Metallurgy and Surfaces group

Czochralski growth of a single crystal of an Al5Fe2 approximant of a decagonal quasicrystalline phase

Czochralski growth of a single crystal of an Al₅Fe₂ approximant of a decagonal quasicrystalline phase

View of a scanning tunneling microscope connected to one of the ultrahigh vacuum platforms (STM, AFM, LEED, XPS, UPS, MBE, SEM, SAM, EBSD)

Atomically resolved STM image (73x73 Å2) of the 5-fold surface of the icosahedral quasicrystal Al-Pd-Mn.

Atomically resolved STM image (73x73 Å²) of the 5-fold surface of the icosahedral quasicrystal Al-Pd-Mn.

Last publications

Heterogeneous nucleation and orientation relationships of icosahedral phase with TiB2 inoculants
Blaž Leskovar, Sašo Šturm, Kemal Delijić, Julian Ledieu, Matejka Podlogar, Sandra Drev, Iztok Naglič, Boštjan Markoli
Journal of Alloys and Compounds, In press, 968, pp.172195. ⟨10.1016/j.jallcom.2023.172195⟩
Revealing the Epitaxial Interface between Al13Fe4 and Al5Fe2 Enabling Atomic Al Interdiffusion
Corentin Chatelier, Kanika Anand, Peter Gille, Marie-Cécile de Weerd, Julian Ledieu, Vincent Fournée, Andrea Resta, Alina Vlad, Yves Garreau, Alessandro Coati, Émilie Gaudry
ACS Applied Materials & Interfaces, 2023, 15 (15), pp.19593-19603. ⟨10.1021/acsami.2c22886⟩
Crystal Structure and Ferromagnetism of the CeFe₉Si₄ Intermetallic Compound
Primož Koželj, Stanislav Vrtnik, Justine Boutbien, Jože Luzar, Andreja Jelen, Sorour Semsari Parapari, Pascal Boulet, Marie-Cécile de Weerd, Gwladys Lengaigne, Magdalena Wencka, Vincent Fournée, Julian Ledieu, Sašo Šturm, Janez Dolinšek
Inorganic Chemistry, 2023, 62 (15), pp.6169-6180. ⟨10.1021/acs.inorgchem.3c00547⟩

Presentation

The Metallurgy and Surfaces research group is conducting research on new intermetallic compounds by studying their structure and properties at the atomic scale, with a particular focus on their surface properties.

These intermetallics are characterized by a large unit cell containing from several tens to several thousands of atoms, arranged into interconnected high-symmetry clusters. Quasicrystals are the ultimate case. They are long-range ordered materials but they lack the translational periodicity characterizing usual crystals. They exhibit classically forbidden symmetries, such as 5-fold or 10-fold rotational symmetries. These complex intermetallics can be found in a large number of binary and ternary systems. Quasicrystalline structures can also occur as 2D oxides or in self-organized molecular thin films.

These materials can have remarkable surface properties (reduced wetting and friction, good corrosion resistance, low thermal conductivity, high catalytic activity and selectivity, etc.). They can find applications as coating materials, as reinforcement particles in composites or as new catalysts for the chemical industry.
Its research seeks for a fundamental understanding of the origin of these properties.
Its activities include:

• Metallurgy of complex intermetallics: synthesis of novel compounds, physical characterization, single crystal growth,
• Experimental investigations of their structure and properties using surface science methods under ultrahigh vacuum conditions (scanning tunneling microscopy, photoemission spectroscopy, low energy electron diffraction, scanning Auger microscopy, electron microscopy)

Keywords

New intermetallic compounds

Surfaces Science

Materials in silico

Catalysis

Scanning tunneling microscopy and Photoemission

2D materials

Research topics

New intermetallic compounds and single crystal growth

The field of intermetallics is extremely rich. It is believed that only a small fraction of existing compounds has been discovered so far: less than 50% of the binary compounds, less than 5% of the ternaries, and probably less than 1% of the quaternaries. Quasicrystalline phases and large unit cell crystals have already been discovered in more than one hundred different systems and the list is constantly growing.
The group is searching for new intermetallic phases, in particular in so-called push-pull systems. These are defined as ternary systems in which two binaries form intermetallic compounds while the third binary does not. Samples are produced by arc-melting, induction melting, sintering or by melt spinning. They are further characterized by differential thermal analysis, X-ray diffraction, or electron and optical microscopy. In favorable cases, large single crystals can be grown by the Czochralski pulling method or by flux. These single crystals are useful to perform surface science experiments and to measure intrinsic physical properties, either at IJL or through national or international collaborations (IRP PAC2S; European CMetAC).

Project:

IRP PAC2S (international associated laboratory between IJL and the Jožef Stefan Institute in Slovenia), 2019-2023.

Article:

Crystalline and electronic structures of the AlV2Sn2-x (x = 0.19) intermetallic compound, Boulet et al., Inorg. Chem.

Surfaces of novel intermetallic compounds

Determining the atomic and electronic structures is essential to understand and optimize the surface properties of these intermetallics. The group has developed an internationally recognized expertise in this field, combining experimental surface science methods and ab initio calculations using the density functionality theory.

Surfaces are investigated at the atomic scale to determine their structure, the surface plane selection mechanisms, the role of chemical bonds, the possible effects of segregation, etc. which lead to specific structure and surface properties.

Projects:

European Integrated Centre for the Development of New Metallic Alloys and Compounds
IRP PAC2S (international associated laboratory between IJL and the Jožef Stefan Institute in Slovenia), 2019-2023.

Articles:

From Surface Structure to Catalytic Properties of Al5Co2(2-10) : a Study Combining Experimental and Theoretical Approaches, Chatelier et al., J. Phys. Chem. C, 2020
Investigation of the (100) and (001) surfaces of the Al5Fe2 intermetallic compound. L. Boulley, D. Kandaskalov, M.C. de Weerd, S. Migot, J. Ghanbaja, S. Sturm, P. Boulet, J. Ledieu, E. Gaudry, V. Fournée.
App. Surf. Sci., 542 (2021) 148540

Thin films and interfaces

The surfaces of intermetallics are used as substrates for the growth of ultra-thin films. In some cases, it is possible to induce some symmetry elements of the substrate into the films and thus to obtain new materials that would not exist otherwise, like quasiperiodic single element metal overlayers or molecular films. 2D quasicrystalline oxide films can also form at the interface by dewetting an epitaxial oxide film grown on a metal substrate.

Interdiffusion can occur at the interface between a thin film and a metal substrate that can result in the formation of intermetallic compounds in the near-surface area, called surface alloying. It allows studying how these complex materials form interfaces with other more conventional ones. The wetting and friction properties also depend on the interfacial structure.

Projects:

OXYQUASI
European Integrated Centre for the Development of New Metallic Alloys and Compounds
IRP PAC2S (international associated laboratory between IJL and the Jožef Stefan Institute in Slovenia), 2019-2023
ANR NOUS

Thèses:

2018-2021, Catalina Ruano-Merchan (MESR)
2018-2021, Dominique Dubaux

Articles:

Metastable Al-Fe intermetallic stabilised by epitaxial relationship. D. Dubaux, E. Gaudry, M.-C de Weerd, S. Sturm, M. Podlogar, J. Ghanbaja, S. Migot, V. Fournée, M. Sicot, J. Ledieu. Applied Surface Science, 533 (2020) 147492
Two-dimensional square and hexagonal oxide quasicrystal approximants in SrTiO3 films grown on Pt(111)/Al2O3(0001). C. Ruano M., T. T. Dorini, F. Brix , L. Pasquier, M. Jullien, D. Pierre, S. Andrieu, K. Dumesnil, S. S. Parapari, S. Šturm, J. Ledieu, M. Sicot, O. Copie, E. Gaudry, and V. Fournée. Phyc. Chem. Chem. Phys., 24 (2022) 7253.

Interactions with the environment

Intermetallic phases exhibit properties of technological interest. Remarkable wetting and friction properties were identified in the group soon after the discovery of quasicrystals and were at the heart of some applications of these materials. The results highlighted unexpected correlations between wetting and friction and the electron density of states. Surface reactivity of these compounds is also investigated currently to understand the mechanisms of oxidation as well as for potential application in heterogeneous catalysis for the chemical industry, aiming to replace noble metals used for certain hydrogenation reactions for example.

Thesis:

Thiago Trevizam-Dorini, 2019-2022, Lorraine University of Excellence (LUE)

Articles:

Catalytic properties of Al13TM4 complex intermetallics: influence of the transition metal and the surface orientation on butadiene hydrogenation, Piccolo et al., Sci. Technol. Adv. Mater., 2019, 20, 557–567.
Non-wetting behavior of Al-Co quasicrystalline approximants owing to their unique electronic structures. K. Anand, V. Fournée, G. Prévôt, J. Ledieu, E. Gaudry. ACS Materials and Interfaces, 12 (2020) 15793–15801

Know-how

Synthesis

Synthesis of novel intermetallic phases (arc melting, induction furnace, melt spinning, sintering) and single crystal growth (Czochralski, flux). Laue diffraction
Preparation of single crystal substrates by ion bombardment and annealing (radiative or electron beam heating) under ultrahigh vacuum conditions
Thin films deposition under ultrahigh vacuum conditions (metal thin films, surface alloying, molecular thin films and oxide thin films).

Characterization

Surface structure determination by low energy electron diffraction (LEED) and scanning tunneling microscopy (STM)
Physical chemistry of metal surfaces by photoemission spectroscopy (XPS, UPS)
Topography, chemistry and structure of solid surfaces at the nanoscale under ultrahigh vacuum conditions (SEM, nanoSAM, EBSD) with the SCAN platform connected to the tube D.A.U.M.

Technology transfer

Development of new composite materials for additive manufacturing technologies in collaboration with the technology research group ‘Materials and processes for additive manufacturing’. Several patents since 2009