Plasma Etching development for the advanced nodes using SADP techniques
The miniaturization of the electronics components involves the development of new processes. Indeed, the 193nm immersion lithography alone does not permit anymore to achieve the dimensional requirements of the most advanced technological nodes (=10nm). Since the last 10 years, multi-patterning techniques have been developed to overcome the i193nm lithography limitations. Herein, we will study the « Self-Aligned Double Patterning » (SADP) technique that divides by two the initial pitch of the lithographical patterns. This technology relies on a conformal deposition of a dielectric film (spacer) over the initial patterns (mandrel). The spacers will be then used as a mask during the pattern transfer by plasma etching. The small targeted dimensions require a perfect control of the etching processes. However, the etching steps can damage the materials used herein leading to a dimension loss. One of the main challenge will be to control the etching steps and so the plasma-induced modification in order to satisfy the specifications (dimension, profile, material consumption, etch rate, uniformity…). Besides, the goal will be also to propose new SADP approaches allowing us to generate different type of patterns in order to produce planar FDSOI transistors, which is currently little reported in literature.
The challenges of this PhD ?
To develop innovative etching processes
To explore new couple of material (spacer/mandrel) and to propose an industrial integration flow that will be validated by electrical tests
To identify the technological obstacles and to propose solutions for overcoming them
To put in place a reliable characterization protocol in order to detect the physical and chemical modifications of the materials used and to accurately measure the final patterns’ dimensions
Impact of plasma activation on reliability of Cu/SiO2 hybrid bonding integrations
In recent years, CEA-LETI emerged as a leading force in the development of advanced microelectronic manufacturing processes. A key focus has been on wafer-to-wafer Cu/SiO2 hybrid bonding (HB) process, an emerging technology increasingly employed for producing compact, high performance and multifunctional devices. Before bonding, a crucial surface activation step is necessary to enhance the mechanical strength of the assembled structures. Different approaches have been developed, and the most used in the industry is N2-plasma activation. However, this process remains controversial due to undesirable effects, the formation of Cu nodules at the bonding interface between particularly electrical pads and the passivation of Cu pads with chemical complexes. These issues can significantly compromise the electric properties and reliability of devices. In collaboration with STMicroelectronics and IM2NP, this PhD aims at studying the impact of plasma activation on Cu/SiO2 HB integrations.
Study of catalysis on stainless steels
The materials (mainly stainless steels) aging of the spent nuclear fuel reprocessing plant is the focus of an important R&D activity at CEA. The control of this aging will be achieved by a better understanding the corrosion mechanisms the stainless steels in nitric acid (the oxidizing agent used in the reprocessing steps).
The aim of the PhD is to develop a model of corrosion on a stainless steel in nitric acid as a function of temperature and the acid nitric concentration. This PhD represents a technological challenge because currently few studies exist on in situ electrochemical measurements in hot and concentrated nitric acid. The PhD student will carry out by coupling electrochemical measurements, chemical analyses (UV-visible-IR spectrometry...) and surfaces analyses (SEM, XPS,…). Based on these experimental results, a model will be developed, which will be incorporated in the future in a more global model of the industrial equipments aging of the plant.
The laboratory is specialized in the corrosion study in extreme conditions. It is composed of a very dynamic and motivated scientific team which has the habit to receive students.
Strain field imaging in semiconductors: from materials to devices
This subject addresses the visualization and quantification of deformation fields in semiconductor materials, using synchrotron radiation techniques. The control of the deformation is fundamental to optimize the electronic transport, mechanical and thermal properties.
In a dual technique approach we will combine the determination of the local deviatoric strain tensor by scanning the sample under a polychromatic nano beam (µLaue) and a monochromatic full field imaging with a larger beam (dark field x ray microscopy, DFXM).
New developments of the analysis will be focused on 1/ the improvement of the accuracy and speed of the quantitative strain field determination, 2/ the analysis of strain gradient distributions in the materials, and 3/ the determination of the dynamic strain field in piezoelectric materials through stroboscopic measurements. To illustrate these points, three scientific cases corresponding to relevant microelectronic materials of increasing complexity will be studied:
1- Static strain fields surrounding metallic contacts, such as high-density through silicon vias (TSV) in CMOS technology.
2- Strain gradients in Ge/GeSn complex heteroepitaxial structures with compositional variations along the growth direction.
3- Dynamical strain in LiNbO3 surface acoustic wave resonators with resonance frequency in the MHz range bulk
Establishing this approach will mean moving a step forward towards more efficient microelectronics and strain engineering.
Mesoscopic simulations and development of simplified models for the mechanical behaviour of irradiated concrete
In nuclear power plants, the concrete biological shield serves as a support for the reactor vessel and as a protective shield against radiation. Over the long term, prolonged exposure to neutron radiation can cause the concrete aggregates to expand through amorphisation, leading to micro-cracking and degradation of its mechanical properties. This is an important issue in studies aimed at extending the life of power plants. At the mesoscale, these phenomena can be modelled by separating the behaviour of the aggregates, the cementitious matrix and the interfacial transition zones. However, it is difficult to describe the initiation and propagation of microcracks in such complex heterogeneous multi-cracked systems. The aim of this thesis, carried out as part of a Franco-Czech ANR project, is to develop a high-performance numerical simulation tool for analysing the effects of neutron irradiation on concrete at the mesoscopic scale. A coupled thermo-hydro-mechanical approach will be used in which the behaviour of the matrix will take into account shrinkage, creep and micro-cracking. The simulations will be validated using experimental data obtained on tested samples, and the numerical tool will then be used to estimate the impact of various factors on the behaviour and performance of concrete subjected to neutron irradiation.
This research project is aimed at a PhD student wishing to develop their skills in materials science, with a strong focus on multiphysical and multiscale modelling and numerical simulations.
Complex 3D structuring based on DNA origami
The rapid evolution of new technologies, such as autonomous cars and renewable energy, requires the development of increasingly complex structures. To achieve this, many surface patterning techniques are available today. In microelectronics, optical lithography is the standard method for creating micro- and nanometric patterns. However, it remains limited in terms of the diversity of shapes it can produce.
In recent years, a promising approach has been developed within the laboratories of CBS (INSERM in Montpellier) and the CEA Leti (Grenoble): DNA origami assembly. This technology exploits the self-assembly properties of the DNA origami polymer chain. The assembly of nanometric DNA origami ultimately forms micrometric structures. The aim of this PhD is to explore new perspectives by combining 2D and 3D origami to create novel structures. These patterns could be of great interest for applications in fields such as optics or energy.
Oxide-clad joint and internal corrosion layer modelling in GERMINAL using experimental data provided by different characterisation techniques
This work will be done in the frame of studies on the thermo-mechanical and physico-chemical behaviour behaviour of the « uranium and plutonium mixed oxide fuel » during irradiation currently considered for the future reactors of 4th generation. Because of its particularly hight thermal level during irradiation this kind of fuel is subject to several physical and chemical phenomena duringf its stay in reactor. Those one can have a strong impact on the behaviour of the whole fuel element (pellet and clad), but we can focus on two specific phenomena that take place at middle and high burnup :
- the formation by evaporation-condensation of a fission products layer between the external surface of the fuel pellet and the inner surface of the cladding material at middle burnup, designed as JOG for Joint Oxyde-Gaine;
- the formation of a corrosion layer on the internal surface of the clad, containing fission products and elements constituting the cladding material at high burnup, and resulting from the FCCI (Fuel-Cladding Chemical Interaction),
The occurence of this two phenomena is a limiting factor for increasing the burnup. Thus it is important de be able to estimate quite precisely the chemical composition of the fuel pellet and of the fuel-to-clad gap during irradiation. Previous experimental work had shown that the JOG consisted mainly of caesium, molybdenum and oxygen, with the presence of other elements such as tellurium and barium. Observations have also shown the presence of chromium, iron and nickel, along with other volatile fission products (VFP), in areas of ROG. These observations were backed up by thermodynamic calculations, which led to the assumption that the JOG consisted mainly of caesium molybdate Cs2MoO4. However, until recently, there had been no direct evidence of the presence of this compound. Recently, more detailed characterisation methods carried out as part of a current thesis on (U,Pu)O2 fuel samples confirmed quantitatively that the JOG was mainly made up of Cs, Mo and O, but also of I and Ba distributed in several phases. Other elements were detected and measured in localised areas, namely Te, Zr as well as U and Pu. With regard to corrosion, phases based on Fe, Te and Pd were observed, as well as the joint presence of Cr and O.
At the same time, work was started on modelling the axial redistribution of caesium, with a view to improving the description currently used in GERMINAL. The chemical element inventory at a given axial dimension has a first-order effect on the calculated JOG thickness and ROG thickness.
The aim of this thesis is to improve the description and modelling of JOG and ROG formation in the GERMINAL scientific calculation tool (OCS), which is dedicated to calculating the thermo-mechanical and physico-chemical behaviour of 4th generation reactor fuel irradiated under nominal and/or incidental conditions.
To this end, research will be developed in three areas:
- Further development of the radial migration methodology adopted in the GERMINAL code through comparison with existing and recently obtained experimental results. This is based on a coupling with a thermochemistry module in which several hypotheses for the release of volatile fission products created in the pellet towards the pellet-cladding gap can be considered.
The aim of this PhD subject consists in improving the JOG and FCCI modeling into the fuel performance code (FPC) GERMINAL, dedicated to the calculation of the thermo-mechanical and physico-chemical behaviour of the 4th generation reactors’ fuel irradiated in normal and off-normal conditions. For that purpose, an acurrate experimental caractherization of some irradiated fuel samples, to which the PhD student will contribute, will be elaborated and coupled to a thermodynamic approach. The research will be based on the two items :
- Determination and experimental identification of the chemical elements and phases located into the fuel pellet, into the gap and at the fuel-to-clad interfaces at the end of the irradiation using the implementation of microprobe-SIMS-SEM/FIB techniques, by combining elemental and isotopic analysis results with microscopic observations.
- Comparison of the results with thermodynamic calculations: type and local quantities of the chemical phases formed in the fuel pellet as well as the phases constituting the JOG and those resulting from the FCCI.
Thus, based on those results, it will be possible to evaluate precisely the chemical composition of the irradiated fuel, of the JOG and of the corrosion compounds by using the FPC GERMINAL, from which the input inventory in chemical elements will be estimated in function of burnup at the different radial and axial localisations.
The PhD student will be attached both to a multi-scale modeling group and to an experimental team having sophisticated tools. Furthermore, academic or international collaborations are possible, in particular in the frame of the OECD/NEA with the development of the TAFID database. The student will have the opportunity to enhance the skills learned in the field of nuclear materials characterisation as well as in the field of thermodynamic calculations and irradiated fuel behaviour simulation.
To this end, the research will be developed along three lines:
- Further development of the radial migration methodology adopted in the GERMINAL code through comparison with existing and recently obtained experimental results. This is based on a coupling with a thermochemistry module in which several hypotheses for the release of volatile fission products created in the pellet towards the pellet-cladding gap can be considered.
- Further development of a [simplified] model for the axial redistribution of caesium and, by extension, of volatile fission products, leading to an initial implementation in the GERMINAL code for testing and preliminary validation of the axial inventories estimated by calculation by comparison with experimental results,
- Finally, thermodynamic calculations to determine the nature and local quantity of the chemical phases formed in the fuel pellet and the constituent phases of the JOG and ROG will be carried out on the basis of the axial inventories estimated by the GERMINAL code.
This will enable a more accurate assessment of the chemical composition of the irradiated fuel, the JOG and the ROG products as a function of the burn-up rate using the GERMINAL OCS as a function of time at the various radial and axial locations.
The PhD student will be integrated into the fuel behaviour study and simulation group(IRESNE Institute, CEA CAdarache) which has or is developing various simulation tools, and will also be able to interact with a characterisation laboratory with cutting-edge experimental tools. Academic and international collaborations are also possible, particularly within the OECD/NEA framework with the development of TAFID database. These will enable the PhD student to make the most of the skills he or she has acquired in the field of characterisation of nuclear materials, as well as in thermodynamic calculations and simulation of the physico-chemical behaviour of irradiated nuclear fuel.
Superlattices for the characterization of diffusion under irradiation at the atomic scale
Metal alloys used in nuclear applications are subjected to relatively low temperatures (below 450°C) for long periods of time (more than 10 years). At these temperatures, the kinetics of the diffusion-controlled microstructure transformations are slow. The appearance of certain undesirable phases, likely to embrittle the material, can occur after several years of service. Therefore, diffusion coefficients play a crucial role as input data for modeling the evolution of these microstructures using phenomenological models. However, experimental determination of diffusion coefficients at low temperatures (T < 600°C) is extremely tricky, especially because of the need to characterize nanometric diffusion lengths, a difficulty made all the more difficult in the presence of irradiation.
With the development of chemical analysis by transmission electron microscopy (TEM) and atom probe tomography (APT), it is now possible to experimentally access very small diffusion lengths and thus determine low-temperature diffusion coefficients using superlattices, which consist of stacking nanometric layers of different chemical compositions. We can even characterize the effect of irradiation on diffusion by performing ion irradiations, enabling us to simulate the changes caused by neutron irradiation without activating the materials. The aim of this thesis is to develop a methodology and characterize diffusion under and outside irradiation in a ternary system of interest (Ni-Cr-Fe), representative of the steels and high-entropy considered in the nuclear industry.
This thesis is an opportunity to work with cutting-edge experimental techniques, in close collaboration with a team of theoretician in the same department, as well as with teams specializing in the development of superlattices at UTBM in Belfort and CINAM in Marseille.
Towards an understanding of the expansive behavior of certain cement-based evaporator concentrates: experimental approach and simplified chemistry-transport-mechanics coupled modeling
In the nuclear industry, evaporation is a commonly used process to reduce the volume of low- or intermediate-level radioactive waste before its conditioning. This results in evaporator concentrates, high-salinity solutions that can contain a wide range of ionic species. These concentrates are then stabilized and solidified in a cement-based matrix, a material with many intrinsic qualities (low cost, availability, ease of implementation, good mechanical resistance, stability under irradiation, etc.). However, the acceptance of cemented waste packages in a repository depends on meeting a number of specifications. For instance, it is necessary to demonstrate the absence of expansion that could damage the matrix when stored in a humid environment.
The thesis will aim to understand the mechanisms governing the volumetric changes of cement matrices when stored underwater. The study will be conducted on synthetic waste, simulated by dissolving salts in water at the desired concentrations. It will begin with an experimental phase that will provide the input data for the building of a simplified physico-chemical model of the cement wasteforms to estimate their macroscopic mechanical behaviour as well as the main leached fluxes.
This research project is aimed at a PhD candidate wishing to develop skills in materials science and open new perspectives for the conditioning of radioactive waste. It will be carried out in collaboration with ONDRAF, the Belgian National Agency for Radioactive Waste Management, and will rely on the expertise of two CEA laboratories: the Laboratory of Formulation and Characterization of Mineral Materials (CEA Marcoule) and the Laboratory for the Study of the Behaviour of Concrete and Clays (CEA Saclay).
Freeze-Casting: ice texturing
The thesis topic focuses on MOX fuels with controlled porosity. The student will have to develop a concentrated aqueous suspension in solid phase, dispersed and stable over time with respect to sedimentation. This suspension will be optimized using an experimental design. The tests to be carried out will typically be zeta potential and rheology measurements. The parameters to be taken into account will be the dry matter content as well as the nature and concentration of certain additives (dispersants, surfactants, organic binders) that can be incorporated into the formulation.
In a second step, the texturing conditions by the controlled growth of ice crystals will be explored, again using an experimental design.
After freeze-drying and sintering, the objective is to obtain a residual porosity controlled in size, morphology and interconnection. The sintered microstructures will be characterized by ceramography, scanning electron microscopy, image analysis and X-ray tomography on a line capable of accommodating radioactive materials.