Physics and confined systems

21/01/19 1

Physics and confined systems

Ques+onnement scien+fique défini lors du projet HCERES en 2015 à Systèmes en interac+on avec les surfaces et interfaces

à Couplages : électron-spin-phonon-structure

Animateurs : R. Busselez (MCF), G. Brotons (MCF HDR) P. Ruello (PR)

21/01/19 2 Electron-phonon coupling

in correlated solids

Phonons in nanostructures Magneto-plasmonics

Magneto-acous8cs Func8onalized &

nanostructured surfaces

Sensors for health and environement SERS and plasmonics

Magne8c nanopar8cles

THz spectroscopy

Physics and confined systems : sub-axes

Numerical simulation

Solid-state physics Materials

science

nanostructures

Surfaces &

interfaces

Core-shell hybrids

Ultrafast phenomena NanopaGerning

Biological interac8ons with surfaces

PlaUorms :

- UV-VIS Spectroscopy - Atomic Force Microscopy - X-ray scaZering

- Femtosecond Lasers

- Compu+ng facili+es (HPC)

21/01/19 3

Membres

3

0 2 4 6 8

distribu8on des âges (PSC principale)

Nombreuses responsabilités : -  Vice-Présidente SEVU

-  Dir. Ecole Doctorale 3M (Bretagne-Loire) -  Co-direc+on IMMM

-  Co-Direc+on Rela+on Interna+onales UFR ST -  Co-Direc+on IUT

-  Responsabilités à INP CNRS

-  Responsables Licences 1,2 3 et Master 1 & 2 Physique

ARNAUD Brice PR UFR ST

BARDEAU J e a n -

François DR CNRS

BRETEAU Jean-Marc PR IUT

BROTONS Guillaume MCF HDR UFR ST

BUSSELEZ Rémi MCF UFR ST

CALVAYRAC Florent PR UFR ST

DANIEL Philippe PR UFR ST

DESERT Anne MCF UFR ST

EDELY Mathieu IR LMU

ERRIEN Nicolas MCF UFR ST

GIBAUD Alain PR UFR ST

GRENECHE Jean-Marc DR CNRS

JUVE Vincent CR CNRS

LABAYE Yvan MCF IUT

LAMY DE LA CHAPELLE Marc PR IUT

MOUNIER Denis MCF ENSIM

NOEL Olivier MCF HDR UFR ST

PEZERIL Thomas CR-HDR CNRS

RANDRIANANTOANDRO Nirina PR UFR ST

RUELLO Pascal PR UFR ST

TEMNOV Vasily CR-HDR CNRS

VAUDEL Gwenaëlle IR CNRS

YAACOUB Nader MCF HDR UFR ST

BENYAHIA Lazhar PR UFR ST

BOULARD BrigiZe MCF UFR

COSTE Sandrine MCF UFR

DEBARNOT Dominique MCF ENSIM

DELORME Nicolas PR IUT

KASSIBA Abdelhadi PR UFR ST

LAGARDE Fabienne MCF IUT

MARTEL Arnaud PR IUT

PILARD J e a n -

François PR UFR ST PONCIN-EPAILLARD Fabienne DR CNRS

à 33 membres = 23 (principal) + 10 (secondaire) Dont 2 DR CNRS, 3 CR CNRS, 1 IR CNRS (recrutement de 4 CNRS en 11 ans)

à 37 thèses (20 soutenues, 17 en cours). 3 abandons.

Nombre de personnes impliquées dans PSC en théma+que secondaire : POL = 6

MI = 3

SO =1

21/01/19 4

Moyens : bon dynamisme renforcé ces 3 dernières années

4

Période 2015-2018 à 7 ANR : 900 k€

à 7 Projets Région Pays de la Loire : 660 k€

à Projets grands organismes (IFREMER, INRA, CEA, ANSES, OSEO) : 330 k€

à Presta+ons Industrielles : 280k€

21/01/19 5

Produc+on scien+fique

•  Ar+cles ACL = 260 pour 23 membres (principaux) sur la période 2015-2018 (4 ans) (source ISI au 14 janv 2019)

•  Moyenne de 3 ar+cles par an par C/EC

•  Journaux à fort Impact : 8.5 % des publica+ons avec IF >7 Nature Photonics, Nature Comm. NanoLeZers, Phys. Rev.

LeZ., ACS Nano, NanoLeZers, Nanoscale, ACS Appl . Materials & Interfaces, Materials Today,

5

21/01/19 6

Interac+ons entre PSC et les autres théma+ques et l’environnement LMU

Nombre de personnes

impliquées dans PSC en théma+que secondaire :

POL = 6

MI = 3

SO =1

21/01/19 7

Highlights

Nanostructuration, SERS and plasmonics

Raman

Tracking of colloids and nanoparticles

Colloids synthesis and stabiliza+on Nanopar+cles on microalgae

Sensors for health and environment

Bacteria iden+fica+on

Physics-biology interactions, interfaces

Proteins Microorganisms attachment

Nano-mechanics of soft matter

Journals :

Nature Communica+ons, Phys.

Rev. LeZ, ACS Nano, ACS Appl.

Mater. Interf., Nanoscale, Sci.

Rep., Talanta, J. Phys. Chem. C, Langmuir, Polymer, Appl.

Spectros. Rev.

21/01/19 8 Probing nanomaterials and nanocontacts

Controlling the Nanocontact Nature and the Mechanical Properties of a Silica Nanoparticle Assembly

J. Avice, ^†,‡ C. Boscher, ^‡ G. Vaudel, ^† G. Brotons, ^† V. Juve , ́ ^† M. Edely, ^† C. Me thivier, ́ ^§ V. E. Gusev, ^∥ P. Belleville, ^‡ H. Piombini, ^‡ and P. Ruello * ^,†

† Institut des Molécules et Matériaux du Mans, UMR CNRS 6283, Le Mans Université, 72085 Le Mans, France

‡ Commissariat ł’Energie Atomique et aux Energies Alternatives, Centre du Ripault, Monts, France

§ Laboratoire de Réactivite ́ de Surface, UMR CNRS 7609, LRC-CEA/UPMC/CNRS no 1, 4 Pl. Jussieu, Université Pierre et Marie Curie, 75252 Paris, France

∥ Laboratoire d’Acoustique, UMR CNRS 6613, Le Mans Université, 72085 Le Mans, France

* ^S Supporting Information

ABSTRACT: Elaborating advanced nanomaterials based on the assembly of nanoparticles (NPs) is a versatile route for targeting and tuning a wide variety of properties like optical, magnetic, and electrical properties or sensing. This route usually employs a so-called soft chemistry which has the advantage of being quite cheap and transferable to an industrial level. However, getting quantitative information on the quality of the mechanical consolidation of the nanoparticle assembly (ordered or disordered) in a nondestructive manner is not often achieved, although it is crucial for applications and integration of materials in devices. Therefore, we present in this Article a complete method where we evaluate the elasticity of weakly (van der Waals nanocontacts) to strongly (covalent-hydrogen nano- contacts) interacting nanoparticle assemblies. This complete

work is realized on a disordered silica nanoparticle network obtained by the sol−gel method. A precise control of the chemical and physical properties of the nanoparticle surface molecular landscape is achieved thanks to infrared, visible, and ultraviolet spectroscopies as well as surface tension measurements and atomic force microscopy, while the nanoparticle assembly elastic sti ff ness is evaluated by ultrafast nanoacoustics based on an optical pump−probe method.

■ INTRODUCTION

Nanomaterial engineering based on the assembly of nano- particles (colloidal fi lms) permits many properties of advanced functionalized fi lm and smart coatings to be tailored. ¹⁻⁵ By adjusting the nanoparticle (NP) volume fraction and the nature of the nanoparticle interconnection, the physical and chemical properties of colloidal fi lms can be designed for speci fi c applications in optics, plasmonics, and photovoltaics. ³ These properties have also been studied as a function of the geometry of the packing, and the role of the nanoparticle/nanocrystals shape has been previously deeply studied. ^3,6,7 While continuous e ff orts have been made to optimize the growth and the control of the properties of these nanoparticle assemblies, ³⁻⁵ including the recent programmable CND-coated assemblies, ^8,9 it is admitted that nanoparticle assemblies su ff er from a poor mechanical reliability and durability. Despite this situation, the control of the physical and chemical nature of the nanocontacts on the collective mechanical integrity has been poorly evaluated ³ although crucial for future integration in any devices and smart coatings. The nature of the chemical bonds involved in the nanocontact is well identi fi ed with traditional

spectroscopic measurements, ³⁻⁵ but the strength of the nanocontacts and the overall elasticity of the NP network are not evaluated usually. ³⁻⁵ Besides the importance of the mechanical integrity of the NP assemblies, ^10,11 the quality of the nanocontact governs many other properties such as electronic ^12,13 or thermal transport. ¹⁴

The nanocontact elastic sti ff ness can be studied with spectroscopic methods such as Brillouin ¹⁵ or Raman spectros- copies. ^16,17 While the spectroscopic methods are based on the analysis of thermally excited vibrations in the solids, the ultrafast optic methods o ff er the possibility to excite and detect with light in an e ffi cient way some mechanical eigenmodes of nanomaterials and nanostructures. This so-called ultrafast nanoacoustics is known indeed as a powerful method to evaluate the elasticity at nanoscale and has already been used to probe nanostructured materials ^11,18,19 and colloidal nanostruc- tures. ^11,20−23 However, to get a full understanding of the

Received: August 23, 2017 Revised: September 29, 2017 Published: September 29, 2017

Article pubs.acs.org/JPCC

© 2017 American Chemical Society 23769 DOI: 10.1021/acs.jpcc.7b08404

J. Phys. Chem. C 2017, 121, 23769−23776 Cite This: J. Phys. Chem. C 2017, 121, 23769-23776

Simulation of magnetic properties of hybrid nanoparticles

Ab-ini+o and molecular dynamics

Semiconducteurs photoactifs

Transfert de Charges étudié par RPE

TiO ₂ , BiVO ₄ , NiTiO ₃ Nanostructuré

Magnetic anisotropy controlled with molecular complexes

reaction, up to Z av ¼ 10.2 nm when B85 complexes were added per nanoparticle in the first step (Supplementary Fig. 1 and Supplementary Table 1). Sample 1, which corresponds to the nanoparticles functionalized by the addition of ca. 60 complexes per particle in the first synthesis step, shows a similar increase.

This can be ascribed to the coordination of the complexes and to the presence around the particles of TMA ^þ counterions, which accompany the modification of the nature of the surface charge (from positively to negatively charged). Indeed, for bare nano- particles, DLS shows a similar increase of the hydrodynamic diameter (from 7.3 to 9.5 nm) when performing the brutal pH change in the absence of complexes: passing from 0a (pH 2.4) to the basified colloidal solution (sample 0b, pH 11) with the addition of TMAOH. For the functionalized nanoparticles, the absence of any additional peaks in DLS indicates that there are neither aggregation of particles nor side nucleation of cobalt oxide—that could have occurred were the complexes unstable. No evolution of the single peak has been observed over weeks.

The addition of 485 complexes per particle induces a dramatic increase of the hydrodynamic diameter, followed by the flocculation of the particles. The latter is probably caused by the loss of the electrostatic repulsion-induced stabilization that should accompany the increase of the grafting rate. In the following we will focus on 0b and 1.

Transmission electron microscopy (TEM) indicates that very similar sizes and distributions are observed for 0b and 1 (5.1 nm, s ¼ 0.12 and 5.0 nm, s ¼ 0.09, respectively; Fig. 1b and Supplementary Fig. 2). Along with the DLS experiments, this supports the absence of aggregation or of higher size particles.

It also indicates that the functionalization has a negligible effect on the size of the objects. X-ray powder pattern analysis shows that 0b and 1 both display the cubic structure of the maghemite

(Fd-3m) while the estimated crystallite sizes are in agreement with TEM imaging (Supplementary Fig. 3 and Supplementary Table 2). High-resolution TEM also confirms the cubic structure for the particles and indicates that no structural evolution has occurred during the functionalization reaction (Supplementary Fig. 4 and Supplementary Table 3). In addition, X-ray photo- electron spectroscopy (XPS) measurement at the Fe 2p edges shows an energy gap between 2p 1/2 and 2p 3/2 (13.7 eV), in agreement with the g-Fe 2 O 3 structure ³⁵ (Supplementary Fig. 5).

XPS measurements at the N 1s edge show two peaks at 404 and 399 eV for 1 (Fig. 2). The spectra of the bare nanoparticles 0b and of the complex display only one peak at 403 and 398 eV, respectively. As the presence of nitrogen atoms can originate from the TMA ^þ counterions in 0b and in 1, and from the TPMA ligand in 1 and in [Co(TPMA)Cl 2 ], the low energy contribution at 399 eV can be assigned to the nitrogen atoms from the TPMA ligand and the high energy peak at 404 eV to the contribution from the TMA ^þ counterion. The experimental Fe/N lig atomic ratio of the peaks has been found equal to 1.00 for sample 1, which differs from the calculated one (10 accounting for the TPMA ligands only). Nevertheless, the experimental Fe/N lig ratio agrees well with the calculated one if only surface iron ions (B10%) are taken into account. Atomic absorption spectroscopy (AAS) measurements made on a precipitated sample of 1 confirm the presence of cobalt(II) ions. The found 46 ± 4 Fe/Co ratio corresponds to 52 complexes per particle (considering 2418 Fe(III) ions for a spherical 5 nm g-Fe 2 O 3 nanoparticle). This would indicate an 86% grafting rate corresponding to a surface density of 0.66 complex per nm ² .

The presence of complexes coordinated to the nanoparticles surface has been further evidenced by X-ray absorption spectro- scopy (XAS) measurements at the L 2,3 edges of the iron and

0a

0b

1 NO

₃^–

+ [Co(TPMA)Cl

₂

]

+ TMAOH + TMAOH

pH 2.4 Z

_av

= 7.3 nm pH 2.4,

Z

_av

= 7.3 nm pH 11

Z

_av

= 10.2 nm D = 5.0 nm

! = 0.09 pH 11

Z

_av

= 9.5 nm D = 5.1 nm ! = 0.12 TMA

⁺

Co N Cl C

30

Count

Size (nm) 20

10

0 3 4 5 6 7

Figure 1 | Enhancing molecular complex and functionalized maghemite nanoparticles. (a) Representation of the [Co(TPMA)Cl

2

] complex used to enhance the magnetic anisotropy of the g -Fe

2

O

3

nanoparticles. (b) TEM image of the g -Fe

2

O

3

nanoparticles functionalized with the cobalt(II) complex: 1 (5.0 nm, s¼ 0.09) and (c) schematic view of the coordination of the complex with the iron ions. (d) Synthesis scheme with measured pH values, hydrodynamic diameters (Z

av

), sizes (D) and distributions ( s ).

NATURE COMMUNICATIONS | DOI: 10.1038/ncomms10139 ARTICLE

NATURE COMMUNICATIONS| 6:10139 | DOI: 10.1038/ncomms10139 | www.nature.com/naturecommunications 3

observed effect necessarily results from the magnetic interaction of the complexes with the particles, leading to an increase of the magnetic anisotropy. The transmission of the anisotropy from the complexes to the particles is possible only if there is an exchange interaction between the Co(II) and the Fe(III) ions. As the observed enhancement of the magnetic properties is important and effective at relatively high temperature, electrostatic interac- tions must be ruled out. Only the occurrence of a chemical bond such as an oxo-bridge between the Co(II) and the Fe(III) ions can support the effective anisotropy enhancement, source of the improved properties.

57 Fe Mo¨ssbauer spectrometry has been performed at 77 K on frozen solutions of 0b and 1 (Fig. 4 and Supplementary Fig. 11) to discriminate the chemical environment and magnetic properties of the different Fe species, through the analysis of the hyperfine interactions ³⁷ . Indeed, this local probe technique remains a powerful tool for investigating Fe-containing nanoparticles and the influence of the functionalization, thanks to its high sensitivity to electron transfer ³⁸ . The 77 K spectra result from a minor central quadrupolar doublet and a prevailing broadened lines magnetic sextet: they have exactly the same isomer shift and their proportions are rather independent of the samples. These two

contributions are unambiguously assigned to Fe species with fast and weak superparamagnetic relaxation phenomena, due to size distributions in the samples. The lack of resolution does not allow the proportions of iron in tetrahedral and octahedral sites to be estimated but they were accurately estimated from in-8 T field Mo¨ssbauer spectra at 12 K (Fe ^Oh (III)/Fe ^Td (III) ¼ 1.70 close to 5/3 as expected for maghemite; Supplementary Fig. 11). The mean values of isomer shift (at 77 K 0.41(2) mm s ^{" 1} ), which probes the electronic density at the ⁵⁷ Fe nuclei, that is the valence state, are consistent with the presence of pure ferric species for both 0b and 1. This excludes the presence of a ferric impurity and the occurrence of Fe ^2þ species or intermediate valence state. It further evidences that no electron transfer is induced by the presence of the Co(II) complexes. The mean hyperfine field distribution profiles, which correspond to the shape of the magnetic lines, indicate clearly that the grafting of the complexes gives rise to both a shrinkage of the distribution and a shift towards larger hyperfine fields, that is a significant increase of the mean hyperfine field (28.4(5) and 35.1(5) T, respectively). These features distinctly attest a slowdown of the relaxation phenomena of the magnetization in 1 because the attached Co(II) complexes increase the magnetic anisotropy of the Fe(III) moments, strengthening thus the magnetization of each nanoparticle, in agreement with the ZFC measurements.

The shape and intensity of the XMCD signals at the Fe L

2,3

edges for 1 are similar to those observed for previously reported maghemite nanoparticles ³⁹ . It bears the signature of antiferromagnetic coupling between Fe(III) ions in tetrahedral sites and Fe(III) ions in octahedral sites (Fig. 5). The magnetic moment for Fe(III) ions in the sub-network of the octahedral Fe(III) is parallel to the external magnetic field. The ratio between the occupation of the tetrahedral and octahedral sites can be determined from the ligand field multiplet analysis of the XMCD shape and a Fe ^Oh (III)/Fe ^Td (III) ratio close to 5/3 is found, as expected for maghemite. Traces of Fe(II) have also been detected.

The latter are due to sample preparation (see methods). The XMCD at Co L

2,3

edges in 1 is mainly negative at the L

3

edge indicating that the Co(II) magnetic moment is, at 6 T, parallel to the octahedral Fe(III) ions and antiparallel to the tetrahedral Fe(III) ions. Element-specific magnetization curves for Fe and Co were also obtained measuring the dependence of the XMCD signal as a function of the applied magnetic field amplitude (see methods). The Co-specific magnetization curve (Fig. 6 and Supplementary Fig. 12) does not show any inversion in the sign of the XMCD when varying the magnetic field, indicating that no inversion of coupling can be expected at low magnetic field. All three curves are superimposed demonstrating that the Co(II) is magnetically coupled to the Fe(III) ions of the maghemite nanoparticle. Moreover, the Co-specific magnetization curve of 1 differs drastically from the XMCD-detected magnetization curve of the [Co(TPMA)Cl

2

] complex. The latter shows a slow increase of the magnetization with no saturation reached at 6.5 T, as expected for a non-interacting paramagnetic Co(II) ion. For 1, the magnetization increases abruptly and saturates above 2 T. This behaviour evidences and confirms that the Co(II) ions within the grafted complexes are magnetically coupled to the iron(III) ions at the nanoparticles surface.

Discussion

We have presented in this work a synthetic strategy, which, in combining molecular and nano chemistry, offers a way towards control and modulation of the magnetic anisotropy in nano- particles. Magnetic measurements, Mo¨ssbauer spectrometry and XMCD measurements show that {Co ^II (TPMA)} ^2þ com- plexes grafted on the surface of maghemite nanoparticles –10

1.000

0.996

0.992 (0b) (1)

(0b) (1) 1.000

0.998

0.996

0.994

12

8

4

0

0 10 20 30 40 50

–10 –5 0

V (mm.s

^–1

)

5 10

Relativ e tr ansmission P (B

hf

)

B

hf

(T)

–5 0 5 10

Figure 4 | Slowdown of the relaxation of the magnetization. Zero field

57

Fe Mo¨ssbauer spectra (circles: experimental; lines: calculated) measured at 77 K for 0b (a) and 1 (b) and corresponding hyperfine field distributions (P(B

hf

)) vs hyperfine field (B

hf

) plot (c).

NATURE COMMUNICATIONS | DOI: 10.1038/ncomms10139 ARTICLE

NATURE COMMUNICATIONS| 6:10139 | DOI: 10.1038/ncomms10139 | www.nature.com/naturecommunications 5

Journals :

Nature Photonics, Nature

Communica+ons, Chem. Mater, Phys. Rev. LeZ, Nanoscale, Chem.

Phys., Phys. Rev. B, ACS Nano,

NanoleZers, ACS photonics, J. Phys.

Chem. C., Sci. Rep.

Electron and phonon dynamics in correlated solids

Coupling acoustic waves and ferromagnons

www.nature.com/scientificreports/

5 Scientific RepoRts | 6:29143 | DOI: 10.1038/srep29143

particular^25,26, with no sensitivity to magnetization dynamics. Apparent discrepancies between the data shown in Figs 2 and 3 arise from the details of the magnetic field alignment for the two data sets. As the angle between applied field and acoustic wavevector is varied, the amplitude at resonance and the near-zero-field Faraday behav- ior changes (and will be the subject of a forthcoming report). The data displayed in Fig. 2 was taken with an angle of 7.5° between k and →H, while the data shown in Fig. 3 below was taken at an angle of 60°. The clear difference ⎯ between these two angles is the appearance of oscillation amplitude at low applie fields when the angle is small.

However, the general features of resonant interaction, i.e. the amplification of precessional motion due to the elastic driving field, are unaffected.

Magnetooptic Sensitivity

The magnetic sensitivity in the Faraday channel relies on a non-trivial interplay between elastically activated mag- netostatic spin waves and the optically induced thermal gradieynt along its period. Over one period of the elastic wave, the magnetization precession samples all phases of oscillation and therefore the detectable net out-of-plane magnetization of the sample would sum to zero. It is additional aspect of thermal excitation that suppresses a portion of this magnetostatic wave, and provides for a net magnetization that is measured in the Faraday config- uration. Thus, the spatial profile of the magnetic wave as well as the thermal profile, and its dynamics, dictate the measurement sensitivity.

The magnetic waves are excited by the underlying elastic waves via inverse magnetostriction. In the TG con- figuration, two counterpropagating elastic waves are generated for both SAW and SSLW. The effects we describe can equally be accounted for by considering the time dependent elastic distortion as a standing wave, with regions of both positive and negative in-plane strain. In either picture, the strain profile results in a spatial distribution of the out-of-plane magnetization component:

= ^−ω.

M x tz( , ) Acos( )kx ei t (1) Equation 1 describes a spatially non-uniform magnetization profile, where the out of plane component grad- ually changes as function of position. In the elastic standing wave picture, we note that nodes in the elastic wave strain (xx) provide no torque to the magnetization, and thus these are regions of space where the magnetization is stationary to a first approximation. On either side of the nodes, magnetization precession is π out of phase.

In addition to this dipolar magnetostatic wave, the TG excitation also generates a spatially periodic thermal profile T(x). Saturation magnetization MS(T) at an elevated temperature decreases with respect to the saturation magnetization at zero temperature MS(0) as described by the Curie-Weiss law. Thus the temperature profile mod- ifies the spatial amplitude of the magnetization. The combined effect of the magnetostatic wave and the tempera- ture profile can be written for out of plane component as:

= ^−ω.

M x t( , ) A M T xM( ( )) kx e (0) cos( )

z S (2)

S i t

The net out-of-plane magnetic vector will be an average of this expression over one full spatial period

∫

<M t> =Ae^{−ω Λ}M T x .

M kx dx

( ) ( ( ))

(0) cos( )

z i t S (3)

0 S

Figure 3. The magnetization precessional amplitude strongly depends on the field applied to the sample.

When the field tuned ferromagnetic resonance frequency (red) matches that of the elastic waves (white), large amplitude oscillations are observed. The elastic frequencies can be determined by the transient grating measurements. Figure reproduced from Janusonis et al.¹⁹.

www.nature.com/scientificreports/

8 Scientific RepoRts | 6:29143 | DOI: 10.1038/srep29143

periodicities begin to coincide with film thickness (the waveguided modes of thin films), magnetoelastic cou- pling could begin to excite and probe the interactions between narrow band elastic modes and exchange coupled magnons. Here the specific choice of grating period, material, and applied field can be used to tune the dispersion relations of both magnon (quantized along the film thickness or in plane in the limit of very small gratings) and the elastic modes to effectively couple the two modes and provide for a new coherent control methodology where the material structure, and it’s deformations, can be used to coherently excited quantized magnetic modes in materials.

The presented technique may also be helpful to provide the direct acces to the fundamental magneto-acoustic non-reciprocity effects. Indeed, the coupling between the magnetic and elastic degrees of freedom leads to for- mation of magneto-elastic surface (eigen)modes with propagation velocities depending on the direction of the external magnetic field and sometimes different for opposite orientations of the external magnetic field. This magneto-elastic non-reciprocity effect is proportional to the magnitude of the magnetostriction coefficient and is quite small for the case of transition metals. However, it can be boosted in giant magneto-strictive materials like Terfenol-D

¹⁵

and we are looking forward to probing the magneto-elastic interactions in functional materials with optimized properties, which would also enable the excitation of large-angle magnetization precession ultimately leading to the nonlinear magnetization dynamics.

Figure 5. Calculation of the time dependent magnetic contrast requires a detailed knowledge of the temperature evolution and the resulting magnetization amplitude. Panels (a–c) show the temperature profiles at three different time slices, t = 0 ps, 35 ps, and 4 ns. Calculation of the initial dynamics is based on the two-temperature model, while subsequent thermalization is calculated using the COMSOL simulation package.

The time axis starts at the moment of the electron-lattice thermalization, typically < 2 ps after the pump pulse, with excitation fluence of 3.6 mJ/cm

²

. Note that the vertical length scale is in microns while the depth length scale is in nanometers. Panels (d–f) show the spatial distribution of the magnetization, where unity represents the magnetization at zero temperature. The dynamics of the hottest and coldest points of the sample are shown in panel (g) for grating periodicities of 1.1 µm and 2 µm, along with the difference in temperature. Panel (h) displays the resultant contrast which incorporates both the precession amplitude and temperature profile.

Also shown are the different contrast curves which incorporate variations in the thermal boundary resistance

between film and substrate. Finally in (i) the Faraday measurement resonant with the SSLW excitation is

corrected for the magnetic contrast.

21/01/19 9

9

Selected Achievements and

projects

21/01/19 10

Physics of confined systems

Magnetic nanoparticles

Numerical simulation

Solid-state physics Materials

science

nanostructures

Surfaces &

interfaces

Core-shell hybrids

Ultrafast phenomena Nanopatterning

Acteurs PSC-Nanostructures:

J.M.Grenèche, N.Randriantonandro,

N.Yaacoub, Y.Labaye, F.Calvayrac, R.Busselez, J.F. Bardeau

Thèses Soutenues: F.Sayed, Z.Nehme, Van Tang Nguyen

Thèses en cours: M. Missaoui

Equipes

21/01/19 11

Fe doping effect in free Rare Earth hard magne8c L1 ₀ phase

Mn-Fe ferromagne+c order in L1 ₀ τ-MnAl phase

Fe doping : improvement of magne+za+on

Equi-atomic τ-MnAl τ-Mn _1+x Al _1-x Fe doped Mn _1+x Al _1-x

FM order in ⁵⁷ Fe Mössbauer experience

Researchers : Van Tang Nguyen, N.

Randrianantoandro, F. Calvayrac, J-M Greneche

V. Tang Nguyen et al, J. of Mag. and Mag.

Mater, 462, 96–104 (2018).

21/01/19 12

Surface Effects in Ultrathin Iron Oxide Hollow Nanopar8cles:

Exploring Magne8c Disorder at the Nanoscale

Researchers : N.Yaacoub, Y.Labaye, J-M Greneche

F. Sayed et al, J. Phys. Chem. C, 122, 7516–7524 (2018).

G. Muscas et al, Nanoscale, 7, 13576–13585 (2015).

Z. Nehme et al, CrystEngComm, 18, 3799–3807 (2016).

F. Sayed et al, J. of Nano. Res.,

18, 279 (2016).

21/01/19 13

13

In situ laser irradia8on effects on

magne8c nanopar8cles and composites

Researchers : Jean-François BARDEAU, Nirina RANDRIANANTOANDRO, Jean-Marc GRENECHE

Phase stability of coated maghemite NPs examined under in situ laser irradia8on

Structural behavior of γ-Fe ₂ O ₃ nanocrystals dispersed in porous silica matrix

Y. El Mendili et al., Sci. and Tech. of Adv. Mater. 2016, 17, 597

M. Saidani et al., J. of All. and Comp. 2017, 695, 183

21/01/19 14

Classical Magne+c models: towards a mul+- scale approach

Researchers: F. Calvayrac, Y.Labaye, R.Busselez

Publica8ons:

K. Brymora and F. Calvayrac, J. Magn. and Mag. Mat, 2017, 434, 14–22.

F. Sayed and al Journal of Nanopar;cle Research, 2016, 18, 279.

Magne+c parameters determina+on coupling ab-ini+o/MD/Phen. Models

Mul+-Scale approach: structure impact on

magne+sm

21/01/19 15

15

Func8onalized &

nanostructured surfaces

Sensors for health and environement SERS and plasmonics

Numerical simulation

Solid-state physics Materials

science

nanostructures

Surfaces &

interfaces

Ultrafast phenomena Biological interac8ons

with surfaces

Physics of confined systems

Acteurs PSC-Surfaces Interfaces:

JF. Bardeau, A. Bulou, N. Delorme, A. Gibaud, P. Daniel, O. Noël ML de la Chapelle, F. Lagarde, N. Errien, M. Edely

R. Busselez, G. Brotons

Thèses Soutenues : K. Ayche, Benavides JC,

Chakaravarthy S., Chauvet R., Cherkas O., Edely M. El Alami A., Fabre H., Kahl P.,

Thèses en cours : Deniel M., Haddar N., Mhiri A.,

Mongol B., Nguyen N., Sulavko S. , Nguyen A.,

Sengdi L., Safar W., Taranamai P., Tsogoo A.

21/01/19 16

Théma8que Polymères Comité HCERES 16-18 décembre 2015

16

Plasmonics and Enhanced Vibra5onal Spectroscopies

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

optical Surface Plasmons

Interaction of Light – metal electrons for E-Field enhancement

RAMAN spectroscopies

For chemicals identification and trace detection

Bilans Publications : …

21/01/19 17

17

Understanding Plasmonic Surface Enhancement in RAMAN Spectroscopy.

ANR NanoBiosensor ANR Louise

ANR Piranex

Size 95 nm Height 7nm

Size 600 nm Height 120nm

10 ^-6 Mol/l Violet

Crystal

Thèse M.Edely

21/01/19 18

18

Plasmonis enhanced RAMAN spectro. and Chemicals / Traces Identification.

Exalted Raman Analysis

Chemical iden8fica8on

Sta8s8cal Analysis (PCA,…) Specific Capture

of Analytes

Projets:

Agrifood, ANSES tech, SeaBioPack, MATIERES

Plasmon assisted Surface Chemistry and Thermo-plasmonics.

RégionPDL XTrem (2019)

⇒ Visite Plateforme IMMM Spectroscopies

⇒ Discussion avec :

Marc Lamy de la Chapelle

dernier recrutement axe PSC-SIF

21/01/19 19

Théma8que Polymères Comité HCERES 16-18 décembre 2015

Reasearchers: 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, Jean-François Pilard.

Material-Science Physics of Interfaces and Thin Films

0.1 0.2 0.3 0.4 0.5 0.6

10

^-12

10

^-7

10

^-2

10

³

PS_130K_1.5g/L_Pressurization

Re flectivity

q _z (Å ^-1 )

0bar 15bars 30bars 50bars 65bars

AFM applied to Wear mechanisms

and Tribology X-Ray

Reflec8vity Polymer Thin Films

Soe-MaGer Physics at Interfaces

TOURS-2015 (col. ST-µ)

21/01/19 20

Soft-Matter-Physics for Biology and Health issues.

Région PDL-Mecacell, COST

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,

and Biological objects

20

Microorganisms Adhesion (Nosocomial Infec+ons)

Région PDL-MatInno (2013-2018),

Immunofluorescence image illustra+ng the adhesion of MIAMI cells on

surfaces of func+onalized microcarrier (PAM)

Stem-cells µ-carriers (PolyAM) Lipid Membrane

Sensors

Nano-Mechanics of Lipid-vesicles (Food Science)

Région PDL-MécaStem

(2015-2019)

21/01/19 21

21

ANR-Nanoplastics (µ et nano-plastiques dans l'environnement marin...., 2016-2020)

ANSES-PROMPT (PROteins-Micro-Plastic Tracking within biological environments, 2019-2022)

TRUMP (TRacking Unique Micro-Particles , 2019-2020) Colloids @ BioInterfaces

µ-organisms imaging techniques (role of oceans acidifica+on) µ-plas8c

pollutants (In bio-relevant and marine environment)

Soft-Matter-Physics for Environment issues.

21/01/19 22

Physics of confined systems

Acteurs PSC-Ultrafast Phenomena:

G. Vaudel, V. Juvé, V. Temnov, T. Pezeril, D. Mounier, P. Ruello R. Busselez, B. Arnaud, F. Calvayrac, M. Edely, N. Delorme

Thèses Soutenues: M. Lejman, I. Chaban, T.

Parpiiev, J. Avice, M. Tran, M. Weis

Thèses en cours: G. Chernouka, A. Levschuk, R. Gu.

Electron-phonon coupling in correlated solids

Phonons in nanostructures Magneto-plasmonics

Magneto-acous8cs

THz spectroscopy

Numerical simulation

Solid-state physics Materials

science

nanostructures

Surfaces &

interfaces

Ultrafast

phenomena

21/01/19 23

Ultrafast magneto-acoustics

Researchers : V. Shalagatskyi (PhD), V. Vlasov (postdoc), A. Lomonosov (inv. prof), T. Pezeril, G. Vaudel, V.V. Temnov

Ferromagne+c resonance driven by

ultrashort surface acous+c transients Linear parametric frequency mixing Magneto-op+cal transient gra+ng spectroscopy on nickel thin films

Coll : J. Janusonis, C.L. Chang, R. Tobey

J. Janusonis et al., Sci. Reports (2016) J. Janusonis et al., Phys Rev. B (2016)

C. Chang et al, Phys. Rev B (2017) Projets : ANRNNN-TELECOM” de la Region Pays de la Loire (2015-2019), French-Russian CNRS-RFBR PRC

“Acousto-magneto-plasmonics” (2017-2019),

21/01/19 24

Ultrafast photogeneration/photodetection of coherent phonons in correlated solids

Researchers : M. Lejman (PhD), M. Weis (PhD), G. Vaudel, I. Chaban, T.

Pezeril, B. Arnaud, V. Juvé, M. Edely, P. Ruello

k _i ^(e)%

k _i ^(o)% k _s ^(o)%

k _s ^(e)%

q _ph ^(e)*(o)%

q _ph ^(o)*(e)%

α"

O p, cal %A xi s% (O A) %

n _e %% n _o %%

q _ph ^(o)*(o)%

q _ph ^(e)*(e)%

Light%

polariza,on%

conversion%

Gigahertz%

acous,c%

phonons%in%

ferroelectrics%

Ultrafast acousto-op+c mode conversion in BiFeO3

Quantum size effect on electron- phonon coupling in Bi2Te3

Topological insulators

Coll : B. Dkhil, P. Gemeiner, C. Paillard, J. Szade, K. Balin, B.

Wilk (Katowice Univ Poland)

Lejman et al, Nature comm. 7, 12345 (2016) Weis et al, Phys. Rev. B, 72, 014301 (2015) Weis et al, Sci. Rep. 7, 13782 (2017)

Projets : ANR UP-DOWN 2018-2021,

21/01/19 25

Nonlinear & topological magneto-plasmonics

Researchers : M. Tran (PhD), A. Alekhin (postdoc), I. Razdolski (inv. prof), D.

Kuzmin (inv. prof), G. Vaudel, V. Juvé, V.V. Temnov

Magneto-plasmonic mul+layers

Phase-matched excita+on and

magne+c control of surface plasmons

Coll : A. Leitenstorfer, D. Seletskiy, Th. Rasing, D. Makarov, I. Bychkov

33%

2 2

2 2

( ) ( )

( ) ( )

I M I M

I M I M

ω ω

ω ω

+ − −

+ + −

Magne+c and topological meta-surfaces

Topologically induced op+cal ac+vity in graphene meta-structures

I. Razdolski et al., ACS Photonics (2016) D. Kuzmin et al., ACS Photonics (2017) D. Kuzmin et al., Nanophotonics (2018)

Projets : NNN-TELECOM” French-Russian CNRS-RFBR PRC

“Acousto-magneto-plasmonics” (2017-2019), French-

German ANR-DFG “PPMI-NANO” (2015-2019)

21/01/19 26

Probing nanomaterials : bondings, elasticity and nanocontacts

Researchers : J. Avice (Ph. D), G. Vaudel, M. Edely, G. Brotons, V. Juvé, P. Ruello Coll : CEA- H. Piombini, C. Boscher, P. Beleville, LAUM - V. Gusev

Projets : CEA Megajoule Laser project

0 2 4 6 8 10 12 14 16 18

1 10 100 1000 10000

Vo lu m e ( Pe rc e n t)

Size (d.nm) Statistics Graph (1 measurements)

Mean with +/-1 Standard Deviation error bar Size

d.nm 0,4000 0,4632 0,5365 0,6213 0,7195 0,8332 0,9649 1,117 1,294 1,499 1,736 2,010 2,328 2,696 3,122 3,615 4,187 4,849

Mean Volume Percent

0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 1,6 6,3

Std Dev Volume Percent

Size d.nm 5,615 6,503 7,531 8,721 10,10 11,70 13,54 15,69 18,17 21,04 24,36 28,21 32,67 37,84 43,82 50,75 58,77 68,06

Mean Volume Percent

12,0 15,5 16,0 14,3 11,4 8,4 5,7 3,7 2,3 1,3 0,7 0,4 0,2 0,1 0,0 0,0 0,0 0,0

Std Dev Volume Percent

Size d.nm 78,82 91,28 105,7 122,4 141,8 164,2 190,1 220,2 255,0 295,3 342,0 396,1 458,7 531,2 615,1 712,4 825,0 955,4

Mean Volume Percent

0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0 0,0

Std Dev Volume Percent

Size d.nm 1106 1281 1484 1718 1990 2305 2669 3091 3580 4145 4801 5560 6439 7456 8635

1,000e4 Mean Volume Percent

0 0

Capteur.sop Measurement Date and Time:

Z-Average (nm):

Sample Name:

SOP Name:

silcol pH6 socomore 140400209 5

Variance:

%Std Deviation: %Std Deviation:

Standard Deviation (kcp... 0 Sample Details

silcol pH6 socomore 140400209.dts

0 13,899

Standard Deviation (nm):

Derived Count Rate (kcps): 5081,9137816...

File Name:

0 0

Variance:

lundi 5 mai 2014 10:46:59

Size Statistics Report by Volume

Malvern Instruments Ltd - © Copyright 2008

v2.0

www.malvern.com Malvern Instruments Ltd

Serial Number : MAL500295 Zetasizer Ver. 7.03

23 mai 2014 16:15:06 Record Number: 5

File name: silcol pH6 socomore 140400209.dts

CH2 CH3 CH3 CH2 SiO ₂

Van der Waals bonds

Hydrogen and covalent bonds

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$#

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"#

$# !"#

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Si O Si

O

H O

Si O H

SiO ₂

SiO ₂

SiO ₂

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*"+)

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*-+)

.)

*/01)234)&1+)

*/01)54)&1+)

6"#%)7'8 ₂ ) 9:-9;#";%)

H ₂ 0

CH ₃ CH ₂ OH

Pump (fs laser)

-  Measurements of mechanical proper+es of lens coa+ngs of the Megajoule Laser with picosecond acous+cs method

-  Probing the molecular interac+on between biological membranes and surfaces.

Coa+ng of the lens

Photoinduced vibra+ons

lens lens

Avice et al, J. of Phys. Chem. C, 121, 23769-23776 (2017) Avice et al, Op+c Express, 25, 23 (2017)

Gusev & Ruello, Appl. Phys. Rev. 5, 031101 (2018)

21/01/19 27

THz ultrafast science

Electro-optic interactions in thick crystals

Personal involved: A. Levchuk (PhD), G. Vaudel, P. Ruello, V. Juvé Coll. : CEA SPEC (M. Viret, JY Chauleau), Inst Phys Katowice Univ (J. Szade).

Elementary excitation in topological insulators

b)

0 5 10 15 20

-0.04 -0.02 0.00 0.02 0.04 0.06 0.08 0.10

ΔΤ / Τ |

osc

(%)

Time delay τ (ps)

0.0 0.5 1.0 1.5 2.0 2.5

0.00 0.25 0.50 0.75 1.00

f~1.85 THz

Magnitude FFT (A. U.)

Frequency (THz) f~0.18 THz

-5 0 5 10 15 20

0.00 0.25 0.50 0.75

ΔΤ / Τ (%)

Time delay τ (ps) a)

Juvé et al, Op+cs. LeZ. 2018 Juvé et al, under prepara+on Projets : RPL

Nanoplasmag, ANR

SANTA 2018-2021