Neus Domingo

Chiral, single-molecule nanomagnets: synthesis, magnetic characterization and natural and magnetic circular dichroism

The first three chiral dodecamanganese clusters that behave as single-molecule magnets are reported. All reveal natural optical activity, which is stronger for the 2-chloropropionate derivative than for either the (S)-6-methoxy-α-methyl-2-naphthaleneacetate or the (S)-2-phenylbutyric acetate compounds. For the cluster with 2-chloropropionate moieties at its periphery, the magnetic circular dichroism was investigated and found to display large optical hysteresis, which depends on the direction in which the magnetic field direction is swept.

Electrocatalytic tuning of biosensing response through electrostatic or hydrophobic enzyme–graphene oxide interactions

The effect of graphene oxidative grades upon the conductivity and hydrophobicity and consequently the influence on an enzymatic biosensing response is presented. The electrochemical responses of reduced graphene oxide (rGO) have been compared with the responses obtained from the oxide form (oGO) and their performances have been accordingly discussed with various evidences obtained by optical techniques. We used tyrosinase enzyme as a proof of concept receptor with interest for phenolic compounds detection through its direct adsorption onto a screen-printed carbon electrode previously modified with oGO or rGO with a carbon-oxygen ratio of 1.07 or 1.53 respectively. Different levels of oGO directly affect the (bio)conjugation properties of the biosensor due to changes at enzyme/graphene oxide interface coming from the various electrostatic or hydrophobic interactions with biomolecules. The developed biosensor was capable of reaching a limit of detection of 0.01 nM catechol. This tuning capability of the biosensor response can be of interest for building several other biosensors, including immunosensors and DNA sensors for various applications.

Exchange bias in a superspin glass system of Co particles in Mn matrix

The magnetic properties of 1.8 nm Co particles dispersed (4.7% volume fraction) in a Mn matrix have been investigated. The results show that the antiferromagnetic matrix provides a strong interface exchange coupling with the ferromagnetic particles and, through it, an effective long range interparticle correlation. This gives rise to a superspin glass type freezing (Tg = 62 K), exchange bias and a remarkable enhancement of thermal stability with respect to the same particles in a Ag matrix, as shown by a shift of the distribution of energy barriers and switching fields to much larger values.

Structuration and integration of magnetic nanoparticles on surfaces and devices

Different experimental approaches used for structuration of magnetic nanoparticles on surfaces are reviewed. Nanoparticles tend to organize on surfaces through self-assembly mechanisms controlled by non-covalent interactions which are modulated by their shape, size and morphology as well as by other external parameters such as the nature of the solvent or the capping layer. Further control on the structuration can be achieved by the use of external magnetic fields or other structuring techniques, mainly lithographic or atomic force microscopy (AFM)-based techniques. Moreover, results can be improved by chemical functionalization or the use of biological templates. Chemical functionalization of the nanoparticles and/or the surface ensures a proper stability as well as control of the formation of a (sub)monolayer. On the other hand, the use of biological templates facilitates the structuration of several families of nanoparticles, which otherwise may be difficult to form, simply by establishing the experimental conditions required for the structuration of the organic capsule. All these experimental efforts are directed ultimately to the integration of magnetic nanoparticles in sensors which constitute the future generation of hybrid magnetic devices.

Interface exchange coupling in Co nanoparticles dispersed in a Mn matrix

The structural and magnetic properties of 1.8 nm Co particles dispersed in a Mn matrix by co-depositing pre-formed mass-selected Co clusters with an atomic vapour of Mn onto a common substrate have been studied by using EXAFS (extended x-ray absorption fine structure), XMCD (x-ray magnetic circular dichroism), magnetometry, and theoretical modelling. At low Co volume fraction (5%) Co@Mn shows a significant degree of alloying and the well-defined particles originally deposited become centres of high Co concentration CoMn alloy that evolves from pure Co at the nanoparticle centre to the pure Mn matrix within a few nm. Each inhomogeneity is a core-shell particle with a Co-rich ferromagnetic core in contact with a Co-depleted antiferromagnetic shell. The XMCD reveals that the Co moment localized on the Co atoms within the Co-rich cores is much smaller than the ferromagnetic moment of the Co nanoparticles deposited at the same volume fraction in Ag. Electronic structure calculations indicate that the small magnitude of the core Co moment can be understood only if significant alloying occurs. Monte Carlo modelling replicates the exchange bias (EB) behaviour observed at low temperature from magnetometry measurements. We ascribe EB to the interaction between the ferromagnetic Co-rich cores and the antiferromagnetic Mn-rich shells.

Synthesis and characterization of a new chiral nanomagnet

The dodecanuclear complexes formed between manganese ions and carboxylate anionic ligands are the single molecule magnets (SMMs) with greatest synthetic accessibility and richness of magnetic properties. In this work, we describe a recently synthesized chiral SMM which presents both spontaneous magnetization and optical activity. This objective has been targeted because of the possibility of observing new phenomena related with the synergy between structural chirality, optical activity, and magnetic ordering.

Surface screening of written ferroelectric domains in ambient conditions

We have combined Piezoresponse Force Microscopy and Kelvin Probe Force Microscopy (KPFM) to study screening charge dynamics in written domains on PbZr0.2Ti0.8O3 (PZT) thin film surfaces under a controlled environment and at variable temperature. The screening dynamics decayed exponentially on a timescale of tens of minutes, consistently with what we expected for water-mediated surface diffusion of ionic species. Variable-temperature KPFM measurements showed variations in surface potential due to temporary unbalanced surface screening charges. Low humidity experiments revealed gradual incorporation of positive charges onto the surface, even in a non-reactive environment (N2), as well as deceleration of the screening dynamics upon reversal of the temperature variation. Our work may serve as a guide for future studies on the dynamics and nature of adsorbates on polarized PZT thin films.

Controlled Positioning of Nanoparticles on Graphene by Noninvasive AFM Lithography

Atomic force microscopy is shown to be an excellent lithographic technique to directly deposit nanoparticles on graphene by capillary transport without any previous functionalization of neither the nanoparticles nor the graphene surface while preserving its integrity and conductivity properties. Moreover this technique allows for (sub)micrometric control on the positioning thanks to a new three-step protocol that has been designed with this aim. With this methodology the exact target coordinates are registered by scanning the tip over the predetermined area previous to its coating with the ink and deposition. As a proof-of-concept, this strategy has successfully allowed the controlled deposition of few nanoparticles on 1 μm(2) preselected sites of a graphene surface with high accuracy.

Metal-radical chains based on polychlorotriphenylmethyl radicals: synthesis, structure, and magnetic properties

We report the synthesis, crystal structures, and magnetic properties of two new metal-radical chains built up from a new class of organic radical-based ligands, the polychlorinated triphenylmethyl (PTM) radicals. Crystal structures of two new 1D coordination polymers, [Cu(2)(PTMDC)(2)(py)(5)(EtOH)].3EtOH (1) and [Co(2)(PTMDC)(2)(DMF)(2)(H(2)O)(6)].5DMF (2) (where PTMDC is a PTM radical functionalized with two carboxylic groups), show similar chain-like structures, in which each of the PTMDC radicals are connecting two Cu(II) or Co(II) metal ions. Therefore, from a magnetic point of view, both structures describe a magnetic chain model based on the PTMDC-M(II) unit. In this manuscript, the magnetic exchange coupling constants between both metal ions and the bridging PTM radicals have been determined. In both cases, the temperature dependence of the magnetic susceptibility reveals antiferromagnetic exchange coupling constants between the PTMDC radicals and Cu(II) (J/k(B) = -42 K) and Co(II) (J/k(B) = -14.6 K) ions based on the exchange Hamiltonian H = -J sum S(A(i))S(A(i+1)).

Ferroelectrics as Smart Mechanical Materials

The mechanical properties of materials are insensitive to space inversion, even when they are crystallographically asymmetric. In practice, this means that turning a piezoelectric crystal upside down or switching the polarization of a ferroelectric should not change its mechanical response. Strain gradients, however, introduce an additional source of asymmetry that has mechanical consequences. Using nanoindentation and contact-resonance force microscopy, this study demonstrates that the mechanical response to indentation of a uniaxial ferroelectric (LiNbO3 ) does change when its polarity is switched, and use this mechanical asymmetry both to quantify its flexoelectricity and to mechanically read the sign of its ferroelectric domains.