Research Activities - Institut des Sciences Chimiques de Rennes

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Solid State Chemistry and Materials group
Prof. M. Guilloux-Viry (University of Rennes 1)
- 34 researchers, professors and assistant professors, 15 technical staff
people
- 20 phD and post-doc
~ 85 peer-reviewed papers / year
~ 3 patents/year
Research covers 3 aspects:
→ New compounds synthesis and identification of their structure and properties
→ Patterning and functionnalization: from bulk to nanomaterials and thin films
→ Study of materials behaviour under used conditions
Research topics & Keywords
→ Materials for energy:
Intermetallics
(U-based),
condensed
clusters
(thermoelectric), oxides (SOFC)
→ Nanosciences: Nanomaterials and thin films, molecular clusters, lanthanides
complexes, hybrids
→ Materials for health: Biomaterials, Eco(nano)toxicity
Materials for energy: Intermetallics,
Condensed clusters, Oxides
Materials for energy: development of U based Intermetallics or Alloys for nuclear
applications
Powder metallurgy
Densification of fuels
Interactions fuel/matrix
Diffusion couples
fuel
Matrix
(Al)
Interaction product µ-DRX, TEM
Dilatometry & thermal analysis
New U(Mo) particles
with controled µ-structure
EBSD of U fuel
Diffusion mechanisms &
phase formations
 J. Allenou, F. Charollais, M. Brothier, X. Iltis, O. Tougait, M. Pasturel, H. Noël., international patent, FR-2969661(A1) 201206-29
 J. Allenou, X. Iltis, F. Charollais, O. Tougait, M. Pasturel, S. Deputier, French patent n°- 11 55551 2011-06-23
Materials for energy: Fondamental Properties of New Uranium and Cerium based
Intermetallics
Phase relations
Crystal structures
Electronic properties
Heavy
Fermions:
χ(T), ρ(T), Cp(T),
mK < T < 400°C
0 T < B < 14T
URu4Si4
P lattice
a = 4.11 Å, c = 15.5 Å
Local structures
U, Ce
XRD
TEM
Isothermal sections:
450°C < T < 1700°C
T: Fe, Co, Ni,
Zr, Nb, Mo,
Ru, Pt, …
η-diffraction,
NMR,
XPS
 R. Troć, M. Pasturel, O. Tougait, A. P. Sazonov, A. Goukassov, C. Sułkowski, H. Noël, Phys. Rev. B 85, 064412 (2012)
 A. Soudé, A. P. Pikul, P. Wiśniewski, O. Tougait, M. Pasturel, D. Kaczorowski, H. Noël, Intermetallics, 19 (2011) 1201-1206
Solid state synthesis, structural characterizations and study of physical
properties of cluster compounds
Structure of Ag3.9Mo9Se11:
 Mo9Se11 cluster units
build large voids
 Statistical occupancy of
Ag sites
 ZT = up 0.9 at 1000 K
[51264]
[512]
Mo4 clusters as building blocks for the
design of inorganic clathrate:
[(Cs2Mo6Cl14)4.77(CsCl)138Cs47][(CsCl)97Cs24][Mo4S4Cl6]136
136 Mo6Si8Cla12 per unit cell, Fd-3m;
a = 42.816(1) Å; V = 78 491 Å3
 T. Zhou, B. Lenoir, M. Colin, A. Dauscher, P. Gougeon, M. Potel, E. Guilmeau - Appl. Phys. Lett. 98, 162106 (2011)
 M. A. Shestopalov, A.Y. Ledneva, S. Cordier, O. Hernandez, M. Potel, T. Roisnel, N.G. Naumov, C. Perrin - Angew. Chem.
Int. Ed., (2010) 49, 3351.
Oxides for SOFC: Synthesis ; Reactivity under operating conditions studied by
neutron/X-ray diffraction and synchrotron X-ray absorption
O3
O2
XANES
Mn K-edge
Maximum
Entropy Method
Real-time in situ XAS
monitoring of topotactic
reduction under H2(g) in
Pr0.5Sr1.5Cr0.5Mn0.5O4-δ
Molecular
Dynamics
Conduction pathways at 900°C
under air in NdBaCo2O6-δ from
NPD/MEM analyses
Real-time in situ NPD
monitoring of topotactic
reduction under H2(g): From
tetragonal
Sr2MnO4
to
monoclinic Sr2MnO3.5
 M. Bahout, F. Tonus, C. Prestipino, D. Pelloquin, T. Hansen, E. Fonda, P. D. Battle, J. Mater. Chem. 22 10560 (2012)
 Y. Hu, O. Hernandez, T. Broux, M. Bahout et al., J. Mat. Chem. 22 18744 (2012)
 T. Broux, M. Bahout, O. Hernandez, F. Tonus, S. Paofai, T. Hansen, C. Greaves, Inorg. Chem. (submitted)
 Y. Kobayashi, O. Hernandez, T. Sakaguchi, T. Yajima, T. Roisnel et al., Nature Materials 11 507 (2012)
Oxydes , Phosphates, structural and physicochemical studies
Spin
frustration
in Solid State NMR studies
triangular
iron
lattice assisted
by
DFT
KFe(HPO3)2
calculations
Structure elucidation of VOPO4
31P
MAS with and
without 51V
decoupling
31P
MQ-MAS
experiments
Synchrotron variable
temperature diffraction
DFT calcultations
 Hamchaoui, F.; Alonzo, V. ; Venegas-Yazigi, D.; Rebbah, H.; Le Fur, E., J. Solid State Chem. 2013, 198, (0), 295
 Hermosilla-Ibanez, P.; Car, P. E.; Vega, A.; Costamagna, J.; Caruso, F.; Pivan, J. Y.; Le Fur, E.; Spodine, E.; Venegas-Yazigi,
D., CrystEngComm 2012, 14, (17), 5604
 Castets, A.; Carlier, D.; Zhang, Y.; Boucher, F.; Marx, N.; Gautier, R.; Le Fur, E.; Le Polles, L.; Croguennec, L.; Menetrier,
M.,. Solid State Nucl. Mag. Res. 2012, 42, 42
 Gougeon, P.; Gall, P.; Cuny, J.; Gautier, R.; Le Polles, L.; Delevoye, L.; Trebosc, J., Chem. Eur. J. 2011, 17, (49), 13806
 Gautier, R.; Audebrand, N.; Furet, E.; Gautier, R.; Le Fur, E., Inorg. Chem. 2011, 50, (10), 4378
Nanosciences: Nanoparticles - Thin Films, Molecular
Clusters, Lanthanides Complexes, Hybrids
Metal atom clusters as building blocks for the design of luminescent hybrid
nanomaterials and redox active molecular junctions
Cluster
Cluster
Cluster
= 1 nm
Lamellar
packing
smectic
phase
Day light
UV light
Luminescent
cluster
co-polymer
(GDR
C’NANO,
action
nanotrans 2009)
STM image of
cluster-modified
surface
of
A
POM
observation
cluster–
Molecular
junction:
cluster Clustomesogens:
immobilzed on a semiconducting based liquid crystals
(US patent n°61/264 888 (2009), CREATE
surface via an organic linker
5636- 2010-2012 Région Bretagne, FP7(ANR CLUSTSURF 2007-2011)
PEOPLE-Marie Curie actions: 1IEF + 1
IIF, projet maturation DV 615)
 Y. Molard, F. Dorson, K. Brylev, M. Shestopalov, Y. Le Gal, S. Cordier, Y. Mironov, N. Kitamura, C. Perrin. Chem. Eur. J., 16(19)
(2010) 5613-5619.
 S. Cordier, B. Fabre, Y. Molard, A.B. Fadjie-Djomkam, N. Tournerie, S. Ababou-Girard, A. Ledneva, N. G. Naumov, A. Moréac, C.
Godet. J. Phys. Chem. C, 114(43) (2010) 18622-18633.
 Y. Molard, F. Dorson, V. Circu, T. Roisnel, F. Artzner, S. Cordier - Angew. Chem. Int. Ed., (2010) 49, 3351-3355
 Y. Molard, A. Ledneva, M. Amela-Cortes, V. Cı̂ rcu, N. G. Naumov, C. Mériadec, F. Artzner, S. Cordier - Chem. Mater., 2011, 23, 5122
Metal atom clusters as building blocks for the design of luminescent and
multifunctional nanoparticles
λ exc = 405 nm
λ exc = 546 nm
K4Re6Se8(OH)6 &
K4Re6Se8(OH)6 @SiO2
UV light
Optical microscope picture
of ((n-C4H9N)4)2Mo6Br14@ZnO
colloid
γFe2O3-Cs2Mo6Br14@SiO2
ZnO-Cs2Mo6Br14@SiO2
 F. Grasset, Y. Molard, S. Cordier, F. Dorson, M. Mortier, C. Perrin, M. Guilloux-Viry, T. Sasaki, H. Haneda. Adv. Mat., 20 (2008) 1710.
 T. Aubert, A. Y. Ledneva, F. Grasset, K. Kimoto, N. G. Naumov, Y. Molard, N. Saito, H. Haneda, S. Cordier. Langmuir, 26(23) (2010)
18512–18518.
 F. Grasset, Y. Molard, F. Dorson, S. Cordier, M. Mortier, V. Demange, C. Perrin, V. Marchi-Artzner, H. Haneda –Chem. Comm., (2008)
4729
 T. Aubert , N. Nerambourg , N. Saito , H. Haneda , N. Ohashi , M. Mortier , S. Cordier, F. Grasset. Part. Part. Syst. Charact. 2013, 30,
90.
Oxides Nanoparticles and Nanocolloids: Synthesis and Characterization
@ZnO
Ferrites, ferrofluids
λ exc = 405 nm
2 nm
--------
6 nm
0.05
10 nm
15 nm
ZFCM (t w = 3600 sec at T w = 15 K)
ZFCM (ref)
0.001
w
= 3600 sec
0.03
ZFCM ref - ZFCM t
ZFCM / emu g
-1
0.04
0.02
0.000
10
0.01
10
Tw
20
Temperature / K
T w 20
30
40
Temperature / K
50
 F. Grasset, S. Cordier, Y. Molard, C. Perrin, V. Nazabal, M. Guilloux-Viry, S. Pechev, N. Saito, H. Ryoken, H. Haneda and T. Sasaki,
Inter. J. Nanotech., 5(6-8), (2008), 708
F. Grasset, Y. Molard, S. Cordier, F. Dorson, M. Mortier, C. Perrin, M. Guilloux-Viry, T. Sasaki, H. Haneda, Adv. Mat., 20 (2008) 1710.
 F. Grasset, O. Lavastre, C. Baudet, T. Sasaki and H. Haneda, J. Colloids Inter. Sci., 317(2), (2008), 493
V. Roullier, F. Grasset, F. Boulmedais, F. Artzner, O. Cador and V. Marchi-Artzner,Chem. Mater., 20, (2008), 6657
 Y. El Mendili, J.-F. Bardeau, N. Randrianantoandro, A. Gourbil, J.-M. Greneche, A.-M. Mercier, F. Grasset, J. Raman Spectrosc., 42,
(2011), 239
Y. El Mendili, J.-F. Bardeau, N. Randrianantoandro, F. Grasset, J.-M. Greneche, J. Phys. Chem. C, 116, (2012), 23785
Thin films for electronics
Oxides ferroelectric and dielectric epitaxial thin films
& multilayers
PLD
CSD ‘Record’ of tunability
66 % (Fr ) @ 120 kV/cm,
10 GHz
Investigation to decrease
dielectric losses
High
ε & Δε/ΔV
Au
KTN
KTN
KTN
Substrate
 Tunable devices (KTa1-xNbxO3), ferroelectricity, electro-optic, piezoelectric
 Nanostructuration
ANR Ecotech Ospégaz 2012-2015 (Oxydes sans plomb pour capteurs de
gaz)
Bi1.5-xZn0.92-yNb1.5O6.92-δ: effect of
microstructure
on
optical
properties
XRD – 4 circles texture
ϕ
ψ
• A. Le Febvrier, A.C. Galca, Y. Corredores, S. Députier, V. Bouquet, V. Demange, X. Castel, R. Sauleau, R. Lefort, L.Y. Zhang, G. Tanné,
L. Pintilie, M. Guilloux-Viry , ACS Appl. Mater. Interfaces, (2012)
• A. Le Febvrier, S. Députier, V. Bouquet, V. Demange, S. Ollivier, A.C. Galca, C. Dragoi, R. Radu, L. Pintilie, M. Guilloux-Viry,, Thin Solid
Films 520 (2012) 4564–4567
• Q. Simon, Y. Corredores, X. Castel, R. Benzerga, R. Sauleau, K. Mahdjoubi, A. Le Febvrier, S. Députier, M. Guilloux-Viry, L. Zhang, P.
Laurent, G. Tanne, Appl. Phys. Lett. 99, 092904 (2011)
• A. Bartasyte, J. Kreisel, W. Peng, M. Guilloux-Viry, Appl. Phys. Lett., 96, 262903 (2010)
Thin films for environment and optics
CuxMo6S8 intercalation compound thin films Oxides
for
photoluminescence
and
deposited by CSD for electrochemistry
photocatalysis (coll. Jao Pessoa, Sao Carlos, Brésil
– CAPES-COFECUB ; Coll. NIMS, CCA UR1-NIMS)
SrSnO3/saphir
Eu3+, Ti4+@ZnO
 Synthesis of Cu2Mo6S8 powders and thin films
from intermediate oxides prepared by polymeric
precursor method
 Electrochemical transfer junction (EJT) for
cation extraction (coll. C. Boulanger, IJL)
 Heavy metal ions sensors
(thèse CIFRE S. Boursicot (21/11/2012)
SrSnO3/SrTiO3
 Substrate controlled allotropic phases and growth
orientation of TiO2 epitaxial thin films
 Synthesis of SrSnO3 thin films by pulsed laser
deposition: Influence of substrate and deposition
temperature
Transparent and luminescent ZnO based thin films
Patent 2963027, BOPI 27/01/2012, S. Seghir, J.M. Lecuire, C. Boulanger, S. Diliberto, V. Bouquet, M. Guilloux-Viry, M. Potel
S. Seghir, C. Boulanger, S. Diliberto, J.M. Lecuire, V. Bouquet, M. Potel, M. Guilloux-Viry, Electrochemistry Communications 12 (2010)
1734–1737
S. Boursicot, V. Bouquet, I. Péron, T. Guizouarn, M. Potel, M. Guilloux-Viry, Solid State Sciences 14 (2012) 719-724
V. F. Silva, V. Bouquet, S. Députier, S. Boursicot, S. Ollivier, I.T. Weber, V.L. Silva, I. M. G. Santos, M. Guilloux-Viry, A. Perrin. J.f App.
Cryst. 43 (2010), 1502-1512
T. Aubert, F. Grasset, M. Potel, V. Nazabal, T. Cardinal, S. Pechev, N. Saito, N. Ohashi and H. Haneda, Sci. Technol. Adv. Mater. 11,
044401, 2010
Lanthanides-Based complexes and Coordination Polymers
Porosity > 2000 m2.g-1
in a rare earth amino
terephtalate
Optical properties: hetero-nuclear
complexes
Magnetic properties
 Y. Luo, G. Calvez, S. Freslon, C. Daiguebonne, T. Roisnel, O. Guillou. Inorganica Chimica Acta, 368, 170-178 (2011).
 D. Kustaryono, N. Kerbellec, G. Calvez, S. Freslon, C. Daiguebonne, O. Guillou. Crystal Growth and Design, 10(2), 775-781 (2010).
 C. Daiguebonne, O. Guillou, N. Kerbellec. (2007). FR2917226-A1 ; WO20088148792-A1 ; WO20088148792-A9 ; EP2152795-A1 ;
CN101711265-A ; CA2690044-A1 ; US2010207067-A1.
 G. Calvez, F. Le Natur, O. Guillou. Demande de brevet Français n°1258525 déposée le 11 septembre 2012.
 X. Yi, ; K. Bernot, F. Pointillart, G. Poneti, G. Calvez, C. Daiguebonne, O. Guillou, R. Sessoli, Chem.-Eur. J. , 18, 11379-11387 (2012)
 G. Cucinotta, M. Perfetti, J. Luzon, M. Etienne, P.-E. Car, A. Caneschi, G. Calvez, K. Bernot, R. Sessoli,. Angew. Chem. 51, 1606 (2012).
MOFs with original ligands:
Rational design of MOF’s
- Synthesis by solvothermal routes and mechanochemitry
- Structure determination: single-crystal / powder XRD (Laboratory, synchrotron)
- In situ powder diffraction & spectroscopy for studying reactivity (temperature, gas,
solvents)
- Example: a new Metal-Organic Framework built on Cu paddle-wheels
and
original
9,9’-spirobifluorene
ligand
with
high
surface
area
and
open metal sites
 potential catalytic applications
Langmuir specific surface area = 1427 m2/g > related MOF-2 (Yaghi et al., 1998)
• F. Moreau, N. Audebrand, C. Poriel, V. Moizan-Basle, J. Ouvry, J. Mater. Chem. , 21, 18715-18722 (2011)
Materials for health:
Biomaterials, Eco(nano)toxicity
Biomaterials
Eco(nano)toxicity
Bioactives glasses:
- Doping (Mg, Sr, Zn) in SiO2-CaO-P2O5-Na2O
glasses
→ Evidence of bioactivity:
Kinetic of bioactivity is tunable according to
the biomedical applications
→ Biological evaluation
hydroxyapatite
SiO2 reach layer
Glassy matrix
H. Oudadesse, E. Dietrich, Y. Le Gal, P. Pellen, B. Bureau, A. Mostafa, G. Cathelineau, Biomed. Mater., 6, (2011), 035006
A. Lucas-Girot, F. Mezahi, M. Mami, H. Oudadesse, A. Harabi, M. Le Floch, J. Non-Cryst. Solids, 357, (2011), 3322
H. Oudadesse, M. Mami, R. Dorbez-Sridi, P. Pellen-Mussi, F. Perez, S. Jeanne, D. Chauvel-Lebret, G. Cathelineau, Key Eng. Mater. 39698, (2009), 107
T. Aubert, A. Burel, M.-A. Esnault, S. Cordier, F. Grasset, F. Cabello-Hurtado, J. Hazardous Mat. 219-220, (2012), 111

Research Activities - Institut des Sciences Chimiques de Rennes

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