Diap 1.

Good morning everybody. Thanks for the presentation. This time, I’m going to talk about some of results
concerning to my PhD project which is relate with multiferroics, particularly the coupling between a FM
bimetallic nanoalloy of FeRh and a FE surface, that is BaTiO3.

Diap 2

First of all, I would like to put in context what is known about FeRh, the ferromagnetic part.

There exists a phase diagram for FeRh in bulk. As you can see, close to the stoquiometric composition, at
room temperature FeRh alloy presents an antiferromagnetic order. In this phase, no appreciable
magnetic moment can be observed in Rh. However, about the transition temperature of 350 K around,
the magnetic phase becomes ferromagnetic and Rh owns an appreciate magnetic moment, while Fe this
value increases. It is worth mentioning that this transition occurs with no change in the B2 phase
structure.

Diap 3.

On the other hand, both magnetic and structural properties have been studied in size-selected FeRh
nanoclusters with 3 nm in diameter and embedded in an amorphous C matrix. The coupling between
crystallographic structure and magnetic order was followed by EXAFS measurements at the Fe K edge.

After the deposition, the nanoclusters show a chemically disordered FCC structure with an average
lattice parameter of 3.64 Å. When the system is submitted to an annealing (around 900 K), the FCC
structure is transformed into the BCC structure. The lattice parameter changes to a=2.98 Å, which
coincides with bulk B2 FeRh.

On the left, HRTEM image for the as-deposited NP’s looks like are composed of several smaller clusters.
After annealing, a remarkable size homogeneity is observed in the right picture, becomes more
spherical. The average NP diameter is 3.3 nm, and the size distribution has a relative dispersion of 10%.
The NPs are perfectly crystalline with a B2 structure

A. Hillion was a PhD student

Diap 4.

Regarding to the B2 phase chemically ordered NP’s, their magnetic behavior is observed at very low
temperature (below 3 K), since XAS and resulting XMCD spectra exhibit strong dichroism for both atomic
species, and thus do not present the AFM-FM transition like in bulk and thin film specimens. However,
the magnetic moments are comparable with those observed in bulk FeRh above the transition
temperature.

Diap. 5

So, all these results show that the competition between AFM and FM order of FeRh is very sensitive to
many parameters and small changes on the system, such crystallographic structure, size, strain,
stoichiometry, doping, and so on, a motivation arises to study this kind of effects on the alloys,
particularly at the nanoscale.

Diap 6.
Concerning to strain effects, one of the most interesting investigations was published by Cherifi and
collaborators. They have reported the grown of FeRh thin films over a FE BaTiO3 substrate. They found
that using a moderate E it can produces a change in the magnetization inducing a transformation of
FeRh from an AFM to a FM state just above room temperature. This effect is mostly driven by V,
inducing strain effects related to the polarization of the substrate.

This was the starting point to the proposal of our current work which consists of assembly FeRh
nanoclusters with the same ferroelectric surface, and eventually applying an electric field over it to tune
their magnetic properties.

Diap 7

Currently we developing studies on two kind of systems:

On the one hand we have FeRh nanoclusters deposited on a BTO thin film which was epitaxially grown
on a STO single crystal

And on the other, NC’s are deposited on a BTO single crystal oriented in 001 direction.

This time, I just want to show you the results about the first configuration.

Diap 8

The BTO thin film was grown on STO by Molecular Beam Epitaxy with around 4-5 nm of thickness. The
REED images on the left, show a very well contrasted patterns with intense 2D strikes, indicating a good
quality of the film. As is well-know, BTO has several phases which are dependent of the temperature,
but at room temperature BTO presents a tetragonal phase. In bulk, the lattice constants have values
around a= 3.992 and c = 4.03 A, while STO has a cubic phase with a lattice constant of 3.905 A. Because
of the very small thickness of BTO film, one can expect a full strained of BTO on STO, which means lattice
parameter in plane of BTO is almost or is the same than STO.

Diap 9

The structure analysis of thin film on the substrate was followed by XRD, and the diffractogram shows
the peaks corresponding to the BTO and STO signal for the out-of-plane axis, and the fast-map on the
right show the STO signal and a very weak highlight corresponding to BTO, just at the same position,
which confirm the BTO film is fully strained on STO.

Diap 10

For FeRh nanoclusters, these were prepared at the Plyra platform located at iLM, by the Low Energy
Cluster Beam Deposition (LECBD) technique which is a physical method for the synthesis of
nanoclusters, using a laser vaporization source focused on a FeRh target to create a plasma. The main
generators consist in a conventional vacuum chamber for the nucleation, and the second part is an
ultra-high vacuum (UHV) chamber dedicated to the deposition. For the mass-selection, a second
chamber contains an electrostatic quadrupole deviator. The electrodes arranged vertically select a slice
of the ions produced in the cluster beam. With this source the deposition rate is significantly low since
the generator only produces 3 to 5% charged clusters that are deviated by the quadrupole.
So, in this case, the density of the nanoclusters was around 8.8 kcluster/mm2 on the BTO surface and 3
nm in size. After the deposition samples were also covered by an amorphous c-layer to protect against
oxidation and of course, samples were annealed in order to obtain the chemical order B2 phase of FeRh.

Diap 11

In order to observe the signal coming from the FeRh nanoparticles a characterization by synchrotron
techniques was performed. Using Grazing Incidence X-Ray Diffraction with the SIXS beamline at the
Soleil synchrotron, a reciprocal space mapping was taken in the HK0 plane. The highlight spots
corresponding to the substrate, that is BTO/STO. Doing a zoom, for instance, in this part we can observe
two rings which should correspond to the nanoparticles.

Diap. 12

if we try to obtain the lattice constants as of the positions of the rings, we conclude both rings belong to
FeRh, since the values are in good agreement with the reported one. So, it means two orientation for
FeRh nanoparticles can be possible on a perfect substrate, the first one corresponds to the traditional
epitaxy at 45° and the second is observed for the first time as cube on cube epitaxy.

Diap. 13

Assuming that BTO adopts the lattice parameter of STO in plane of course, one can try to determine the
lattice mismatch, now between the interface of the nanocluster and the thin film taking into account the
interfacial planes could be Fe for the nanocluster and TiO2 for the thin film. So, we found that both
orientations have a similar lattice mismatch if we consider 10 cells for BTO and 9 cells for the first case
and 3 cells for BTO and 4 cell FeRh in the second case.

Diap 14

On the other hand, regarding to the magnetic characterization, XMCD measurements were performed
at DEIMOS beamline, also at SOLEIL synchrotron. This is XAS for the L3,2 edges for Fe. The spectra were
taken at room temperature. In these conditions, is possible to observe the characteristic peak for
metallic Fe, but is clear the sample isn’t pure, because of the other small peak at this position. In fact,
this signal means a possible bonding between another thing. Could be oxygen, carbon, we are not sure.
However, we were able to rescue a small XMCD signal, as you can see. Like XMCD is proportional to the
magnetic moment, so, it means at room temperature is possible to see a small magnetic character.

Diap. 15

To finish with this sample, we obtained also the XLD for the L3,2 edges for Ti. In XAS, there seems to be
no difference between vertical linear and horizontal linear polarization. What is clear is that XAS
corresponds to a tetragonal structure, which indicates the detection of BTO even when it has a very
small film thickness.