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MATISEN team: Materials for information technology, sensing and energy conversion.

Nanomaterials for electronics and sensors

De MATISEN team: Materials for information technology, sensing and energy conversion.
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Electronics is nowadays confronted with miniaturization in order to increase storage densities, which leads to research involving the dimensionality of materials. In this context, the use of quasi-2D (nanometric thin films) or 1D (nanometric-sized nanoparticles) materials with superior electronic, opto-electronic or optical properties (quantum confinement, 2D conductivity, etc.) is essential. Our team studies more particularly the physical processes of elaboration of this type of materials by advanced techniques (laser ablation, ion implantation, ...) and uses adequate post-deposition treatments (thermal or thermo-catalytic treatments under controlled atmosphere, laser, ...) for the ad hoc synthesis of low dimensional materials on/in substrates directly usable or easily integrable for the specifically targeted applications.
By the way, the growing need for sensors accompanies the progress of various techniques for the development of nanomaterials or nano-architected materials based on dielectrics, semiconductors and/or hybrid materials. In this context, the main activities of the Functional Materials and Sensors theme of our team are part of the study of (i) thermal conductivity of materials, (ii) plasmonic sensors based on semiconductor nanoparticles, (iii) chemical sensors based on organic field effect transistors (OFETs) and (iv) quantum sensors. In general, the sensors developed by the team target applications in the fields of energy, health and environment.

Developed topics

Atomic scale modelling of the thermal conductivity of amorphous materials

Member involved : Evelyne Martin, Carlo MASSOBRIO, Mauro BOERO

Collaborations : Guido ORI (IPCMS).

The objective of this activity is to identify reductions in thermal conductivity at nanoscale in amorphous materials used in technology. The calculation is based on first-principles molecular dynamics (FPMD) which uses the density functional theory (DFT) to obtain the interatomic forces. The thermal conductivity is extracted using the Approach-to-Equilibrium Molecular Dynamics (AEMD) method.

Image AEMD.png

This method, the computer analogue of the «Thermal transient gratings» experiment, is based on the creation and exploitation of a sinusoidal temperature profile, the amplitude of which decreases with time. The decay time is directly related to the thermal conductivity of the material. The use of a transient regime makes it possible to obtain thermal conductivity more quickly than with traditional approaches (Green-Kubo, NEMD). The application of AEMD in first-principles molecular dynamics enables to achieve an excellent prediction of experimental and macroscopic values, and to demonstrate a systematic reduction at the nanoscale at dimensions that are nevertheless greater than the range of order in the amorphous materials studied.

Image AEMD2.png

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Plasmonic biosensors based on semiconductor nanoparticles

Persons involved: G. Ferblantier, E. Steveler, D. Muller

Collaborations: IJL (Nancy), CEMES (Toulouse), Mc Master (Canada).

Semiconductor nanoparticles (Nps-SC), especially of silicon, integrated in a dielectric matrix, have aroused great interest in recent decades because of their many possible applications in optoelectronics (IR photonic conversion, heterojunction photovoltaic cells, efficient absorbers). In recent years, electrically doped Nps-SCs have attracted a lot of attention because of the possibility of obtaining localized surface plasmon resonances (LSPRs) whose position can be adjusted according to the amount of free carriers in the particles. This adjustment, which is impossible for metallic nanoparticles, represents a major advance in the use of LSPRs in the field of sensors.
Currently, one of the team's activities is to explore the possibility of using these hyperdoped semiconductor nanoparticles (fabricated by sputtering, PECVD or ion implantation) to generate surface electron waves, i.e., surface plasmons, to detect chemical and/or biological agents by modifying the localized plasmon wave.

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Nanoparticle engineering by ion implantation

Persons involved: G. Ferblantier, E. Steveler, D. Muller

Collaborations: GPM (Rouen)

For many years we have been developing processes based on ion implantation and/or irradiation to fabricate, deform, dope and functionalize nano-objects buried in a matrix to make sensors, memories or optical devices.
The ability to dope quantum dots, and in particular silicon nanocrystals (Si-NC), is a key technological issue for their use in optoelectronic applications. For example, low doping levels are needed to enable applications such as Si-NC-based tandem cells and high doping levels are needed to achieve promising tunable optical properties (via Local Surface Plasmon Resonance - LSPR). (see topic "Functional materials and sensors").
In particular, we have demonstrated the possibility of synthesizing by ion implantation silicon nanocrystals doped with phosphorus and arsenic buried in a matrix of SiO2. This method of synthesis offers good control of the size distribution of the synthesized nanocrystals and of the quantity of dopants incorporated in these nanocrystals. Ion beam synthesis allows the elaboration of silicon nanocrystals with an average size of a few nm. The volume density of dopant-containing nanocrystals ranges from 1018 to a few 1019 particles.cm-3 with an average atomic concentration of dopant in the nanocrystals of ~ 8%. Similar studies are underway to characterize the effect of boron doping.

Figure 6: Spatial distribution of dopants in a Si nanoparticle (left) and concentration profile around a doped nanoparticle determined by Atomic Probe Tomography (APT).

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Chemical sensors based on organic semiconductors

Persons involved: S. Fall, G. Ferblantier, T. Heiser

Collaborations : V. Frick, P.Lévêque (SMH, ICube), J. B. Schell (SMH, ICube), STELORG

Chemical sensors based on organic field effect transistors (OFETs) are currently facing a number of technological challenges such as improving sensitivity, selectivity, ambient stability and manufacturing costs. In ICube's MaCEPV team, we are exploring the performance of different types of organic semiconductor (OSC) based materials in the detection of gas species through morphology control and molecular engineering.
The use of blends of materials makes it possible to increase the selectivity of OFET sensors and the nature of the solubilizing chains increases the sensitivity to certain species. The development of suitable electronics makes it possible to envisage the use of portable sensors based on OFETs. [1]

[1] : V. Frick, P. Lévêque, U. Soysal, T. Heiser, 23rd IEEE International Conference on Electronics Circuits and Systems (ICECS), Monaco, France 2016, doi:10.1109/ICECS.2016.7841194.

Image OFET.png
Structure of an OFET (bottom gate/bottom contact) using a donor material and an electron acceptor material blended in the channel (left) and corresponding transfer characteristic (right).

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Quantum sensors

Persons involved: J. Tribolet, D. Muller

Collaborations: M. Lazar (L2n Troyes)

The "Double Electron Electron Resonance" (DEER), allows the measurement of the magnetic dipole coupling between 2 electron spins using pump-probe magnetic resonance experiments with two different microwave frequencies. Associated with spins of the colored centers obtained by ion implantation (for example the NV center of diamond), this technique allows the detection of a small number of qubits, or even a single spin qubit. We plan to develop this technique (OD-DEER by optical detection of photoluminescence) in order to reach sensitivities of a single spin probe which could eventually have important biomedical applications. However, to achieve such ultimate sensitivity, the DEER methods must be combined with a quantum sensor having one or more optically detectable colored centers near the surface. We are working on developing by ion implantation such colored centers with adequate localization and especially maintaining a sufficient coherence time (qq 10µs) at room temperature.

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Developing topics

Control of qubits in wide gap semiconductor

Persons involved:  : J. Tribolet, D. Muller

Collaborations: C. Couteau, M. Lazar (L2n Troyes)

Quantum technologies are based on the exploitation of the properties of quantum physics for tomorrow's applications: quantum communications, computers and quantum simulators, but also high-resolution sensors (see "Functional materials and sensors" theme). Several wide-gap semiconductors such as diamond, ZnO and SiC will be studied. One part of the studies will consist in positioning by ion implantation paramagnetic defects or coloured centres in diamond or SiC for quantum sensor devices or for the realisation of a quantum register of a few qubits of spins but also for diamond-based photonic devices. Another approach will consist in incorporating by ion implantation magnetic atoms into epitaxial quantum boxes which have shown in the past that they can give rise to couplings between the electron spin of the box exciton and the magnetic spin of the defect in the vicinity of the box. The challenge is to duplicate the phenomenon in diamond and to demonstrate a spin-spin coupling between the spin of a coloured diamond center and the magnetic spin of an atom that would have been implanted not far from the center.

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Archive: old topics

Quasi-D2D graphitic carbon films on insulating substrate for transparent electrode

Persons involved: F. Le Normand, C. Speisser, N. Javahiraly, D. Muller, N. Boubiche

Collaborations: Prof. M. Abdesselam (University of Alger), F. Djeffal (University of Batna II)

For the production of transparent conductive films, a very thin graphite (graphenic) layer can be obtained directly on the surface by partial or total transformation of a Diamond Like Carbon (DLC) film deposited on quartz or glass followed by heat or thermocatalytic treatments. By pulsed laser ablation of graphite at room temperature, a whole class of DLC materials with variable properties (density, sp2/sp3 hybridization ratio, ...) can be obtained depending on the deposition conditions (fluence, thickness, ...). Heat or thermocatalytic treatments change the very thin precursor graphitic layer into a surface graphitic layer by aggregation of the graphitic domains and/or phase transformation of the sp3 carbon (diamond type) (Figure 1). From this point of view, the addition of a very small quantity of transition metal catalyst (less than one monolayer of Fe, Co, Ni), obtained by MBE (at the IPCMS, Strasbourg), proves very beneficial in lowering the temperature and kinetics of these transformations. In addition to its rigidity/hardness, chemical inertness, very low roughness (< 1 nm), the film is transparent in the visible and becomes conductive on the surface.

Figure 1: (left) Experimental film preparation scheme: metal@graphic film/DLC/quartz. (right) Figures of merit (conductivity of transparency) of Ni@graphic film/DLC/quartz and graphic film/DLC/quartz.

The figures of merit for these multilayer systems (graphic film/DLC/quartz or catalyst/graphic film/DLC/quartz) are of the same order of magnitude as for ITO/quartz-based electrodes. In the case of the nickel catalyst, these figures of merit (conductivity of transparency) are even much better than ITO (> 105 Siemens/cm from 400°C), whereas without the catalyst it is necessary to go up to 800-1100°C (Figure 2). The thickness of the initial DLC film, the laser fluence, the gaseous environment of the treatment, the nature rather than the metal concentration, the temperature and the kinetics are the parameters currently studied. They should allow us to develop an efficient device as transparent electrodes but also for other applications such as sensors.

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Nanocrystals of GaN obtained by implantation in dielectric matrices and heat or thermocatalytic treatments in a nitrogenous reducing atmosphere

Persons involved: F. Le Normand, C. Speisser, N. Javahiraly, D. Muller

Collaborations: Lilia Aggar (PhD student), Prof D. Bradai, M. Abdesselam (University of Alger) / C. Bouillet, M. Gallart (IPCMS/Strasbourg)

The formation of GaN nanocrystals in SiO2/Si was obtained by implantation of Ga+ and N+ ions followed by heat or thermocatalytic treatment at 450 to 950°C in nitrogen reducing atmospheres. Analyses by high-resolution electron microscopy (HRTEM), scanning electron microscopy (SEM), high-resolution X-ray diffraction (XRD), absorption fine structure spectroscopy (XAFS) at the K threshold of Ga, and photoelectron (XPS) and Raman spectroscopy show the formation of very small nanocrystals of GaN with wurtzite structure (2-5 nm). The addition of a surface catalyst controls and activates the decomposition of the dinitrogen to mono nitrogen, preventing the diffusion of ions at the surface, selectively activating the formation of GaN (at the expense of Ga or Ga2O3 formation) and increasing the crystallographic quality of the buried GaN particles (Figure 4).

Figure 4: (left) MET image of an implanted layer of GaN on thermal SiO2 in the presence of catalyst; (right) HRTEM of wurtzite GaN particles of size 3-6 nm.

In the presence of the catalyst, photoluminescence spectra characteristic of intense excitonic emission around 3.45 eV and little "yellow light" characteristic of a material where light is emitted by radiative recombination on defects are obtained. The effect of the dielectric matrix, the nature of the gaseous environment being processed and the temperature is currently being actively studied.

The aim is to control the average size (in a range below 3 nm where quantum confinement effects and a shift towards high energies are expected), density and depth distribution of these nanoparticles. In particular, it is envisaged to use this method to build photovoltaic tandem structures by implantation of GaN in transparent DLC.

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Synthesis of graphene by implantation/diffusion of carbon in a metal matrix

Persons involved: F. Le Normand, C. Speisser, D. Muller

We approached the growth of graphene films by a specific process of carbon ion implantation in a thick metal matrix (Ni, Cu), followed by annealing diffusing the carbon either on the surface or at the interface, depending on the depth of implantation, with eventually a specific application concerning transparent electrodes for photovoltaics. The segregation of carbon films at the surface at low energy (20 keV) and at the interface at high energy (180 keV) was demonstrated. While low-pressure nucleation by such a method strongly limits the obtaining of a graphene film, on the other hand, at the interface with a substrate (MgO(111) or SiO2) it has been possible to obtain homogeneous films with both Cu and Ni. This process has also been tested to produce very thin hexagonal boron nitride films by N and B ion implantation and annealing. We will use for this purpose the new potential of very low energy ion implantation being installed in the C3-Fab platform (1 to 10 keV).

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Plasmonic nano-sensors for gas detection

Persons involved: Nicolas Javahiraly, François Le-Normand, Nacer Boubiche

Collaborations: University of Lyon 1.

Hydrogen is presented as the sustainable energy vector of the future, because the hydrogen cycle is one of the most ecological among energy solutions. Hydrogen can be used to produce, store and transport energy and its possible applications are very varied.
However, the use of hydrogen presents a significant risk if it is not controlled because it is explosive at 4% in the air, hence the current need for the development of hydrogen leakage nano-sensors for security issues.
This group activity is devoted to the search for innovative optical hydrogen leakage sensors exploiting the properties of MIM (Metal Insulator Metal) structures, original nanoparticles (simple NPs, core-shell systems, etc.) and their effects (SPR and LSPR ), to bring real progress in detection performance, for example in terms of sensitivity and response time (ANR NHYLEDECT (lead: Nicolas Javahiraly) in collaboration with the University of Lyon 1).

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Figure 1: Example of results obtained in the case of a MIM multilayer structure (Au/ SiO2/Pd) on optical fiber. We will note in dotted line the hydrogenated case.

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Micro-pollutant plasmonic sensors

Persons involved: Nicolas Javahiraly, François Le-Normand

Collaborations: IPCMS, University of Lyon 1.

The detection of micro pollutants by original systems constitutes one of the important challenges of our society. The cancer agency of the WHO (World Health Organization) has classified five pesticides as "possible" or "probable" carcinogens for humans. This activity of the MACEPV group is dedicated to the study of innovative pollutant sensors exploiting the interaction properties between light and original nanostructured materials. The detection is based on the variation of the, for example, optical properties of the materials used in the presence of the molecule to be detected. Several avenues of investigation are being studied: detection by Surface Plasmon Resonance (SPR) or Local Surface Plasmon Resonance (LSPR) and secondly, that using carbonized structures (Diamond-Like Carbon - DLC)) functionalized but also those exploiting the effects of variations of different parameters (conductivity, resistivity, etc.).

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