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Black phosphorus (BP) is a stack of monoatomic layers of phosphorus, bound together by Van der Waals forces. This 2d material is today attracting a great interest due to its widely tunable band gap, depending on the thickness of the material, the very high mobility of its carriers, for its application in field effect transistors (FETs), and the possible emergence of topologically protected states. It has been shown that electrostatic action or evaporation of alkali metals, as electron donors, can be successfully used for doping the PB from a semiconductor phase to a semi-metallic phase with Dirac cone transport channels (with linear dispersion).

Experimentalists and theoreticians at the Laboratory for Irradiated Solids (LSI) have thus studied the excited electronic states of black phosphorus after deposition of an increasing dose of alkaline atoms. The FemtoARPES (angle-resolved photoemission) experimental device at the LSI was used to monitor the band gap closure with unprecedented accuracy. This engineering of the electronic band structure would enable the design of devices with improved and optimized electronic and optoelectronic functionality.

de Oliveira-Silva, Rodrigo; Bélime, Agathe; Le Coeur, Clémence; Chennevière, Alexis; Helary, Arnaud; Cousin, Fabrice; Judeinstein, Patrick; Sakellariou, Dimitrios; Zanotti, Jean-Marc

In soft condensed matter, Small Angle Neutron Scattering (SANS) is a central tool to probe structures with characteristic sizes ranging from 1 to 100 nm. However, when used as a standalone technique, the dynamic properties of the sample are not accessible. Nuclear Magnetic Resonance (NMR) is a versatile technique which can easily probe dynamical information. Here, we report on the coupling of a low-field NMR system to a SANS instrument. We show that this original set-up makes it possible to obtain structural information and to simultaneously extract in situ on a same sample, long-range translational diffusion coefficient, T1T1 and T2T2 nuclear spin relaxation times. Such a feature is of major interest when a sample experiences a transient physical state or evolves rapidly. We illustrate the capabilities of alliancing these experimental methods by following the critical temperature-induced phase separation of a concentrated Poly(Methacrylic Acid) solution at its Lower Critical Solution Temperature. The characteristic size related to the domain growth of the polymer-rich phase of the gel is monitored by the evolution of the SANS spectra, while the dynamics of the sol phase (H2O and polymer) is simultaneously characterized by NMR by measuring T1T1, T2T2 and the diffusion coefficient. Great care has been taken to design a cell able to optimize the thermalization of the sample and in particular its equilibration time. Details are given on the sample cell specifically designed and manufactured for these experiments. The acquisition time needed to reach good signal-to-noise ratios, for both NMR and SANS, match: it is of the order of one hour. Altogether, we show that in situ low-field NMR/SANS coupling the NMR is meaningful and is a promising experimental approach.

DOI

M. Ruminy, S. Guitteny, J. Robert, L.-P. Regnault, M. Boehm, P. Steffens, H. Mutka, J. Ollivier, U. Stuhr, J. S. White, B. Roessli, L. Bovo, C. Decorse, M. K. Haas, R. J. Cava, I. Mirebeau, M. Kenzelmann, S. Petit, and T. Fennell

Tb2Ti2O7 presents an ongoing conundrum in the study of rare-earth pyrochlores. Despite the expectation that it should be the prototypical unfrustrated noncollinear Ising antiferromagnet on the pyrochlore lattice, it presents a puzzling correlated state that persists to the lowest temperatures. Effects which can reintroduce frustration or fluctuations are therefore sought, and quadrupolar operators have been implicated. One consequence of strong quadrupolar effects is the possible coupling of magnetic and lattice degrees of freedom, and it has previously been shown that a hybrid magnetoelastic mode with both magnetic and phononic character is formed in Tb2Ti2O7 by the interaction of a crystal field excitation with a transverse-acoustic phonon. Here, using polarized and unpolarized inelastic neutron scattering, we present a detailed characterization of the magnetic and phononic branches of this magnetoelastic mode, particularly with respect to their composition, the anisotropy of any magnetic fluctuations, and also the temperature dependence of the different types of fluctuation that are involved. We also examine the dispersion relations of the exciton branches that develop from the crystal field excitation in the same temperature regime that the coupled mode appears, and find three quasidispersionless branches where four are expected, each with a distinctive structure factor indicating that they are nonetheless cooperative excitations. We interpret the overall structure of the spectrum as containing four branches, one hybridized with the phonons and gaining a strong dispersion, and three remaining dispersionless.

https ://doi.org/10.1103/PhysRevB.99.224431

La métrologie (spectroscopie, mesures de temps ou de distances) ou encore la réalisation de réseaux optiques quantiques nécessitent des sources de photons uniques efficaces. Une équipe du SPEC à Saclay, en collaboration avec l'IQST d'Ulm en Allemagne, démontre expérimentalement une voie originale pour obtenir une source de photons microonde uniques, simple, efficace et brillante. Cette nouvelle voie exploite un régime de fort couplage lumière-matière rendu accessible grâce aux développements récents des circuits électriques quantiques.

 

Souha Ben Mahmoud, Wafa Essafi, Annie Brûlet and François Boué

The chain conformation in sulfonated polystyrene PSSNa of a degree of sulfonation 0.34 ≤ f ≤ 1, i.e., of various hydrophobicity, is followed in mixtures of water and increasing content of tetrahydrofuran (THF), a good solvent of the hydrophobic polystyrene moieties (which improves the solvent quality of the mixture). This is achieved by measuring the chain form factor by small-angle neutron scattering using the zero average contrast method (ZAC). Polymer concentrations 0.17 and 0.34 M correspond in our case to the semidilute regime or its limit with dilute regime depending on the chain conformation. The main result is the monitoring with added THF of the pearl necklace conformation. This heterogeneous structure, made of wormlike chain parts (strings) and pearls, was observed formerly in water: when f decreases, the string contribution decreases, and the pearls size, characterized by a maximum in Kratky q2S1(q) representation, slightly increases. Here we see that in the presence of increasing content of added THF (i) the pearls contribution decreases, as expected, and (ii) their size does not change by more than 10% in most cases (30% at the most). Among different modeling, the most complete has been done following the pearl necklace models of Schweins, Huber et al. and Lages, Huber et al.; beyond the size and distribution of pearls, it addresses the radius of gyration, the correlation distance between spheres, weakly visible, and, importantly their number N. The values of Rg, as well as the modeling, suggest that while the sphere size varies a few, N decreases clearly with added good solvent. A link with the simulation of Liao et al. can be found. A second result, important in practice, is that all modeling of the scattering establishes that THF addition makes vanish an excess of low q scattering due to large compact spheres present in water. A third result is obtained after a “THF treatment” procedure, consisting of adding THF and then removing it by evaporation: (i) the spherical aggregates are washed out, and (ii) the pearl necklace conformation of the chain returns to the one in water solution before treatment. Therefore, the pearl necklace conformation of the hydrophobic polyelectrolyte in aqueous solution appears to be in an annealed equilibrium state resulting from hydrophobic attraction and electrostatic repulsion.

DOI: 10.1021/acs.macromol.8b00990

Béatrice Gillon, Albert Hammerschmied, Arsen Gukasov, Alain Cousson, Thomas Cauchy, Eliseo Ruiz, John A. Schlueter, Jamie L. Manson

We report neutron‐diffraction investigations of the quasi‐2D MnII(dca)2(pym)(H2O) (pym = N2C4H4) compound, where high‐spin MnII ions are bridged by dicyanamide anions, [N(CN)2] (herein abbreviated dca). Inside the layers, Mn2+ ions are connected by single or double dca bridges. The magnetic phase diagram was established by neutron diffraction on a single crystal. In the low‐field phase, the MnII ions are antiferromagnetically ordered in the layers, with moments nearly parallel to the c axis, and the layers are antiferromagnetically coupled. The spin‐flop phase corresponds to ferromagnetic coupling between the antiferromagnetic layers, in which the MnII moments are nearly perpendicular to the c axis. The induced spin‐density distribution in the paramagnetic phase, determined by polarized neutron diffraction, visualizes the superexchange pathways through the dca ligands within the layers and through H bonding between neighboring layers. The theoretical spin density obtained by bidimensional periodic DFT calculations is compared with the experimental results. Furthermore, quantum Monte Carlo simulations have been performed to compare the DFT results with experimental susceptibility measurements.

https://doi.org/10.1002/ejic.201700971

We report on the self-assembly behavior of poly(2-methyl-2-oxazoline)–block–poly(2-octyl-2-oxazoline) comprising different terminal perfluoroalkyl fragments in aqueous solutions. As reported previously [Kaberov et al. (2017)] such polyphiles can form a plethora of nanostructures depending of the composition and on the way of preparation. Here we report, for the first time, detailed information on the internal structure of the nanoparticles resulting from the self-assembly of these copolymers. Small-angle neutron and X-ray scattering (SANS/SAXS) experiments unambiguously prove the existence of polymersomes, wormlike micelles and their aggregates in aqueous solution. It is shown that increasing content of fluorine in the poly(2-oxazoline) copolymers results in a morphological transition from bilayered or multi-layered vesicles to wormlike micelles for solutions prepared by direct dissolution.

In contrast, nanoparticles prepared by dialysis of a polymer solution in a non-selective organic solvent against water are characterized by SAXS method. The internal structure of the nanoparticles could be assessed by fitting of the scattering data, revealing complex core-double shell architecture of spherical symmetry. Additionally, long range ordering is identified for all studied nanoparticles due to the crystallization of the poly(2-octyl-2-oxazoline) segments inside the nanoparticles.

DOI : https://doi.org/10.1016/j.eurpolymj.2018.01.007

D. Bounoua, R. Saint-Martin, S. Petit, P. Berthet, F. Damay, Y. Sidis, F. Bourdarot, and L. Pinsard-Gaudart, Phys. Rev. B 95, 224429

The low energy magnetic excitations spectra of the pristine and doped quasi-one-dimensional spin chains cuprates SrCuO2 have been investigated by inelastic neutron scattering. The momentum-integrated magnetic dynamical structure factor yields a constant integrated intensity with regard to energy in the pure compound, while it shows a strong decay, at low energies, in the compounds doped with nonmagnetic impurities, namely, SrCu0.99M0.01O2 (with M=Zn or Mg) and Sr0.99La0.01CuO2 (Cu+ carrying S=0 created within the chains). These results evidence the opening of a spin pseudogap in the two-spinon continuum of SrCuO2 upon doping, stemming from disruptions of the spin chains by quantum impurities.

Fractionalized excitations that emerge from a many-body system have revealed rich physics and concepts, from composite fermions in two-dimensional electron systems, revealed through the fractional quantum Hall effect, to spinons in antiferromagnetic chains and, more recently, fractionalization of Dirac electrons in graphene and magnetic monopoles in spin ice. Even more surprising is the fragmentation of the degrees of freedom themselves, leading to coexisting and a priori independent ground states.

This puzzling phenomenon was recently put forward in the context of spin ice, in which the magnetic moment field can fragment, resulting in a dual ground state consisting of a fluctuating spin liquid, a so-called Coulomb phase, on top of a magnetic monopole crystal. In a Nature Physics publication it is reported that, by means of neutron scattering measurements, such fragmentation occurs in the spin ice candidate Nd2Zr2O7. A spectacular coexistence of an antiferromagnetic order induced by the monopole crystallization and a fluctuating state with ferromagnetic correlations is observed. Experimentally, this fragmentation manifests itself through the superposition of magnetic Bragg peaks, characteristic of the ordered phase, and a pinch point pattern, characteristic of the Coulomb phase. These results highlight the relevance of the fragmentation concept to describe the physics of systems that are simultaneously ordered and fluctuating.

 

H. le Sueur, P. Joyez, H. Pothier, C. Urbina, and D. Esteve

The Editors of the journal Physical Review Letters recently awarded the label "Editor's suggestion" to an article from the  Quantronics group of SPEC (Laboratory of Condensed Matter Physics) : "Phase Controlled Superconducting Proximity Effect Probed by Tunneling Spectroscopy, Phys. Rev. Lett. 100 (2008) 197002". By this label publishers aim to put forward a small number of items they regard as particularly clear and likely to attract readers outside their specialty.

This paper provides for the first time a neat, clear and complete overview of "the superconducting proximity effect." Such an effect occurs at the interface between metal superconductor (S) and metals with "normal" resistivity (N), in which superconductivity can locally expand within the normal metal and make it non-resistive.

P. Bourges et Y. Sidis IRAMIS/LLB

LLB researchers have published several papers in 2008 in the prestigious journal Science [1-2] and Nature [3]. These results show the full potential of the neutron diffraction techniques at the forefront of research on new materials.

(1,2) B. Toudic, P. Garcia, C. Odin, P. Rabiller, C. Ecolivet and E. Collet,
P. Bourges3, G.J. McIntyre4, M.D. Hollingsworth5, T. Breczewski6

structure urée-alcane

1 Institut de Physique de Rennes, CNRS UMR 6251, Univ. Rennes 1, 35042 Rennes, France
2 CNRS, UMR 6251, IPR, 263 Avenue du Général Leclerc, 35042 Rennes Cedex, France.
3 Laboratoire Léon Brillouin, CEA-CNRS, CEA Saclay, 91191 Gif-sur-Yvette, France
4 Institut Laue-Langevin, 38042 Grenoble Cedex 9, France.
5 Department of Chemistry, Kansas State University, Manhattan, KS 66506, USA.
6 Facultad de Ciencias, Universidad del Pais Vasco, Apdo 644, Bilbao, Spain.


Symmetry and order are essential properties in the description of the various states of matter and their physical properties. These have long been synonymous with periodicity for solids, also used to define the notion of crystal, paradigm for many topics of condensed matter during the XXth century.

One way to probe the structure of matter at the atomic scale is to use radiation diffraction (such as X-rays, or the wave associated with particles: neutrons, electrons ...). The presence of a long-distance order is then characterized by the presence of diffraction peaks, forming an image reflecting the symmetry of the object. This led to the discovery in the recent decades of non-periodic materials, but still with long range order as evidenced by discrete peaks in their diffraction spectrum. Physicists represent this type of crystals as periodic crystals but in a super-space (with dimension 3 + d, which represent the 3 usual dimensions of space and the dimension d of the internal space).

Spectre de diffraction

The systems understudy are aperiodic supramolecular model systems consisting of an urea single crystal (host structure) and alkane molecules (invited molecules), whose length is determined by the number nC of carbon atoms in the molecule (nC>7). Crystalline plane of urea have a structure of hexagonal symmetry. Along the C perpendicular axis, the structure exhibits a double helix forming channels in which alkane molecules may be inserted. At room temperature, these molecules are ordered along the C axis of the urea lattice, but according to an aperiodic order.

 

 


Neutron diffraction spectrum along the C* axis. Crossing the first critical temperature Tc1 superstructure rods (h = 1/2) along C* appear that indicates a change in the symmetry of the system. Along the rods, incommensurate discrete diffraction peaks are characteristic of the new aperiodic ordered structure. This mesh doubling is completely original because the observed phase transition between the two incommensurate phases can be only properly described by means of the 4-dimensional space. A second structural phase appears below Tc2.


 

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