kamari; A. Zalouk-Vergnoux (2018), Abundance and characteristics of microplastics in Atlantic coastal sediments, Environmental Pollution, 243(Pt A), DOI: 10.1016/j.envpol.2018.08.0322018.

• R. Gillibert, M. Triba, Marc Lamy de la Chapelle, Surface Enhanced Raman Scattering Sensor for Highly Sensitive and Selective Detection of Ochratoxin A, Analyst, 143, 339, 2018.

• R. Gillibert, J. Q. Huang, Y. Zhang, W. L. Fu, M. Lamy de la Chapelle Explosive detection by Surface Enhanced Raman Scattering, Trend in Analytical Chemistry, 105, 166, 2018

• R. Gillibert, J. Q. Huang, Y. Zhang, W. L. Fu, M. Lamy de la Chapelle Food quality control by Surface Enhanced Raman Scattering, Trend in Analytical Chemistry, 105, 185, 2018

• N. N. Phuong; L. Poirier; Q. T. Pham; F. Lagarde; A. Zalouk-Vergnoux (2018), Factors influencing the microplastic contamination of bivalves from the French Atlantic coast:

Location, season and/or mode of life? Marine Pollution Bulletin, 129(2), 664-674, https://doi.org/10.1016/j.marpolbul.2017.10.054.

• M. Cottat, R. Yasukuni, Y. Homma, N. Lidgi-Guigui, N. Varin-Blank, M. Lamy de la Chapelle, C.

Le Roy, Phosphorylation impact on Spleen Tyrosine kinase conformation by Surface Enhanced Raman Spectroscopy, Scientific Reports 7, 39766, 2017

• Nguyen, H., F. Lagarde, G. Louarn, and P. Daniel. “A New Way to Discriminate Polluted Wood

by Vibrational Spectroscopies.” Talanta 167 (2017).

https://doi.org/10.1016/j.talanta.2017.02.032.

• N. N. Phuong; A. Zalouk-Vergnoux; A. Kamari; C. Mouneyrac; F. Amiard; L. Poirier; F. Lagarde (2017), Microplastics in blue mussels (Mytilus edulis) of the French Atlantic coast: protocol set-up and preliminary data on the contamination, Environmental Science and Pollution Research, DOI: 10.1007/s11356-017-8862-3.

• Chauvet, R., F. Lagarde, T. Charrier, A. Assaf, G. Thouand, and P. Daniel. “Microbiological Identification by Surface-Enhanced Raman Spectroscopy.” Applied Spectroscopy Reviews 52, no. 2 (2017). https://doi.org/10.1080/05704928.2016.1209760.

• Alami, A. El, F. Lagarde, U. Tamer, M. Baitoul, and P. Daniel. “Enhanced Raman Spectroscopy Coupled to Chemometrics for Identification and Quantification of Acetylcholinesterase

Inhibitors.” Vibrational Spectroscopy 87 (2016).

https://doi.org/10.1016/j.vibspec.2016.09.005.

• N. N. Phuong, A. Zalouk-Vergnoux, L. Poirier, A. Kamari, A. Châtel, C. Mouneyrac, F. Lagarde (2016), Is there any consistency between the microplastics found in the field and those used in laboratory experiments?, Environmental Pollution, 211, Pages 111–123.

• Peng-Ubol, T., P. Phinyocheep, F. Lagarde, P. Daniel, J.-F. Pilard, W. Panbangred, G. Thouand, and M.-J. Durand-Thouand. “Functionalized Polyurethane Applied for Foodborne Pathogen Detection.” Journal of Food Measurement and Characterization 9, no. 3 (2015).

https://doi.org/10.1007/s11694-015-9230-y.

• M. Cottat, C. D’Andrea, R.Yasukuni, N. Malashikhina, R. Grinyte, N. Lidgi-Guigui, B. Fazio, A.

Sutton, O. Oudar, N. Charnaux, V. Pavlov, A. Toma, E. Di Fabrizio, P. G. Gucciardi M. Lamy de la Chapelle , High Sensitivity, High Selectivity SERS Detection of MnSOD Using Optical Nanoantennas Functionalized with Aptamers,J. Phys. Chem. C 119 15532, 2015.

v Organization of synthetic and natural micro and nano-objects

Investigation by X-ray holotomography of the 3D microstructure of microorganisms to understand their role of their biological functions. A. Gibaud

Projets:

Publication(s), book chapter(s), patent(s):

• T. Beuvier, B. Suchéras Marx, L. Beaufort, I. Probert, Y. Chushkin, F. Zontone and A. Gibaud, 2018, Nat.Com

• A Mcheik, S Cassaignon, J Livage, A Gibaud, S Berthier, PJ Lopez, Frontiers in Marine Science 5, 123, 2018

• O. Cherkas, T. Beuvier, D.W. Breiby, Y. Chushkin, F. Zontone and A. Gibaud, 2017, 17 (8), pp 4183–

4188

Ultrafast Phenomena 2015-2018

1- Electron and phonon ultrafast dynamic in solids exhibiting exotic coupling between charge, spin and structure.

Researchers: V. Juvé, G. Vaudel, T. Pezeril, M. Edely, B. Arnaud, R. Busselez, P. Ruello.

Coll. B. Dkhil, C. Paillard, SPMS Centrale Supelec, J. Szade, K. Balin, Institute of Physics, Katowice (Poland). Laboratoire International Associé France-Japon (LIA-IM-LED)

v Ultrafast photostriction in ferroelectrics and multiferroics

Abstract: The control of the photoinduced coherent acoustic phonon in ferroelectric and multiferroic compounds have been investigated in order to investigate the electron- phonon coupling and the coherent acoustic phonon detection processes. This research has permitted to reveal an original ultrafast optical-light mode conversion in BiFeO3 and LiNbO3. We have shown that it was possible to switch the light polarization from the ordinary to the extraordinary component (and vice-versa) with coherent acoustic phonon and this, up to hundreds of GHz (10ps). This mechanism is based on the modulation of the birefringence of the uniaxial crystal (BiFeO

, LiNbO

) induced, through the acousto-optic effect, by the coherent acoustic phonons (left panel in the figure below) [1]. This work has been selected by INP CNRS as a “highlight” [2]. This research is still going on with a focus on new possible way to generate acoustic phonon [3] (transformation of light energy into mechanical energy) with an ANR project UP- DOWN (IMMM leader) that has started in October 2018. The extension of the coupling between coherent acoustic phonons with the magnetic order and in particular with antiferromagnons will be investigated in the ANR SANTA (SPEC-CEA Leader) that has started in October 2018 as well.

Ultrafast light-mode conversion in birefringent ferrolectric materials.

Ultrafast electron and phonon dynamics in Topological insulators

k_i^(e)%

k_i^(o)% k_s^(o)%

k_s^(e)%

q_ph^(e)*(o)%

q_ph^(o)*(e)%

α"

Op,cal%Axis%(OA)%

n_e%% n_o%%

q_ph^(o)*(o)%

q_ph^(e)*(e)%

Light%

polariza,on%

conversion%

Gigahertz%

acous,c%

phonons%in%

ferroelectrics%

Projets : Lmac Région Pays de la Loire (Ferrotransducteur 2015-2019), ANR UP-DOWN 2018-2021.

Publication(s), book chapter(s), patent(s):

[1]Ultrafast acousto-optic mode conversion in optically birefringent ferroelectrics, Mariusz Lejman, Gwenaelle Vaudel, Ingrid C Infante, Ievgeniia Chaban, Thomas Pezeril, Mathieu Edely, Guillaume F Nataf, Mael Guennou, Jens Kreisel, Vitalyi E Gusev, Brahim Dkhil, Pascal Ruello, Nature comm. 7, 12345 (2016)

[2] http://www.cnrs.fr/inp/spip.php?article4895

[3] Photothermal optomechanics, P Ruello, Nature Photonics 10 (11), 692 (2016).

v Ultrafast electron and phonon dynamics in topological insulators.

Abstract: In this work we have investigated ultrathin films of topological insulator (4- 15nm). We have first studied the influence of the substrate and the microstructure (single versus polycrystalline structure on the femtosecond pulse-induced electron and phonon dynamics. While the optical phonons (zero group velocity) have frequency and damping dynamics nearly unaffected, the acoustic phonon signature (propagating wave) is clearly different revealing the importance of acoustic phonon scattering on grains boundaries and at interface between the nanometric film and the substrate [1]. In a second study, we have in particular measured the dynamic of hot carriers in Bi

Te

compound and have shown the existence of a strong quantum confinement appearing for thickness as thin as 5-6nm. A dramatic enhancement of the hot carriers relaxation is observed (right panel in the figure above). Such quantum confinement is also revealed in a thickness dependence of the process of generation of coherent acoustic phonons and in the anomalous damping of a Raman active mode A1g mode, together with a slight A1g mode softening. These phenomena evidence a drastic evolution of the electron-phonon coupling in a highly confined system. We have proposed with a simple model, that the band gap increases with decreasing the thickness is an indication of the increase of the electron-longitudinal acoustic phonon deformation potential. A more advanced theoretical work is now required to extract a more precise microscopic picture.

Nevertheless, these experimental results are important to tailor the proper thickness of such material for future integration in more complex devices where for example spin-to- charge conversion will be investigated.

Projets : French-Polish project, Bourse Ambassade de France (M. Weis), thèse co-tutelle (Le Mans, Insttut de Physique Katowice).

Publication(s), book chapter(s), patent(s):

- Ultrafast light-induced coherent optical and acoustic phonons in few quintuple layers

of the topological insulator Bi

Te

, M Weis, K Balin, R Rapacz, A Nowak, M Lejman, J

Szade, P Ruello, Physical Review B 92 (1), 014301 (2015)

- Quantum size effect on charges and phonons ultrafast dynamics in atomically controlled nanolayers of topological insulators Bi

Te

, M. Weis, B Wilk, G Vaudel, K.

Balin, R. Rapacz, A Bulou, B Arnaud, J Szade, P Ruello, Sci. Rep. 7, 13782 (2017)

2- Nonlinear acousto-magneto-plasmonics v Topological and nonlinear magneto-plasmonics

Researchers: V. Juvé, G. Vaudel, V.V. Temnov; D. Kuzmin, I. Bychkov (Chelyabinsk State University, CNRS-RFBR PRC partner university).

Abstract: In functional magnetic nanostructures acoustic, magnetic and plasmonic excitations can co-exist and interact on nanometer spatial and ultrafast time scales.

Optical spectroscopy with femtosecond laser pulses highlights a variety of nonlinear and spatio-temporal dynamical phenomena, which are not only used to monitor individual excitations in real time, but also to study their mutual interaction mechanisms [1].

Hybrid metal-ferromagnet multilayer structures [2] of periodically patterned plasmonic thin films in various topological configurations [3] can display unique linear and nonlinear magneto-optical properties; some of them can be probed by magnetic second- harmonic (SH) generation.

Nonlinear magneto-plasmonic experiments on metal-ferromagnet multilayer films exploit a significant dispersion of surface plasmon polaritons (SPPs) at fundamental and SH frequencies, which can be excited at different incidence angles in Kretschmann configuration using femtosecond laser pulses [1,2]. This angular dependence and magnetic control of second-order nonlinear-optical interactions at noble metal- ferromagnet interfaces enable the detailed study of phase-matching conditions governing the excitation of SPPs.

Periodic nanostructuring of magnetic thin films introduces new degrees of freedom in magneto-optical measurements allowing for the transition between optical gratings (large periodicity compared to optical wavelength) and metasurfaces (small periodicity) to be observed. As a first step in understanding of this new class of functional magneto- optical nanomaterials we have investigated the Wood’s diffraction anomaly on periodic arrays of nickel nanodimers. A periodic structure acting as a meta-surface at the fundamental frequency and as a diffraction grating at the double SH frequency has been identified using concepts of linear and nonlinear Wood’s anomalies [4].

Projets : This research is by now currently supported by a Strategie Internationale

“NNN-TELECOM” de la Region Pays de la Loire (2015-2019), French-Russian CNRS- RFBR PRC “Acousto-magneto-plasmonics” (2017-2019), European COST action MP1403

“Nanoscale quantum optics”, the ITMO University St. Petersburg (Research

professorship program 2019-2021).

Nonlinear magneto-plasmonics [1,2] Topological plasmonics [3]

Publication(s), book chapter(s), patent(s):

[1] V.V. Temnov et al., J. Opt. 18, 093002 (2016) [2] I. Razdolski et al., ACS Photonics 3, 179 (2016)

[3] D.A. Kuzmin et al., ACS Photonics 4, 1633 (2017); Nanophotonics 7, 597 (2018) [4] M. Tran et al., Phys. Rev. B 98, 245425 (2018)

v Ultrafast acoustics and magneto-acoustics with surface acoustic waves Researchers: V.V. Temnov; V.S. Vlasov, A. Golov, L.N. Kotov (Syktyvkar State University, CNRS-RFBR PRC partner university), D. Seletsky, A. Leitenstorfer (Konstanz University, ANR-DFG partner university).

Abstract:

Optical spectroscopy with femtosecond laser pulses highlights a variety of nontrivial spatio-temporal dynamics, which are not only used to monitor individual excitations in real time, but also study interaction mechanisms between them, often observed in frequency mixing phenomena. In acoustics and magnetism they are often dominated by parametric resonances, where system parameters are modulated at frequencies comparable to the natural oscillation frequencies, typically in the MHz-GHz range.

In recent experiments [1,2] the magnetization in a Ni/glass sample is excited by two distinct transient surface acoustic waves (denoted as SAW and SSLW, respectively, and recently quantified in time-resolved x-ray diffraction experiments [3]). Magnetic tuning of the FMR frequency in resonance to their SHG, sum- and difference frequencies demonstrates the full variety of frequency mixing phenomena [2]. In contrast to nonlinear optics, the frequency mixing is dominated by the parametric effect in the externally driven FMR oscillator. An analytical model based on the resonant enhancement of frequency-mixed signals explains the experimental observations [2].

The detailed understanding of magneto-interactions in nickel thin films motivates realistic concepts for acoustic magnetization switching at the nan-scale. For example, we have performed realistic modeling for nickel nanostructures to show that an elliptical nickel nanoparticle placed in a weak external magnetic field can be switched with small- amplitude pulses of surface acoustic waves [4].

Extending our theoretical modeling beyond the acoustically-driven FMR precession

allows us to study intriguing interactions between ultrashort acoustic pulses and

standing spin waves (exchange magnons) in thin ferromagnetic films. A practical

application of these findings to magneto-elastic switching in bi-stable systems, i.e. nickel nanomagnets, is under way [4].

Projets : This research is by now currently supported by a Strategie Internationale

“NNN-TELECOM” de la Region Pays de la Loire (2015-2019), French-Russian CNRS- RFBR PRC “Acousto-magneto-plasmonics” (2017-2019), French-German ANR-DFG

“PPMI-NANO” (2015-2019), the ITMO University St. Petersburg (Research professorship program 2019-2021).

Parametric magneto-acoustic frequency mixing [2] Elastic switching of nanomagnets [4]

Publication(s), book chapter(s), patent(s):

[1] J. Janusonis et al., Phys. Rev. B 94, 024415(2016) [2] C.L. Chang et al., Phys. Rev. B 95, 060409 (2017) [3] M. Sander et al., Phys. Rev. Lett. 119, 075901 (2017) [4] V.S. Vlasov et al., Crystals (to appear in 2019)

3- Ultrafast terahertz spectroscopy

Researchers: G. Vaudel, V. V. Temnov, P. Ruello, T. Pezeril, V. Juvé. Coll. JY CHauleau, M.

Viret, CEA-SPEC, J. Szade Institute of Physics Katowice (Poland), Laboratoire International Associé CNRS, France-Japon (LIA-IM-LED)

v THz polarization modulation of visible light by THz pulses

Abstract: Over the last decade, ultrafast Terahertz spectroscopy has gained tremendous

attention thanks to the development of high-power ultrafast laser systems, which

allowed generating intense single-cycle picosecond pulses of electric field at THz

frequencies. Their relatively long optical cycle period (1 ps for 1 THz) and high electric

field (from hundred of kV/cm to few MV/cm) provide a new tool for studying

fundamental aspects of light-matter interactions. Field-resolved detection of ultra-short

THz pulses is well known since many years and the most common technique is based on

free-space electro-optic sampling. This leads to the polarization change of an optical pulse, which is detected by the polarization sensitive scheme, and to the field-resolved detection of a THz pulse. Here we evidenced efficient non-resonant and noncollinear χ

-type type light-matter interaction in femtoseconds polarization sensitive time- resolved optical measurements. Such nonlinear optical interaction of visible light and ultra-short THz pulses leads to THz modulation of visible light polarization in bulk LiNbO

crystal. Theoretical simulations based on the wave propagation equation capture the physical processes underlying this nonlinear effect [1].

Left: A femtosecond optical pulse and a THz pulse, delayed in time respect to each other, are overlapping in a LiNbO3 crystal. Right: Non-resonant and noncollinear χ⁽²⁾-type light-matter interaction leads to a rotation Δθ of the optical pulse polarization at THz frequencies.

Projets : Région Pays de la Loire (Pari Scientifique NanoPlasmag 2018-2021), ANR SANTA 2018-2021.

Publication(s), book chapter(s), patent(s)

[1] V. Juvé, G. Vaudel, Z. Ollmann, J. Hebling, V. Temnov, V. Gusev and T. Pezeril, Optics Letters 43 (2018)

v Ultrafast THz emission by spin to charge current conversion (ferroic materials and topological insulators)

Abstract: Topological insulators (Bi

Se

, Bi

Te

etc…) are a new class of material, which

is stated to be at the core of the next generation of electronics devices. Their structure

consists of a bulk small bandgap insulator together with spin polarized surface states,

which can lead to surface spin current. Studying and controlling the surface spin current

is of interest for the scientific community. Using ultrafast THz spectroscopy, with photon

energy smaller than the band gap, one can try to have access to the surface states

dynamics and, thus, to the spin dynamics. High quality samples, which are well

characterized of Bi

Te

, are provided by the University of Silesia in Poland [1].

Left: Simplified band structure of topological insulators, which consists of a combination of a small band gap together with spin-polarized Dirac cones. Right: Relative change of the transmission induced by a THz pulse (2 meV photon energy) measured with a 3.1 eV photon energy for a Bi2Te3

sample of 15nm thickness.

We also have started to investigate the emerging field related to spin-to-chareg conversion (vice-versa). spin bursts can be produced by direct excitation of hot electrons in a ferromagnetic layer triggered by a femtosecond laser pulse. During the relaxation processes the diffusion lifetime and mobility differ for majority and minority spin carriers, resulting in the emission of angular momentum on a timescale of picoseconds. This effect, combined with Inverse Spin Hall Effect in an adjacent non- magnetic layer (Pt), was recently used to make efficient THz generation devices [2].

Based on this principle, we have already carried out preliminary measurement with CoFeB on Pt by shining femtosecond laser pulses to inject spin current bursts. As the direction of spin current is determined by the magnetization of the Ferromagnetic, the mechanism provides an easy and efficient way of controlling the direction of spin torque with a small magnetic field. This project is part of the Santa ANR (2018-2021) lead by Michel Viret (CEA/SPEC) within which IMMM is involved (starting Oct 2018).

Left: Principle of the spin to charge current conversion leading to THz emission (taken from Seifert et al Nat.

Phot. 2016). Right: Ultrafast THz emission measured by electro-optic sampling after ultrafast photoexcitation in a FeCoB(5nm)/Pt(3nm) sample. Reversing the external magnetic field leads to a change of sign of the THz electric field.

Projets : Région Pays de la Loire (Pari Scientifique NanoPlasmag 2018-2021), ANR

SANTA 2018-2021.

Publication(s), book chapter(s), patent(s):

[1] V. Juvé et al, in preparation

[2] T. S. Seifert, N. M. Tran, O. Gueckstock, S. M. Rouzegar, L. Nadvornik, S. Jaiswal, G. Jakob, V. V.

Temnov, M. Münzenberg, M. Wolf, M. Kläui and T. Kampfrath. J. Phys. D Appl. Phys. (2018)

4- Ultrafast Acoustics

Researchers: R. Busselez, T. Pezeril, G. Vaudel, V. Juvé, G. Brotons, N. Delorme, P. Ruello.

Coll. H. Piombini, P. Belleville CEA Le Ripault, V. Gusev, S. Raetz, N. Chigrev LAUM Le Mans Univ (Lmac Project). K. Nelson, C. Klieber (MIT, USA)

❖ Vibrational properties of liquids and interfacial liquids Abstract:

At Solid-Liquid interface, a drop of liquid film thickness towards nanoscale induces deep modifications of the liquid properties such as heat or particle transport, fluid rheology and lubrication. Among the properties impacted by the fluid size reduction and liquid- solid interface, the importance of the modifications in vibrational properties are actually scrutinized and debated. Despite this interest in interfacial liquids, experimental measures are not easily accessible at exceptions of Surface Force Apparatus and Atomic Force Microscopy techniques. We recently develop a home-built Time Dependant Brillouin Scattering permitting to reach the GHz dynamics range for liquids of thickness comprises between few microns to tenth of nanometers permitting to access to viscoelastic properties from the bulk liquids to thin films and may shed a new light on the comprehension of interfacial fluid properties.

TDBS measurements are also supported by molecular dynamics simulations which permits to bridge a gap between the length and time scales of both techniques and may relate modifications of macroscopic values such as viscoelastic properties to microscopic aspects.

Figure 6: Left: TDBS spectra of glycerol at different temperatures. Right: Velocity of longitudinal and transverse sound as a function of frequency obtained with molecular dynamics simulation of glycerol at different temperatures

Projects: ANR PlusDil

Related papers:

[1]I. Chaban, H. D. Shin, C. Klieber, R. Busselez, V. E. Gusev, K. A. Nelson and T. Pezeril, Time-domain Brillouin scattering for the determination of laser-induced temperature gradients in liquids, Review of Scientific Instruments, 2017, 88, 074904.

[2]R. Busselez, T. Pezeril and V. E. Gusev, Structural heterogeneities at the origin of acoustic and transport anomalies in glycerol glass-former, The Journal of Chemical Physics, 2014, 140, 234505.

v Probing elasticity at the nanoscale

Abstract: The ability to generate and to detect with femtosecond lasers coherent acoustic phonons with very high frequency (10-100s GHz) offers an unique possibility to directly measure the propagation speed of these acoustic phonons in nanostructures and then to investigate the elasticity [1]. Within this context, we have applied our method to probe the elasticity of different systems. First of all, we have studied assemblies of silica nanoparticles (10nm). These are the central element in advanced coating of many lenses in the French project Laser MégaJoule of CEA-DAM. The realization of coating with NPs assemblies permits to remove the coating quite often after each LaserMegaJoule Impact and to renew then the lenses. However, no advanced investigations of the mechanical properties of these coating were achieved up to now.

This was our task. In this study, we have been able then to reveal the nature of the contact between nanoparticles (Van der Waals or Hydrogen, Covalent) directly by evaluating how fast the coherent acoustic phonon propagate within a thin film made of this nanoparticle (see figure below). The transformation of such bond (called hardening process) was realized by chemists of CEA. We have been then able to extract the characteristic elastic modulus of films as thin as 70nm (but the technique can be applied to thinner system) [2]. This research has been selected by CEA DAM as one of the 25 more important results in 2017 of research at CEA DAM.

We have also recently applied this method to detect a phase transition in thin films of the multiferroic compound BiFeO3. In particular, we are able to distinguish the transition from the rhombhedral to tetragonal phase by analyzing the values of the sound velocity measured in sub-micrometric films [3].

Left: principal of a pump-probe method on a thin film made of an assembly of nanoparticles. The pump laser can induced mechanical resonances of the film that in turn induce some periodic modulation in time on the optical reflectivity. The latter one is measured with the probe beam Typicall mechanical oscillations are shown on the right where the change of frequency of the two first eigenmode clearly indicate the modification of the nanoscontact strength.

Projets : Contrat CEA (2015-2018) avec Bourse cofinancé CEA-Région Pays de la Loire.

Publication(s), book chapter(s), patent(s):

[1] Advances in applications of time-domain Brillouin scattering for nanoscale imaging, VE Gusev, P Ruello, Applied Physics Reviews 5 (3), 031101 (2018)

[2] Controlling the Nanocontact Nature and the Mechanical Properties of a Silica Nanoparticle Assembly, J Avice, C Boscher, G Vaudel, G Brotons, V Juvé, M Edely, C Méthivier, Vitalyi E Gusev, Philippe Belleville, Herve Piombini, Pascal Ruello The Journal of Physical Chemistry C 121 (42), 23769-23776 (2017)

[3] Evaluation of the structural phase transition in multiferroic (Bi1-x Prx)(Fe0.95 Mn0.05)O3 thin films by a multi-technique approach including picosecond laser ultrasonics, Samuel Raetz, Alexey Lomonosov, Sergey Avanesyan, Nikolay Chigarev, Elton de Lima Savi, Alain Bulou, Nicolas Delorme, Zheng Wen, Qiao Jin, Maju Kuriakose, Anthony Rousseau, Gwenaëlle Vaudel, Pascal Ruello, Di Wu, Vitalyi Gusev, in revision in Applied Sciences.

5- Simulation of ultrafast phenomena Researchers: B. Arnaud, F. Calvayrac

❖ Electron and phonon dynamics in photoexcited solids Abstract:

Pump probe experiments like optical pump probe experiments, time resolved X-ray diffraction, or time resolved photoemission experiments are currently used to study electron and phonon dynamics in nanostructures on time scales ranging from a few femtoseconds to a few picoseconds. Among the aforementioned techniques, optical pump probe experiments allow to study the coherent phonon generation mechanisms or

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even the possibility to demagnetize a sample with an ultrashort laser pulse. It is often difficult to interpret experimental results without resorting to models whose parameters can be inferred from ab-initio calculations. There are few calculations because of the need to describe non-equilibrium phenomenon occurring on different time scales and length scales. Nonetheless, ab-initio calculations combined with models already shed new light on ultrafast physics, especially on the coherent phonon generation, on the non thermal melting processes or on the energy transfer from the electronic degrees of freedom to the the vibrational degrees

of freedoms.

Figure 7: Schematic view of relaxation processes in photoexcited silicon

Related Papers:

Isabel González Vallejo, Geoffrey Gallé, Brice Arnaud, Shelley A. Scott, Max G. Lagally, Davide Boschetto, Pierre-Eugene Coulon, Giancarlo Rizza, Florent Houdellier, David Le Bolloc’h, and Jerome Faure,

“Observation of large multiple scattering effects in ultrafast electron diffraction”, Phys. Rev. B 97, 054302 (2018).

❖ TDDFT approaches to compute excited states of finite systems

Abstract: The PW-TELEMAN project aims at developing an open source (under GPL3)

and easy accessible package of real-time TDDFT libraries and codes, based on programs

developed over the past 20 years in a Toulouse-Erlangen collaboration which spread to

Le Mans and China via former students. At the time being no available code truly

accounts for a complete non-adiabatic electron-ions coupling allowing a full follow-up of

a whole dynamical scenario from early excitation (fs or sub-fs) to long time response

(ps) of a given physical system. To the best of our knowledge, the Toulouse-Erlangen