Lucien Datas

Higher Dispersion Efficacy of Functionalized Carbon Nanotubes in Chemical and Biological Environments

Aqueous dispersions of functionalized carbon nanotubes (CNTs) are now widely used for biomedical applications. Their stability in different in vitro or in vivo environments, however, depends on a wide range of parameters, such as pH and salt concentrations of the surrounding medium, and length, aspect ratio, surface charge, and functionalization of the applied CNTs. Although many of these aspects have been investigated separately, no study is available in the literature to date, which examines these parameters simultaneously. Therefore, we have chosen five types of carbon nanotubes, varying in their dimensions and surface properties, for a multidimensional analysis of dispersion stability in salt solutions of differing pH and concentrations. Furthermore, we examine the dispersion stability of oxidized CNTs in biological fluids, such as cellular growth media and human plasma, and their toxicity toward cancer cells. To enhance dispersibility and biocompatibility, the influence of different functionalization schemes is studied. The results of our investigations indicate that both CNT dimensions and surface functionalization have a significant influence on their dispersion and in vitro behavior. In particular, factors such as a short aspect ratio, presence of oxidation debris and serum proteins, low salt concentration, and an appropriate pH are shown to improve the dispersion stability. Furthermore, covalent surface functionalization with amine-terminated polyethylene glycol (PEG) is demonstrated to stabilize CNT dispersions in various media and to reduce deleterious effects on cultured cells. These findings provide crucial data for the development of biofunctionalization protocols, for example, for future cancer theranostics, and optimizing the stability of functionalized CNTs in varied biological environments.

Surfactant-free CZTS nanoparticles as building blocks for low-cost solar cell absorbers

A process route for the fabrication of solvent-redispersible, surfactant-free Cu₂ZnSnS₄ (CZTS) nanoparticles has been designed with the objective to have the benefit of a simple sulfide source which advantageously acts as (i) a complexing agent inhibiting crystallite growth, (ii) a surface additive providing redispersion in low ionic strength polar solvents and (iii) a transient ligand easily replaced by an carbon-free surface additive. This multifunctional use of the sulfide source has been achieved through a fine tuning of ((Cu²⁺)(a)(Zn²⁺)(b)(Sn⁴⁺)(c)(Tu)(d)(OH⁻)(e))(t⁺), Tu = thiourea) oligomers, leading after temperature polycondensation and S²⁻ exchange to highly concentrated (c > 100 g l⁻¹), stable, ethanolic CZTS dispersions. The good electronic properties and low-defect concentration of the sintered, crack-free CZTSe films resulting from these building blocks was shown by photoluminescence investigation, making these building blocks interesting for low-cost, high-performance CZTSe solar cells.

Controlled growth of CNT in mesoporous AAO through optimized conditions for membrane preparation and CVD operation.

Anodic aluminium oxide (RAAO) membranes with a mesoporous structure were prepared under strictly controlling experimental process conditions, and physically and chemically characterized by a wide range of experimental techniques. Commercial anodic aluminium oxide (CAAO) membranes were also investigated for comparison. We demonstrated that RAAO membranes have lower content of both water and phosphorus and showed better porosity shape than CAAO. The RAAO membranes were used for template growth of carbon nanotubes (CNT) inside its pores by ethylene chemical vapour deposition (CVD) in the absence of a catalyst. A composite material, containing one nanotube for each channel, having the same length as the membrane thickness and an external diameter close to the diameter of the membrane holes, was obtained. Yield, selectivity and quality of CNTs in terms of diameter, length and arrangement (i.e. number of tubes for each channel) were optimized by investigating the effect of changing the experimental conditions for the CVD process. We showed that upon thermal treatment RAAO membranes were made up of crystallized allotropic alumina phases, which govern the subsequent CNT growth, because of their catalytic activity, likely due to their Lewis acidity. The strict control of experimental conditions for membrane preparation and CNT growth allowed us to enhance the carbon structural order, which is a critical requisite for CNT application as a substitute for copper in novel nano-interconnects.

In situ characterization of infrared femtosecond laser ablation in geological samples. Part A: the laser induced damage

Infrared femtosecond laser induced damage has been studied in order to determine, with analytical protocols, the processes involved in laser ablation in this regime. Transmission Electron Microscopy (TEM) coupled with Focused Ion Beam (FIB) milled cross-sections of natural ablated monazite were used. Craters were formed using N = 1 and 3 shots, E0 = 0.1 and 0.8 mJ per pulse and τ = 60 fs. Observations revealed that laser settings induce little changes in the nature and size of damaged structures. The crater bottom forms a ∼0.5 μm layer composed of melted and recrystallized monazite grains, and spherical ∼10 nm voids. The underlying sample shows lattice distortions, progressively attenuated with depth, typical of mechanical shocks (thermoelastic relaxation and plasma recoil pressure). No chemical difference appears between these two domains, excluding preferential vaporization and thus laser induced chemical fractionation. Correlations with existing molecular dynamics (MD) simulations indicate that the deep distorted lattice probably undergoes spallation whereas the upper layer rather goes through homogeneous nucleation. Nevertheless, these processes are not pushed forward enough to induce matter removal in the present conditions. In consequence, photomechanical fragmentation and vaporization, requiring higher energy density states, would rather be the main ablation mechanisms. This hypothesis was supported by an additional study focused on the laser produced aerosols. Further links to LA-ICP-MS measurements can then be developed.

Transmission electron microscopy for elucidating the impact of silver-based treatments (ionic silver versus nanosilver-containing coating) on the model yeast Saccharomyces cerevisiae

After exposure to ionic silver or nanosilver-containing plasma coating, the same visual aspect of scanning transmission electron microscopy (STEM) images was observed for the model yeast Saccharomyces cerevisiae. The main common feature was the presence of electron-dense nodules all over the cell. However, high resolution TEM (HRTEM), STEM, energy dispersive x-ray microanalysis spectroscopy (EDS) and electron microdiffraction revealed some striking differences. Regarding ionic silver exposure, the formation of electron-dense nodules was related to the Ag(+) reactivity towards sulfur-containing compounds to form clusters with Ag(2)S-like structures, together with the production of a few silver nanocrystals, mainly at the cell wall periphery. For nanosilver-based treatment, some sulfur-containing silver clusters preferentially located at the cell wall periphery were detected, together with nodules composed of silver, sulfur and phosphorus all over the cell. In both silver-based treatments, nitrogen and silver signals overlapped, confirming the affinity of silver entities for proteinaceous compounds. Moreover, in the case of nanosilver, interactions of silver with phosphorus-containing subcellular structures were indicated.

Dominance of mechanical over thermally induced damage during femtosecond laser ablation of monazite

Effects of infrared femtosecond laser ablation (800 nm, 60 fs, 5 Hz, 85 μJ/pulse, objective × 15) of a well-characterized monazite on its micro- and nano-structure were investigated. Craters were produced by single and multiple pulses ( N = 10, 20, 50, 150 and 300) to follow the evolution of laser-induced damage in monazite using Scanning Electron Microscope (SEM), and Transmission Electron Microscope (TEM) coupled with Focused Ion Beam (FIB) sample preparation, in order to characterize this damage. Voids are observed within craters from the first pulse and cracks appear already after 10 pulses, at the sample surface; radial cracks are well-defined for 50 pulses, and become conchoidal after 150 pulses, indicating high-strain fields in the vicinity of craters. After the first pulse, the monazite lattice is highly strained to depths greater than ~1 μm with a spotty ring diffraction pattern demonstrating that the damaged monazite is a mosaic crystal. Under this area monazite is moderately strained over 6 μm in depth. Crack formation within the crystal is observed from the first pulse. Cracks formed at the surface and propagated over 2 μm into the crystal. Their number increased notably after 10 pulses, with some cracks propagating 8 μm into the crystal. Increasing lattice defects (mosaic crystal, twins) and fracture intensities demonstrate that a cumulative effect exists. Part of the energy carried by the laser is stored within the crystal and used in the formation of defects. This study highlights the intense damages that are created during a femtosecond laser ablation in monazite. Mechanical effects dominate thermal ones, limited to a thin layer (200 nm–1 pulse) of resolidified monazite, and are induced by high-pressure shock wave from plasma expansion.

Micro-Raman scattering of selenium-filled double-walled carbon nanotubes: Temperature study

Selenium-filled double-walled carbon nanotubes (Se@DWNT) have been studied by high resolution transmission electron microscopy (HRTEM) and micro-Raman spectroscopy in the temperature interval from 80to600K employing 785nm excitation wavelength. The temperature dependences of the dominant bands (G-band and G′-band) are analyzed in terms of the model developed by Klemens [Phys. Rev. 148, 845 (1966)], Hart et al. [Phys. Rev. B 1, 638 (1970)], Cowley [J. Phys. (France) 26, 659 (1965)] and extended by Balkanski et al. [Phys. Rev. B 26, 1928 (1983)] for anharmonic decay of optical phonons. The findings were compared to analogous study for empty double-walled carbon nanotubes (DWNTs). The DWNT interatomic force constant modification as a result of the presence of the Se atoms inside the tubes is revealed through larger anharmonicity constants describing the temperature dependences of the G′-band and the inner tube tangential modes (G-band).

The Unexpected Complexity of Filling Double-Wall Carbon Nanotubes With Nickel (and Iodine) 1-D Nanocrystals

A variety of iodine-based one-dimensional (1-D) nanocrystals were introduced into double-wall carbon nanotubes (DWCNTs) using the molten phase method, as an intermediate step for ultimately obtaining encapsulated metal nanowires. Based on high-resolution transmission electron microscopy (HRTEM) observations using different imaging modes (bright field, dark field, and scanning TEM) and associated analytical tools (electron energy loss spectroscopy), it is revealed that the reality of nanotube filling is much more complex than expected. For some iodides (typically NiI 2), earlier decomposition during the filling step was observed, which could not be anticipated from the known data on the bulk material. Other filling materials (e.g., iodine) show a variety of atomic structuration inside and outside the CNTs, which is driven by the available space being filled. Most of the encapsulated structures were confirmed by modeling.

The unexpected complexity of filling double-wall carbon nanotubes with iodine-based 1D nanocrystals

A variety of iodine-based 1D nanocrystals were introduced into double-wall carbon nanotubes using the molten phase method, as an intermediate step for ultimately obtaining encapsulated metal nanowires. Based on HRTEM observations using different imaging modes (bright field, dark field, STEM) and associated analytical tools (EELS), it is revealed that the reality of nanotube filling is much more complex than expected. For some halides (typically Nih), earlier decomposition during the filling step was observed, which could not be anticipated from the known data on the bulk material. Others (e.g., iodine) show a variety of atomic structuration inside and outside the CNTs which is driven by the available space being filled, and was ascertained by modelling. Overall, the whole study reveals a variety of filling efficiencies, the reason of which is discussed.

Nanostructured materials with highly dispersed Au–Ce0.5Zr0.5O2 nanodomains: A route to temperature stable Au catalysts?

Our strategy to inhibit Au(0) growth with temperature involves the preparation of ultrafine Au clusters that are highly dispersed and strongly interacting with a thermally stable high-surface-area substrate. Temperature-stable Au-cluster-based catalysts were successfully prepared through the controlled synthesis of 3.5 nm Ce0.5Zr0.5O2 colloidal building blocks containing tailored strongly bound Au-cluster precursors. With the objective of stabilizing these Au clusters with temperature, grain growth of Ce0.5Zr0.5O2 nanodomains was inhibited by their dispersion through Al2O3 nanodomains. High surface area Au–Ce0.5Zr0.5O2–Al2O3 nanostructured composites were thus designed highlighting the drastic effect of Au cluster dispersion on Au(0) cluster growth. High thermal stability of our Au(0)-cluster-based catalysts was shown with the surprising catalytic activity for CO conversion observed on our nanostructured materials heated to temperatures as high as 800 °C for 6 h.