Etienne Talbot

Evidence of superparamagnetic co clusters in pulsed laser deposition-grown Zn0.9Co0.1O thin films using atom probe tomography.

Nanosized Co clusters (of about 3 nm size) were unambiguously identified in Co-doped ZnO thin films by atom probe tomography. These clusters are directly correlated to the superparamagnetic relaxation observed by ZFC/FC magnetization measurements. These analyses provide strong evidence that the room-temperature ferromagnetism observed in the magnetization curves cannot be attributed to the observed Co clusters. Because there is no experimental evidence of the presence of other secondary phases, our results reinforce the assumption of a defect-induced ferromagnetism in Co-doped ZnO diluted magnetic semiconductors.

Si nanoparticles in SiO2 An atomic scale observation for optimization of optical devices

Three-dimensional imaging of silicon nanoclusters array in silicon-rich silicon oxide layers was evidenced and studied. The atom probe tomography technique allows to give the composition of the nanoclusters and the composition of the interface with the silica matrix. These results give new insights for the understanding of the properties of Si-based photonic devices.

Investigation at the atomic scale of the Co spatial distribution in Zn(Co)O magnetic semiconductor oxide

A sputtered Zn0.95Co0.05O layer was chemically analyzed at the atomic scale in order to provide an accurate image of the distribution of Co atoms in the ZnO matrix. The investigation of the magnetic properties shows that the as-deposited Zn0.95Co0.05O is ferromagnetic at room temperature. Atom probe tomography reveals a homogeneous distribution of all chemical species in the layer and the absence of any Co clustering. This result proves that the ferromagnetic properties of this magnetic semiconductor cannot be attributed to a secondary phase or to metallic Co precipitates within the layer.

Nanoscale evidence of erbium clustering in Er-doped silicon-rich silica

Photoluminescence spectroscopy and atom probe tomography were used to explore the optical activity and microstructure of Er3+-doped Si-rich SiO2 thin films fabricated by radio-frequency magnetron sputtering. The effect of post-fabrication annealing treatment on the properties of the films was investigated. The evolution of the nanoscale structure upon an annealing treatment was found to control the interrelation between the radiative recombination of the carriers via Si clusters and via 4f shell transitions in Er3+ ions. The most efficient 1.53-μ m Er3+ photoluminescence was observed from the films submitted to low-temperature treatment ranging from 600°C to 900°C. An annealing treatment at 1,100°C, used often to form Si nanocrystallites, favors an intense emission in visible spectral range with the maximum peak at about 740 nm. Along with this, a drastic decrease of 1.53-μ m Er3+ photoluminescence emission was detected. The atom probe results demonstrated that the clustering of Er3+ ions upon such high-temperature annealing treatment was the main reason. The diffusion parameters of Si and Er3+ ions as well as a chemical composition of different clusters were also obtained. The films annealed at 1,100°C contain pure spherical Si nanocrystallites, ErSi3O6 clusters, and free Er3+ ions embedded in SiO2 host. The mean size and the density of Si nanocrystallites were found to be 1.3± 0.3 nm and (3.1± 0.2)×1018 Si nanocrystallites·cm−3, respectively. The density of ErSi3O6 clusters was estimated to be (2.0± 0.2)×1018 clusters·cm−3, keeping about 30% of the total Er3+ amount. These Er-rich clusters had a mean radius of about 1.5 nm and demonstrated preferable formation in the vicinity of Si nanocrystallites.

Atomic characterization of Si nanoclusters embedded in SiO2 by atom probe tomography

Silicon nanoclusters are of prime interest for new generation of optoelectronic and microelectronics components. Physical properties (light emission, carrier storage...) of systems using such nanoclusters are strongly dependent on nanostructural characteristics. These characteristics (size, composition, distribution, and interface nature) are until now obtained using conventional high-resolution analytic methods, such as high-resolution transmission electron microscopy, EFTEM, or EELS. In this article, a complementary technique, the atom probe tomography, was used for studying a multilayer (ML) system containing silicon clusters. Such a technique and its analysis give information on the structure at the atomic level and allow obtaining complementary information with respect to other techniques. A description of the different steps for such analysis: sample preparation, atom probe analysis, and data treatment are detailed. An atomic scale description of the Si nanoclusters/SiO2 ML will be fully described. This system is composed of 3.8-nm-thick SiO layers and 4-nm-thick SiO2 layers annealed 1 h at 900°C.

Quantitative analysis of doped/undoped ZnO nanomaterials using laser assisted atom probe tomography: Influence of the analysis parameters

In the last decade, atom probe tomography has become a powerful tool to investigate semiconductor and insulator nanomaterials in microelectronics, spintronics, and optoelectronics. In this paper, we report an investigation of zinc oxide nanostructures using atom probe tomography. We observed that the chemical composition of zinc oxide is strongly dependent on the analysis parameters used for atom probe experiments. It was observed that at high laser pulse energies, the electric field at the specimen surface is strongly dependent on the crystallographic directions. This dependence leads to an inhomogeneous field evaporation of the surface atoms, resulting in unreliable measurements. We show that the laser pulse energy has to be well tuned to obtain reliable quantitative chemical composition measurements of undoped and doped ZnO nanomaterials.

Simultaneous quantification of indium and nitrogen concentration in InGaNAs using HAADF-STEM.

To unambiguously evaluate the indium and nitrogen concentrations in In(x)Ga(1-x)N(y)As(1-y), two independent sources of information must be obtained experimentally. Based on high-resolution scanning transmission electron microscopy (STEM) images taken with a high-angle annular dark-field (HAADF) detector the strain state of the InGaNAs quantum well is determined as well as its characteristic HAADF-scattering intensity. The strain state is evaluated by applying elasticity theory and the HAADF intensity is used for a comparison with multislice simulations. The combination of both allows for determination of the chemical composition where the results are in accordance with X-ray diffraction measurements, three-dimensional atom probe tomography, and further transmission electron microscopy analysis. The HAADF-STEM evaluation was used to investigate the influence of As-stabilized annealing on the InGaNAs/GaAs sample. Photoluminescence measurements show an annealing-induced blue shift of the emission wavelength. The chemical analysis precludes an elemental diffusion as origin of the energy shift--instead the results are in agreement with a model based on an annealing-induced redistribution of the atomic next-neighbor configuration.

Atomic scale investigation of silicon nanowires and nanoclusters

In this study, we have performed nanoscale characterization of Si-clusters and Si-nanowires with a laser-assisted tomographic atom probe. Intrinsic and p-type silicon nanowires (SiNWs) are elaborated by chemical vapor deposition method using gold as catalyst, silane as silicon precursor, and diborane as dopant reactant. The concentration and distribution of impurity (gold) and dopant (boron) in SiNW are investigated and discussed. Silicon nanoclusters are produced by thermal annealing of silicon-rich silicon oxide and silica multilayers. In this process, atom probe tomography (APT) provides accurate information on the silicon nanoparticles and the chemistry of the nanolayers.

Observation of a nanoscale phase separation in blue-emitting Ce-doped SiO1.5 thin films

Both the optical and structural properties of Ce-doped SiO1.5 thin films were investigated. The Ce-related blue luminescence, which can be seen even at room temperature for as-grown films, exhibits a rather complex evolution with the annealing temperature. In particular, a strong decrease is observed when the films are annealed at 900 °C. Structural characterizations combining scanning transmission electron microscopy and atom probe tomography reveal the formation of Si- and Ce-rich clusters at this temperature, thus demonstrating that the decreasing Ce-related luminescence is due to concentration induced quenching. For annealing temperatures higher than 900 °C, the Ce-related luminescence increases. The different structural characterizations provide clear experimental evidence of a phase separation occurring at the nanoscale between pure Si nanocrystals and Ce-rich clusters having a stoichiometry close to the cerium silicates Ce2Si2O7 or Ce4.667(SiO4)3O. The latter compounds are optically active thereby explaining the increased Ce-related luminescence observed at the highest annealing temperature.

Structural and optical study of Ce segregation in Ce-doped SiO1.5 thin films

Cerium doped SiO1.5 thin films fabricated by evaporation and containing silicon nanocrystals were investigated by atom probe tomography. The effect of post-growth annealing treatment has been systematically studied to correlate the structural properties obtained by atom probe tomography to the optical properties measured by photoluminescence spectroscopy. The atom probe results demonstrated the formation of Ce-Si rich clusters upon annealing at 900 °C which leads to a drastic decrease of the Ce-related luminescence. At 1100 °C, pure Si nanocrystals and optically active cerium silicate compounds are formed. Consequently, the Ce-related luminescence is found to re-appear at this temperature while no Si-nanocrystal related luminescence is observed for films containing more than 3% Ce.