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International audience; We perform quantitative analysis of the X-ray absorption data taken in situ during the earliest cycles of the ZnO atomic layer deposition on atomically flat InGaAs (001) surfaces. As deposition progresses, we observe a transition from an amorphous structure to a nanocrystalline one. The former retains much of the characteristics of a ZnO crystal in the Zn coordination shell, while the latter shows atomic ordering up to at least the third neighbor shell of Zn atoms, despite the absence of Bragg X-ray diffraction peaks. We show that the different chemical preparation of the substrate surface affects the ZnO local structure and that, counterintuitively, a stronger short-range order is obtained in the nanostructures characterized by lower local order at the interface. We propose a model that accounts for these findings.

In the present study we combined, in the same synchrotron x-ray experiment, reciprocal space mapping, multiwavelength anomalous diffraction and diffraction anomalous fine structure, to determine the strain, crystallographic polarity, alloy composition and ordering at the atomic scale in [0001]-oriented AlGaN nanowires grown by molecular beam epitaxy on GaN nanowire bases. The information that we obtained was averaged over a macroscopic ensemble of NWs. We found from the diffraction anomalous fine structure that there were an isotropic increased number of Ga-Ga pairs in the Ga next nearest coordination shell (cation sublattice) with respect to what is expected for the AlGaN alloy composition determined by anomalous diffraction. This significant deviation from random alloy atomic distribution is present whatever the AlN molar fraction and growth conditions. Our results are consistent with nanoscale composition fluctuations expected from both alloy disorder or kinematically driven spontaneous ordering, both effects being suspected to account for the physical properties of AlGaN ternary alloys., MB was supported by GANEX laboratory of excellence (ANR-11-LABX-0014). Financial support for this work by ANR project ANR-15-CE24-0006 is gratefully acknowledged. We thank the French CRG and SOLEIL commitees for beamtime allocation (proposal number 20151044) and facilities placed at our disposal at beamline BM2-D2AM, and in particular N Boudet and N Blanc, for their help with the experimental setup. MGP acknowledges the Spanish MICINN Grants No. MAT2015-66726-R, and DGA Grant No. E10-17D and Fondo Social Europeo.

International audience; We report on the initial stages of ZnO Atomic Layer Deposition (ALD) on In 0.53 Ga 0.47 As (InGaAs), studied by monitoring the ZnO film thickness in situ with spectroscopic ellipsometry. Using diethylzinc (DEZn) and water, at a substrate temperature equal to 120 • C, we found the presence of two different ZnO growth regimes prior to the steady growth: a slow ZnO nucleation on InGaAs, 0.005 nm.cy −1 (growth delay), then a substrate inhibited growth of type II. Increasing the DEZn injection time, the growth delay shortened from 30 cycles down to 3 cycles, concomitantly the steady growth rate increased from 0.18 to 0.23 nm.cy −1. The DEZn residence time and pressure increase during the first ALD cycle, allowing to suppress the growth delay, instead, no change is observed when performing the same experiment with water. Atomic Force Microscopy (AFM) images showed that the InGaAs surface roughened after the first cycle with a long DEZn pulse and residence time. The rough surface is likely at the origin of the growth delay elimination.

International audience; This study reports the influence of the magnesium incorporation into cuprous oxide (Cu2O) on its transformation in cupric oxide (CuO). Thermal treatments under oxidizing conditions are performed on undoped and magnesium-doped cuprous oxide thin films, Cu2O and Cu2O:Mg respectively, deposited by aerosol-assisted metal organic chemical vapour deposition. The oxidation kinetics of these films shows a slower rate in the Cu2O:Mg system, since the complete oxidation into CuO occurs at a higher temperature when compared to undoped Cu2O. The increased stability of Cu2O:Mg can be explained by the inhibition of the formation of split copper vacancies, the defect most frequently associated with the CuO nucleation. Annealing treatments performed on Cu2O thin films provide new insights on the dopant influence on the mechanism to generate simple and split copper vacancies as well as the transformation of Cu2O into CuO.

InGaAs is one of the III-V active semiconductors used in modern high-electron-mobility transistors or high-speed electronics. ZnO is a good candidate material to be inserted as a tunneling insulator layer at the metal-semiconductor junction. A key consideration in many modern devices is the atomic structure of the hetero-interface, which often ultimately governs the electronic or chemical process of interest. Here, a complementary suite of in situ synchrotron X-ray techniques (fluorescence, reflectivity and absorption) as well as modeling is used to investigate both structural and chemical evolution during the initial growth of ZnO by atomic layer deposition (ALD) on In0.53Ga0.47As substrates. Prior to steady-state growth behavior, we discover a transient regime characterized by two stages. First, substrate-inhibited ZnO growth takes place on InGaAs terraces. This leads eventually to the formation of a 1 nm-thick, two-dimensional (2D) amorphous layer. Second, the growth behavior and its modeling suggest the occurrence of dense island formation, with an aspect ratio and surface roughness that depends sensitively on the growth condition. Finally, ZnO ALD on In0.53Ga0.47As is characterized by 2D steady-state growth with a linear growth rate of 0.21 nm cy-1, as expected for layer-by-layer ZnO ALD.

ZnO thin films are interesting for applications in several technological fields, including optoelectronics and renewable energies. Nanodevice applications require controlled synthesis of ZnO structures at nanometer scale, which can be achieved via atomic layer deposition (ALD). However, the mechanisms governing the initial stages of ALD had not been addressed until very recently. Investigations into the initial nucleation and growth as well as the atomic structure of the heterointerface are crucial to optimize the ALD process and understand the structure–property relationships for ZnO. We have used a complementary suite of in situ synchrotron x-ray techniques to investigate both the structural and chemical evolution during ZnO growth by ALD on two different substrates, i.e., SiO2 and Al2O3, which led us to formulate an atomistic model of the incipient growth of ZnO. The model relies on the formation of nanoscale islands of different size and aspect ratio and consequent disorder induced in the Zn neighbors’ distribution. However, endorsement of our model requires testing and discussion of possible alternative models which could account for the experimental results. In this work, we review, test, and rule out several alternative models; the results confirm our view of the atomistic mechanisms at play, which influence the overall microstructure and resulting properties of the final thin film.

The polarity in ZnO nanowires is an important issue since it strongly affects surface configuration and reactivity, nucleation and growth, electro-optical properties, and nanoscale-engineering device performances. However, measuring statistically the polarity of ZnO nanowire arrays grown by chemical bath deposition and elucidating its correlation with the polarity of the underneath polycrystalline ZnO seed layer grown by the sol-gel process represents a major difficulty. To address that issue, we combine resonant x-ray diffraction (XRD) at Zn K-edge using synchrotron radiation with piezoelectric force microscopy and polarity-sensitive chemical etching to statistically investigate the polarity of more than 107 nano-objects both on the macroscopic and local microscopic scales, respectively. By using high temperature annealing under an argon atmosphere, it is shown that the compact, highly c-axis oriented ZnO seed layer is more than 92% Zn-polar and that only a few small O-polar ZnO grains with an amount less than 8% are formed. Correlatively, the resulting ZnO nanowires are also found to be Zn-polar, indicating that their polarity is transferred from the c-axis oriented ZnO grains acting as nucleation sites in the seed layer. These findings pave the way for the development of new strategies to form unipolar ZnO nanowire arrays as a requirement for a number of nanoscale-engineering devices like piezoelectric nanogenerators. They also highlight the great advantage of resonant XRD as a macroscopic, non-destructive method to simultaneously and statistically measure the polarity of ZnO nanowire arrays and of the underneath ZnO seed layer.

International audience; The growth of zinc oxide thin films by atomic layer deposition is believed to proceed through an embryonic step in which three-dimensional nanoislands form and then coalesce to trigger a layer-by-layer growth mode. This transient initial state is characterized by a poorly ordered atomic structure, which may be inaccessible by X-ray diffraction techniques. In this work, we apply X-ray absorption spectroscopy in situ to address the local structure of Zn after each atomic layer deposition cycle, using a custom-built reactor mounted at a synchrotron beamline, and we shed light on the atomistic mechanisms taking place during the first stages of the growth. We find that such mechanisms are surprisingly different for zinc oxide growth on amorphous (silica) and crystalline (sapphire) substrate. Ab initio simulations and quantitative data analysis allow the formulation of a comprehensive growth model, based on the different effects of surface atoms and grain boundaries in the nanoscale islands, and the consequent induced local disorder. From a comparison of these specttoscopy results with those from X-ray diffraction reported recently, we observe that the final structure of the zinc oxide nanolayers depends strongly on the mechanisms taking place during the initial stages of growth. The approach followed here for the case of zinc oxide will be of general interest for characterizing and optimizing the growth and properties of more complex nanostructures.

International audience; We present a new beamline of Synchrotron SOLEIL dedicated to the study of thin films, nanostructures, and advanced materials via X-ray diffraction and spectroscopy in the energy range 1.4–12 keV. This range covers most of the absorption edges of interest in the fields of semiconductors and functional oxides. In order to meet the increasing demand of advanced real-time characterization of nanoscale materials, the beamline optics and instrumentation have been designed with remarkable dynamic characteristics. SIRIUS presently ends in two experimental stations used for in situ X-ray characterization: a baby chamber and a chemical reactor, both mounted on a large seven-circle diffractometer. The rector is dedicated to atomic layer deposition and metal organic chemical vapor deposition of oxide materials. The third end-station, an in-vacuum diffractometer, will be operative by the end of 2016. SIRIUS offers several synchrotron radiation techniques which can be performed simultaneously or quasi-simultaneously on the same sample. We show here some examples of the first in situ results obtained at the beamline.

International audience; A complementary suite of in situ synchrotron X-ray techniques is used to investigate both structural and chemical evolution during ZnO growth by atomic layer deposition. Focusing on the first 10 cycles of growth, we observe that the structure formed during the coalescence stage largely determines the overall microstructure of the film. Furthermore, by comparing ZnO growth on silicon with a native oxide with that on Al2O3(001), we find that even with lattice-mismatched substrates and low deposition temperatures, the crystalline texture of the films is dependent strongly on the nature of the interfacial bonds.

International audience

International audience; A detailed investigation of the mechanisms related to the low temperature oxidation of nanocrystalline magnetite thin films into maghemite is presented. Despite strong differences in the functional properties of these two phases, structural similarities make it difficult to distinguish between them, and to quantify the oxidation process, particularly in the case of nanostructured polycrystalline layers. Contrary to the case of bulk materials or monocrystalline films and particles, the oxidation processes in nanocrystalline thin film have only scarcely been studied. In this work, structural and optical techniques, including X-ray diffraction (XRD), EXAFS/X-ray absorption near edge structure, FTIR, and Raman scattering, have been used to estimate the oxidation rate of magnetite. The overall oxidation reaction rates are discussed in the framework of two limiting cases corresponding to intra grain diffusion and to grain boundary diffusion. SIMS profiling and electrical measurements were also carried out to better assess the oxidation quantification in order to conclude on the predominant oxidation mechanisms in this heterogeneous material. We propose a qualitative model for the structure, in terms of insulating zone distribution, for partially oxidized films. (C) 2013 American Institute of Physics. [http://dx.doi.org/10.1063/1.4772714]

International audience; Nucleation of GaN nanowires grown by plasma-assisted molecular beam epitaxy is studied through a combination of two in situ tools: grazing incidence x-ray diffraction and reflection high energy electron diffraction. Growth on bare Si(111) and on AlN/Si(111) is compared. A significantly larger delay at nucleation is observed for nanowires grown on bare Si(111). The difference in the nucleation delay is correlated to a dissimilarity of chemical reactivity between Al and Ga with nitrided Si(111).

We applied Grazing Incidence Diffraction Anomalous Fine Structure to the study of the structure of Ge dome-shaped nanoislands, grown by Molecular Beam Epitaxy on Si (0 0 1) substrates at a temperature of 650 °C. We determined the vertical composition of the islands showing the presence of a strong Ge/Si intermixing that is nearly constant from bottom to top. In particular, an abrupt change is found at the substrate interface where the composition switches from pure Si to Ge 0.6Si 0.4. The analysis of the Diffraction Anomalous Fine Structure oscillations of the spectra is crucial to obtain the true composition profile. We performed atomistic simulations to investigate the role of the strained substrate underneath the dome on the diffraction results and to quantify the resolution of our method. Anomalous Diffraction spectra and Diffraction Anomalous Fine Structure oscillations have been simulated for a real size and real shape cluster including faceting, giving a more detailed data interpretation and understanding of the Ge-Si intermixing mechanism. © 2011 Elsevier B.V. All rights reserved., MGP and NAK acknowledge support of Spanish Ministry of Science and Education project MAT2008-03074, J.Z. and G.B. the FWF, Vienna (SFB025).

International audience; no abstract

International audience; Silicon nanowires were grown by gold-catalyzed chemical vapor deposition in the vapor liquid solid mode. In this paper, we use grazing incidence X-ray diffraction and multiwavelength anomalous diffraction to investigate the presence of gold and its effects on silicon nanowire strain after different chemical and physical treatments. We especially focus on the efficiency of the "thermal oxidation-oxide etching" cycle to remove the gold contamination. Analysis reveals a decrease of the contamination and a "core-shell like" spatial distribution of gold, but also shows that this technique is not efficient enough to remove all traces of gold from the nanowires.

International audience

Scattering maps from strained or disordered nano-structures around a Bragg reflection can either be computed quickly using approximations and a (Fast) Fourier transform, or using individual atomic positions. In this article we show that it is possible to compute up to 4.10^10 $reflections.atoms/s using a single graphic card, and we evaluate how this speed depends on number of atoms and points in reciprocal space. An open-source software library (PyNX) allowing easy scattering computations (including grazing incidence conditions) in the Python language is described, with examples of scattering from non-ideal nanostructures., Comment: 7 pages, 4 figures

The growth of GaN nanowires by means of plasma assisted molecular beam epitaxy directly on Si(1 1 1) has been investigated as a function of temperature. Statistical analysis of scanning electron microscopy pictures taken for different growth temperatures has revealed that density, diameter, length and length dispersion of nanowires were strongly dependent on temperature. Length dispersion, in particular, was found to be significant at high temperature. These features have been assigned to the different duration of the nucleation process with temperature, namely to the dependence with temperature of the time necessary for the size increase of the three-dimensional precursors up to a critical value.

International audience; In this paper, we measure experimentally the strains in silicon nanowires using Grazing Incidence X-ray Diffraction. Silicon nanowires have been grown with a gold-catalytic method and have a crystalline character. Bragg's diffraction peak is measured and analyzed. A lattice mismatch parameter between the silicon substrate and silicon nanowires is found and accurately measured. The influence of the presence of the gold catalyst in the wires is investigated, and reveals a small decrease of the lattice mismatch parameter when the gold catalyst is removed. A residual strain is measured and a possible origin is proposed. An estimation of the surface and bulk stress is calculated and presented. (C) 2011 Elsevier B.V. All rights reserved.

Growth of catalyst-free AlN nanowires has been achieved by plasma-assisted molecular beam epitaxy on SiO2/Si (100), by taking advantage of Volmer–Weber growth mode of AlN on amorphous SiO2. Using a combination of high resolution transmission electron microscopy and Raman spectroscopy, it is found that AlN nanowires are completely relaxed, which has been assigned to the compliant character of SiO2. Elastic strain relaxation of AlN nanowires has been further confirmed by photoluminescence experiments, showing in addition that spectra are dominated by near-band edge emission.

International audience; Real-time in-situ X-rays scattering experiments were performed to study the nucleation process of GaN nanowires grown by plasma-assisted molecular beam epitaxy on AlN(0001)/Si(111). From the comparison between the case of nanowires and the case of GaN quantum dots, it is concluded that nanowire precursor islands are completely relaxed from the beginning. Next, based on high resolution electron microscopy analysis, it is demonstrated that relaxation of nanowire precursors is associated to formation of dislocations at the AlN/GaN interface, establishing that three-dimensional islanding and plastic strain relaxation of GaN are two necessary conditions for nanowire growth. Along the same lines, we demonstrate that three-dimensional islanding of AlN on SiO2 leads to formation of AlN nanowires with structural and optical properties characteristic of high quality relaxed material. (C) 2010 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim

The molecular-beam epitaxy growth of AlN/GaN nanowire superlattices has been studied by using a combination of in situ x-ray diffraction experiments, high-resolution electron-microscopy analysis and theoretical calculations performed in a valence force field approach. It is found that the nanowire superlattices are in elastic equilibrium, in contrast with the two-dimensional case but in line with the predicted increase in the critical thickness in the nanowire geometry.

Medium energy ion scattering (MEIS) has been used to measure at the monolayer scale the strain profile of self-organized GaN quantum dots grown on (11–20) or a-plane AlN by molecular-beam epitaxy. By confronting the MEIS results with a structural analysis carried out by atomic force microscopy, it is established that the strain profile is anisotropic, i.e., fully elastic along [1–100] and a combination of plastic and elastic along [0001]. High resolution transmission electron microscopy measurements reveal the presence of misfit dislocations with 1/2 [0001] Burgers vector, consistent with MEIS data.

Since the discovery of graphene, lamellar transition metal disulfides (TMD), such as MoS2 and WS2 , have obtained enormous attention from scientific community. MoS2 and WS2 possess interesting semiconducting properties, and at monolayer, they exhibit remarkable properties, providing benefits in many fields of technology especially in more-than-Moore devices (chemical sensor, photodetector, nanobatteries, etc.). However, it is necessary to fabricate lamellar transition metal disulfide thin films at high temperature (> 850 °C) to obtain crystalline phase with the desired properties. Such high temperature is actually limiting the choice of substrate and prevents the direct integration of lamellar transition metal disulfides on integrated circuit (IC). Therefore, in this thesis, I have studied two approaches to fabricate lamellar transition metal disulfide thin films at lower temperature, based on sulfurization of metal or metal oxide thin film with organosulfur precursor. The first approach involves the use of a metal promotor which is capable to enhance crystallization of group 6B transition metal disulfides and therefore decrease the temperature required to get a sufficiently crystalline layer. In this approach, I studied sulfurization of W metal film with 1,2-ethanedithiol (EDT) in the presence of Ni to produce WS2 thin film. Ni promotor strongly enhances the crystallization of WS2 above 650 °C. However, WS2 layers produced through this approach are contaminated with NiSx residues, whose selective removal remains challenging. The second approach is the selection of a non-transition metal disulfide sharing similar structures and properties with lamellar transition metal disulfides, but having a much lower melting point: SnS2 . Highly crystalline and oriented SnS2 thin films are successfully obtained by sulfurizing SnO2 thin films with di(t-butyl)disulfide (TBDS) at 350 °C, and upon changing the organosulfur precursor from di(t-butyl)disulfide (TBDS) to t-butylthiol (TBT), the sulfurization can also produce the lamellar SnS phase below 400 °C. Thanks to their low sulfurization temperatures, SnS2 and SnS can be directly fabricated on integrated circuit, and they can be used in a photodetector or neuromorphic devices.; Depuis la découverte du Graphène, les disulfures de métaux de transition lamellaires (tels que MoS2 ou WS2) ont suscité un grand intérêt au sein de la communauté scientifique. MoS2 et WS2 montrent des propriétés semi-conductrices intéressantes et lors de l’épaisseur de monocouche, ils présentent des propriétés remarquables bénéficiant à plusieurs domaines d’applications, et plus particulièrement le « More-than-Moore » (capteurs chimiques, photodétecteurs, nano-batteries). En revanche, l’élaboration de ces sulfures lamellaires nécessite des températures très élevées (> 850 °C) afin d’obtenir un matériau cristallin, et donc d’obtenir les propriétés recherchées. Ces températures élevées limitent le choix du substrat, et s’empêchent l’intégration directe sur circuit intégré (IC). Dans cette thèse, j’ai étudié deux approches permettant d’obtenir des couches minces de disulfure de métaux de transition lamellaire à basse température en utilisant un procédé de sulfuration d’une couche mince de métal ou d’oxyde de métal par des molécules organosoufrées. La première approche consiste à utiliser un promoteur (ou dopant) permettant de faciliter la cristallisation des sulfures de métaux de transition du groupe 6B, et ainsi diminuer la température nécessaire à l’obtention de couches minces suffisamment cristallines. Dans cette partie, j’ai étudié la formation d’une couche mince de WS2 par sulfuration d’un film de tungstène en présence de nickel. La présence de Nickel a permis d’améliorer significativement la cristallinité des films de WS2 à partir de 650 °C, et d’obtenir des tailles de grains de l’ordre du µm. Néanmoins, les films de WS2 obtenus par cette approche sont contaminés par des résidus de NiSx dont le retrait sélectif reste un challenge. La seconde approche consiste à utiliser un disulfure alternatif à MoS2 et WS2 présentant des propriétés physico-chimiques semblables, mais présentant un point de fusion beaucoup plus bas : SnS2 . La sulfuration de couches minces de SnO2 en présence de disulfure de di-t-butyle (TBDS) à 350 °C a ainsi permis d’obtenir des films de SnS2 orientés et présentant une excellente cristallinité. J’ai également pu démontrer l’influence du précurseur organosoufré sur la phase de sulfure d’étain formée, et pu obtenir des couches minces de SnS au-dessous de 400 °C en utilisant le t-butylthiol (TBT). Grâce à leurs basses températures de sulfuration, SnS2 et SnS pourraient être directement fabriqués sur circuit intégré (IC) et utilisés dans un photodétecteur ou des dispositifs neuromorphiques.

This work focuses on the study of the initial stages of ZnO atomic layer deposition (ALD) on atomically flat (100) In0.57Ga0.43As surface, notably by using in situ synchrotron techniques. Due to high electron mobility, III-V InGaAs semiconductor has been recognized as a promising material to replace Silicon channel in the metal-oxide-semiconductor-field-effect transistors (MOSFET). Ultrathin ZnO layer on InGaAs can be used as a passivation layer at the interface with the gate transistor dielectric, as well as tunneling layer inserted in between metal/InGaAs contact to decrease the Schottky barrier height and the contact resistance. In the recent years, ALD technique based on self-limiting surface chemical reactions has received world-wide attention for manufacturing highly conformal and homogeneous thin films with sub-nanometer thickness control at low temperatures compatible with industry specifications. However, the growth behavior strongly differs depending on the substrate surfaces. Thus for the creation of few monolayers thick films, the study of ALD in the initial stages of growth is of particular interest for improving the understanding of the growth mechanisms.For that purpose, we have developed and upgraded a thermal ALD reactor (MOON:MOCVD/ALD growth of Oxide Nanostructures) dedicated to monitor the growth of materials by in situ characterization techniques. The MOON reactor can be moved to synchrotron centers for monitoring material growth in situ by using X-ray based techniques, notably X-ray fluorescence, X-ray absorption, XRR, and grazing incidence diffraction. Also, optical in situ techniques can be used in the laboratory. In this work, we show the results of experiments obtained at two synchrotron beamlines, i.e. SIRIUS (SOLEIL, Saint-Aubin (France)) and ID3 (ESRF, Grenoble (France)).We show that ZnO growth in the initial stages is inhibited by the (100) InGaAs substrate, leading to a transient regime prior to the steady ALD is achieved. We report a detailed investigation of this transient regime and find that an ultra-thin (~1-nm-thick) 2D layer is indeed fabricated but with a growth rate so low that one may believe that nothing has been deposited on the surface. We identify the structural and chemical properties of that ultra-thin layer. Only afterward does the substrate inhibited of type 2 growth mode begins: as the cycle number increases, the growth per cycle (GPC) increases, then reaches a maximum and level down to a constant value (steady growth). For a better understanding of the 3D growth mode by reproducing the experimental growth per cycle curves we have developed a geometric model that schematizes the growth of hemispheroid islands by ALD. We show that this model allows obtaining quantitative growth parameters.When water is used as a reactant, we showed that by changing the water flow during the ALD process, it is possible to control the time delay (or cycle number) prior to 3D growth begins. It is very likely that the water flow controls the density of hydroxyl groups on the InGaAs surface. We also demonstrated ZnO ALD for different InGaAs substrate temperatures. By combining in situ X-ray absorption and grazing incidence scattering techniques, we identified a short-range-order atomic structure of the ZnO material, with an embryonic ZnO wurtzite, prior to 3D growth, then a long-range-order structure is detected both by X-ray absorption and X-ray diffraction, together with the appearance of a microstructure. At higher growth temperature, outside of the ALD window, we observed the well-known ZnO texturing when the layer thickness increases.At last, we report on the use of ultrathin ZnO layers on InGaAs in the electrical contact structure. The contact resistance of metal/ZnO/InGaAs samples was measured using Transfer Length Method (TLM). We show that specific contact resistivity of Al/p-InGaAs pads is reduced by inserting a ZnO tunnel layer in between Al and p-doped InGaAs.; Ce travail porte sur l'étude des étapes initiales du dépôt de couches atomiques de ZnO (ALD) sur une surface (100) de In0,57Ga0,43As, par l'utilisation de techniques de caractérisation in situ (rayonnement synchrotron). En raison de la grande mobilité des électrons, le semi-conducteur III-V InGaAs est un matériau potentiel pour remplacer le canal de Silicium dans les transistors à effet de champ (MOSFET). Afin de diminuer la hauteur de la barrière Schottky et la résistance de contact, une couche ultra-mince (tunnel) de ZnO peut être insérée entre le métal et le semiconducteur InGaAs. Au cours de ces dernières années, la technique ALD, compatible avec les spécifications de l'industrie et basée sur des réactions chimiques de surface auto-limitantes, est utilisée pour la fabrication de films minces conformes et homogènes avec un contrôle sub-nanométrique de l’épaisseur. Cependant, le comportement au cours de la croissance diffère fortement en fonction de la surface du substrat. Ainsi, l'étude des premières étapes ALD est particulièrement intéressante afin d’améliorer la compréhension des mécanismes de croissance en vue de la création de films ultra-minces.Pour ce faire, nous avons développé et mis à niveau un réacteur thermique ALD (MOON) dédié. Il peut être installé sur des lignes de lumière synchrotron afin d’étudier la croissance des matériaux in situ avec des techniques telles que la fluorescence X, l’absorption X, la spectroscopie des rayons X ainsi que la diffraction X en incidence rasante. De plus, des techniques optiques de caractérisation in situ peuvent être utilisées en laboratoire ou couplées en milieu synchrotron. Les expériences au synchrotron ont été réalisées sur les lignes de lumière SIRIUS (SOLEIL, Saint-Aubin (France)) et ID3 (ESRF, Grenoble (France)).Nous montrons que dans sa phase initiale, la croissance ALD de ZnO est inhibée par le substrat (100) InGaAs, ce qui conduit à un régime transitoire avant le régime de croissance ALD stable. La première phase du régime transitoire conduit à la formation d’une couche d’oxyde de Zinc, ultra-mince (~1 nm d'épaisseur), fabriquée avec un taux de croissance très faible. L'absorption X et la diffusion X en incidence rasante montrent qu’à ce stade le matériau ZnO est désordonné (non cristallisé) et présente un ordre à courte distance caractérisé par une structure wurtzite embryonnaire. Ensuite, le régime transitoire entre dans une deuxième phase (croissance 3D), le taux de croissance par cycle (GPC) augmente, atteint un maximum puis diminue jusqu'à une valeur constante (croissance ALD stable). Afin de mieux comprendre le mode de croissance 3D nous avons développé un modèle géométrique qui schématise la croissance d’îlots hémisphériques par ALD. Ce modèle permet d'obtenir des paramètres quantitatifs de croissance.En modifiant le débit d’eau (H2O) utilisée comme réactif pendant le processus ALD, il est possible de contrôler le délai (ou le nombre de cycles) avant le début de la croissance 3D. Cet effet est très probablement lié à la variation de la densité des groupes hydroxyle à la surface de l'InGaAs. Par ailleurs, nous avons caractérisé la croissance ALD de ZnO pour différentes températures du substrat InGaAs (dans et hors fenêtre ALD). Les cartes de diffusion des RX réalisées en cours de dépôt, montrent l’apparition d’une phase cristallisée à longue distance en lien avec le démarrage de la croissance 3D. À température élevée, hors de la fenêtre ALD, nous observons une texturation de la couche ZnO lorsque son épaisseur augmente. Aucune relation d’épitaxie n’est observée.Enfin, nous rendons compte de l'utilisation de couches ZnO ultraminces sur InGaAs pour les contacts électriques. La résistance de contact des échantillons de métal/ZnO/InGaAs a été mesurée à l'aide de la méthode Transfert Length Method (TLM). Nous montrons que la résistivité de contact spécifique des tampons Al/p-InGaAs est réduite par l’insertion d’une couche tunnel ZnO entre l'Al et l'InGaAs dopé p.

This work focuses on the study of the initial stages of ZnO atomic layer deposition (ALD) on atomically flat (100) In0.57Ga0.43As surface, notably by using in situ synchrotron techniques. Due to high electron mobility, III-V InGaAs semiconductor has been recognized as a promising material to replace Silicon channel in the metal-oxide-semiconductor-field-effect transistors (MOSFET). Ultrathin ZnO layer on InGaAs can be used as a passivation layer at the interface with the gate transistor dielectric, as well as tunneling layer inserted in between metal/InGaAs contact to decrease the Schottky barrier height and the contact resistance. In the recent years, ALD technique based on self-limiting surface chemical reactions has received world-wide attention for manufacturing highly conformal and homogeneous thin films with sub-nanometer thickness control at low temperatures compatible with industry specifications. However, the growth behavior strongly differs depending on the substrate surfaces. Thus for the creation of few monolayers thick films, the study of ALD in the initial stages of growth is of particular interest for improving the understanding of the growth mechanisms.For that purpose, we have developed and upgraded a thermal ALD reactor (MOON:MOCVD/ALD growth of Oxide Nanostructures) dedicated to monitor the growth of materials by in situ characterization techniques. The MOON reactor can be moved to synchrotron centers for monitoring material growth in situ by using X-ray based techniques, notably X-ray fluorescence, X-ray absorption, XRR, and grazing incidence diffraction. Also, optical in situ techniques can be used in the laboratory. In this work, we show the results of experiments obtained at two synchrotron beamlines, i.e. SIRIUS (SOLEIL, Saint-Aubin (France)) and ID3 (ESRF, Grenoble (France)).We show that ZnO growth in the initial stages is inhibited by the (100) InGaAs substrate, leading to a transient regime prior to the steady ALD is achieved. We report a detailed investigation of this transient regime and find that an ultra-thin (~1-nm-thick) 2D layer is indeed fabricated but with a growth rate so low that one may believe that nothing has been deposited on the surface. We identify the structural and chemical properties of that ultra-thin layer. Only afterward does the substrate inhibited of type 2 growth mode begins: as the cycle number increases, the growth per cycle (GPC) increases, then reaches a maximum and level down to a constant value (steady growth). For a better understanding of the 3D growth mode by reproducing the experimental growth per cycle curves we have developed a geometric model that schematizes the growth of hemispheroid islands by ALD. We show that this model allows obtaining quantitative growth parameters.When water is used as a reactant, we showed that by changing the water flow during the ALD process, it is possible to control the time delay (or cycle number) prior to 3D growth begins. It is very likely that the water flow controls the density of hydroxyl groups on the InGaAs surface. We also demonstrated ZnO ALD for different InGaAs substrate temperatures. By combining in situ X-ray absorption and grazing incidence scattering techniques, we identified a short-range-order atomic structure of the ZnO material, with an embryonic ZnO wurtzite, prior to 3D growth, then a long-range-order structure is detected both by X-ray absorption and X-ray diffraction, together with the appearance of a microstructure. At higher growth temperature, outside of the ALD window, we observed the well-known ZnO texturing when the layer thickness increases.At last, we report on the use of ultrathin ZnO layers on InGaAs in the electrical contact structure. The contact resistance of metal/ZnO/InGaAs samples was measured using Transfer Length Method (TLM). We show that specific contact resistivity of Al/p-InGaAs pads is reduced by inserting a ZnO tunnel layer in between Al and p-doped InGaAs., Ce travail porte sur l'étude des étapes initiales du dépôt de couches atomiques de ZnO (ALD) sur une surface (100) de In0,57Ga0,43As, par l'utilisation de techniques de caractérisation in situ (rayonnement synchrotron). En raison de la grande mobilité des électrons, le semi-conducteur III-V InGaAs est un matériau potentiel pour remplacer le canal de Silicium dans les transistors à effet de champ (MOSFET). Afin de diminuer la hauteur de la barrière Schottky et la résistance de contact, une couche ultra-mince (tunnel) de ZnO peut être insérée entre le métal et le semiconducteur InGaAs. Au cours de ces dernières années, la technique ALD, compatible avec les spécifications de l'industrie et basée sur des réactions chimiques de surface auto-limitantes, est utilisée pour la fabrication de films minces conformes et homogènes avec un contrôle sub-nanométrique de l’épaisseur. Cependant, le comportement au cours de la croissance diffère fortement en fonction de la surface du substrat. Ainsi, l'étude des premières étapes ALD est particulièrement intéressante afin d’améliorer la compréhension des mécanismes de croissance en vue de la création de films ultra-minces.Pour ce faire, nous avons développé et mis à niveau un réacteur thermique ALD (MOON) dédié. Il peut être installé sur des lignes de lumière synchrotron afin d’étudier la croissance des matériaux in situ avec des techniques telles que la fluorescence X, l’absorption X, la spectroscopie des rayons X ainsi que la diffraction X en incidence rasante. De plus, des techniques optiques de caractérisation in situ peuvent être utilisées en laboratoire ou couplées en milieu synchrotron. Les expériences au synchrotron ont été réalisées sur les lignes de lumière SIRIUS (SOLEIL, Saint-Aubin (France)) et ID3 (ESRF, Grenoble (France)).Nous montrons que dans sa phase initiale, la croissance ALD de ZnO est inhibée par le substrat (100) InGaAs, ce qui conduit à un régime transitoire avant le régime de croissance ALD stable. La première phase du régime transitoire conduit à la formation d’une couche d’oxyde de Zinc, ultra-mince (~1 nm d'épaisseur), fabriquée avec un taux de croissance très faible. L'absorption X et la diffusion X en incidence rasante montrent qu’à ce stade le matériau ZnO est désordonné (non cristallisé) et présente un ordre à courte distance caractérisé par une structure wurtzite embryonnaire. Ensuite, le régime transitoire entre dans une deuxième phase (croissance 3D), le taux de croissance par cycle (GPC) augmente, atteint un maximum puis diminue jusqu'à une valeur constante (croissance ALD stable). Afin de mieux comprendre le mode de croissance 3D nous avons développé un modèle géométrique qui schématise la croissance d’îlots hémisphériques par ALD. Ce modèle permet d'obtenir des paramètres quantitatifs de croissance.En modifiant le débit d’eau (H2O) utilisée comme réactif pendant le processus ALD, il est possible de contrôler le délai (ou le nombre de cycles) avant le début de la croissance 3D. Cet effet est très probablement lié à la variation de la densité des groupes hydroxyle à la surface de l'InGaAs. Par ailleurs, nous avons caractérisé la croissance ALD de ZnO pour différentes températures du substrat InGaAs (dans et hors fenêtre ALD). Les cartes de diffusion des RX réalisées en cours de dépôt, montrent l’apparition d’une phase cristallisée à longue distance en lien avec le démarrage de la croissance 3D. À température élevée, hors de la fenêtre ALD, nous observons une texturation de la couche ZnO lorsque son épaisseur augmente. Aucune relation d’épitaxie n’est observée.Enfin, nous rendons compte de l'utilisation de couches ZnO ultraminces sur InGaAs pour les contacts électriques. La résistance de contact des échantillons de métal/ZnO/InGaAs a été mesurée à l'aide de la méthode Transfert Length Method (TLM). Nous montrons que la résistivité de contact spécifique des tampons Al/p-InGaAs est réduite par l’insertion d’une couche tunnel ZnO entre l'Al et l'InGaAs dopé p.

The work presented in this manuscript deals with the structural investigation of III-nitrides semiconductor heterostructures with one of the most powerful tools of materials science: the synchrotron radiation. We used high resolution reciprocal space mapping, multi-wavelenght anomalous diffraction, x-rays absorption spectroscopy and diffraction anomalous fine structure to characterize the structure at the atomic scale of complex nano-structured systems. First, we show that GaN nanowires on Si(111) are N-polar and we suggest a nucleation mecanism. Then, we highlight a strain assited inter-diffusion phenomenon in the GaN / AlN quantum dots annealed at high temperature. Finally, we observe the presence of short-range order in InGaN / GaN core-shell nanowires. This atomic organization could be induced by the presence of stress and we have begun a study of the anisotropic ordering to explore this hypothesis.; Le travail illustré par ce manuscrit de thèse présente l'étude structurale d'hétéro-structures semi-conductrices à base de nitrures d'éléments III avec l'un des outils les plus puissants de la recherche scientifique: le rayonnement synchrotron. La cartographie haute résolution de l'espace réciproque, la diffraction anomale multi-longueur d'onde, la spectroscopie d'absorption X et la spectroscopie en condition de diffraction nous ont permis de caractériser la structure à l'échelle atomique de différentes régions d'un même système. Dans un premier temps, nous montrons que les nanofils GaN sur Si(111) ont une polarité N et proposons un mécanisme de nucléation. Dans un second temps, nous mettons en évidence un phénomène d'inter-diffusion stimulée par la contrainte dans les boîtes quantiques GaN / AlN recuites à haute température. Enfin, nous observons la présence d'un ordre local à courte distance dans les nanofils coeur-coquille InGaN / GaN. Cette organisation atomique pourrait être induite par la présence de contrainte, nous avons initié une étude de l'anisotropie de l'ordre à courte distance pour explorer cette hypothèse.

The work presented in this manuscript deals with the structural investigation of III-nitrides semiconductor heterostructures with one of the most powerful tools of materials science: the synchrotron radiation. We used high resolution reciprocal space mapping, multi-wavelenght anomalous diffraction, x-rays absorption spectroscopy and diffraction anomalous fine structure to characterize the structure at the atomic scale of complex nano-structured systems. First, we show that GaN nanowires on Si(111) are N-polar and we suggest a nucleation mecanism. Then, we highlight a strain assited inter-diffusion phenomenon in the GaN / AlN quantum dots annealed at high temperature. Finally, we observe the presence of short-range order in InGaN / GaN core-shell nanowires. This atomic organization could be induced by the presence of stress and we have begun a study of the anisotropic ordering to explore this hypothesis., Le travail illustré par ce manuscrit de thèse présente l'étude structurale d'hétéro-structures semi-conductrices à base de nitrures d'éléments III avec l'un des outils les plus puissants de la recherche scientifique: le rayonnement synchrotron. La cartographie haute résolution de l'espace réciproque, la diffraction anomale multi-longueur d'onde, la spectroscopie d'absorption X et la spectroscopie en condition de diffraction nous ont permis de caractériser la structure à l'échelle atomique de différentes régions d'un même système. Dans un premier temps, nous montrons que les nanofils GaN sur Si(111) ont une polarité N et proposons un mécanisme de nucléation. Dans un second temps, nous mettons en évidence un phénomène d'inter-diffusion stimulée par la contrainte dans les boîtes quantiques GaN / AlN recuites à haute température. Enfin, nous observons la présence d'un ordre local à courte distance dans les nanofils coeur-coquille InGaN / GaN. Cette organisation atomique pourrait être induite par la présence de contrainte, nous avons initié une étude de l'anisotropie de l'ordre à courte distance pour explorer cette hypothèse.

This work focuses on the growth by plasma-assisted molecular beam epitaxy and on the characterization of GaN nanowires (NWs) and of GaN/AlN NW heterostructures. We first investigate GaN NW morphology (density, mean length, mean diameter, length dispersion) dependence on the growth parameters. Using reflection high energy electron diffraction, GaN NW morphology is correlated to their nucleation dynamics. In situ grazing-incidence X-ray diffraction experiments performed at the ESRF allow clarifying GaN NW nucleation processes on bare Si(111) and when usinga thin AlN buffer deposited on Si(111). The use of resonant X-ray diffraction for the determination of GaN NW polarity is then successfully demonstrated. GaN NWs grown on bare Si(111) are shown to be N-polar. Additional KOH selective etching tests reveal that both GaN NWs grown using a thin AlN buffer on Si(111) and when pre-depositing Ga on the Si(111) surface are N-polar, too. Regarding GaN-AlN NW heterostructures, the growth of an AlN shell around GaN NWs is studied as a function of various growth parameters. The AlN shell aspect ratio is described by a geometrical model. Using a combination of multiwavelength anomalous diffraction, high resolution transmission microscopy and theoretical calculations, GaN core strain state is investigated as a function of the AlN shell thickness. This strain is shown to increase with the shell thickness as long as AlN grows homogeneously around GaN NWs. When the shell is asymmetric, the system relaxes plastically. Eventually, we study the possibility to fabricate island-like GaN insertions in AlN NWs. We determine the critical AlN NW radius above which GaN undergoes a 2D to 3D shape-transition. Regarding optical properties of these novel structures, the presence of multiple localized states is identified., Ce travail de thèse porte sur la croissance par épitaxie par jets moléculaires assistée plasma et sur la caractérisation de nanofils (NF) de GaN et d'hétérostructures filaires de GaN/AlN. Dans un premier temps, la morphologie des NFs de GaN (densité, longueur moyenne, diamètre moyen, dispersion de longueurs) est étudiée en fonction des paramètres de croissance. Via la diffraction d'électrons rapides, la morphologie des NFs GaN est corrélée à la dynamique de nucléation de ces derniers. Des expériences de diffraction de rayons X en incidence rasante effectuées à l'ESRF permettent également de clarifier les processus de nucléation des NFs GaN. Nous démontrons ensuite l'utilisation de la diffraction de rayons X résonnante pour déterminer la polarité des NFs GaN. Nous montrons que ces derniers sont de polarité N lorsque fabriqués sur Si nu. Des tests complémentaires de gravure sélective au KOH révèlent que les NFs GaN fabriqués sur un substrat de Si recouvert d'un fin buffer d'AlN ainsi que ceux dont la fabrication est initiée après pré-déposition de Ga sur la surface du Si, sont aussi de polarité N. Concernant les hétérostructures filaires GaN-AlN, la croissance d'AlN autour et sur les nanofils de GaN est étudiée en fonction de divers paramètres de croissance. Le rapport d'aspect des coquilles d'AlN (longueur/épaisseur) est décrit par un modèle géométrique. En utilisant une combinaison de diffraction anomale multi-longueurs d'onde, de microscopie en transmission de haute résolution et des calculs théoriques, l'état de contrainte des coeurs de GaN est analysé en fonction de l'épaisseur de la coquille. Cette contrainte augmente avec l'épaisseur de la coquille tant que l'AlN croît de manière homogène autour des NFs de GaN. Dès lors que la coquille est asymétrique, le système relaxe plastiquement. Nous étudions enfin la possibilité de fabriquer des îlots de GaN dans des NFs AlN. Nous déterminons le rayon critique de NFs AlN au-dessus duquel le GaN déposé subit une transition de forme de 2D à 3D. L'analyse des propriétés optiques de ces nanostructures originales revèle la présence de nombreux états localisés.

The works presented in this manuscipt focus on the structural (size, strain, composition) investigation of GaN/AlN quantum dots, by means of x-ray spectroscopy in diffraction condition and x-ray anomalous diffraction and scattering. Those works are associated to Reflection High-Energy Electron Diffraction (RHEED), Transmission Electron Microscopy (TEM), Atomic Force Microscopy (AFM) and Medium-Energy Ion Scattering (MEIS) measurements.The measurement of fine structure oscillation in diffraction condition (x-ray spectroscopy in diffraction condition) and anomalous diffraction, using a grazing incidence setup, which is necessary for the study of nanoobjects, promoted specific experimental developments. Together with those developments, efforts were undertaken to properly take into account dynamical effects occuring in grazing incidence, for the quantitative analysis of the experimental results. Moreover, experimental results were compared with simulations of x-ray diffraction diagrams, fine structure signal in diffraction condition and anomalous diffraction spectrum, performed on the basis of simulations of the strain fields in the quantum dots.The capping of (0001) GaN quantum dots by AlN, which is supposed to modifiy noticeably the structural and therefore optoelectronic properties of the dots, was studied in situ during growth and ex situ, by anomalous diffraction, x-ray spectrocopy in diffraction and absorption conditions, by TEM and AFM. Those studies put in evidence a pecular capping mecanism, and the evolution of the quantum dots structural properties. The stacking of GaN quantum dots planes, and the associated vertical correlation effects of the dots, were also analyzed in situ by anomalous diffraction and grazing incidence small angle scattering. Using RHEED as a tool to monitor the overall strain in the dots, a prelimianry analysis of the (0001) GaN quantum dots ripening under vacuum was carried out. At last, AFM, TEM and MEIS allowed to investigate the structural and optoelectronic properties of self-organized (11-20) GaN quantum dots., Les travaux présentés dans ce manuscrit sont consacrés à l'étude structurale (taille, déformation, composition) de boîtes quantiques GaN/AlN, par spectroscopie X en condition de diffraction et par diffraction et diffusion anomale des rayons X. Ces travaux sont appuyés par des analyses par diffraction des électrons rapides en réflexion (RHEED), par microscopies électronique en transmission (TEM) et à force atomique (AFM), et par diffusion des ions de moyenne énergie (MEIS).La mesure des structures fines en conditions de diffraction (spectroscopie X en condition de diffraction) et de la diffraction anomale, dans une géométrie en incidence rasante indispensable pour l'étude de nanoobjets, à nécessité des développements expérimentaux spécifiques. Conjointement, un effort particulier a été porté sur la prise en compte des effets dynamiques associés à l'utilisation d'une incidence rasante, dans l'analyse quantitative des résultats. En outre, les résultats ont été confrontés à des simulations des diagrammes de diffraction, des structures fines en condition de diffraction et de la diffraction anomale, sur la base de simulations des champs de déformations dans les boîtes quantiques.L'encapsulation de boîtes quantiques GaN (0001) par AlN, susceptible de modifier les propriétés structurales et donc optoélectroniques des boîtes, a été étudié, in situ pendant la croissance et ex situ, par diffraction anomale et spectroscopie X en condition de diffraction ou d'absorption, par TEM et AFM. Ces mesures ont permis de proposer un mécanisme d'encapsulation original, et de mettre en évidence l'évolution des propriétés structurales des boîtes pendant l'encapsulation. L'empilement de plans de boîtes quantiques, et les effets de corrélations verticale de la position des boîtes associés, ont par ailleurs été étudié in situ, par diffraction anomale et diffusion aux petits angles en incidence rasante. Par RHEED, une étude préliminaire structurale du mûrissement des boîtes quantiques GaN (0001) a été entreprise. Enfin, AFM, TEM et MEIS ont permis d'analyser les propriétés structurales et optoélectroniques de boîtes quantiques GaN (11-20) auto-organisées.