Lionel Patrone

Photoluminescence of silicon nanoclusters with reduced size dispersion produced by laser ablation

We report a photoluminescence study of silicon nanoclusters produced by laser ablation. It was found that by varying the preparation parameters it was possible to change the mean cluster size in the range 1–5 nm. Within this size variation, the photoluminescence band shifts in a wide spectral region from near ultraviolet to near infrared. This size-dependent photoluminescence of Si nanoclusters is consistent with a quantum confinement effect. The observed influence of cluster oxidation on the luminescence properties also supports the quantum confinement interpretation. We proposed a discrete size model which supposes that the spectral position of the luminescence band is essentially determined by the volume of clusters with a complete outer atomic layer. In the framework of this model, we were able to deconvolute the observed luminescence bands into a set of fixed Gaussian bands. The model is supported by the observation of a size selective doping of Si nanoclusters whose effect was well explained by Auge...

Strategy of nanocluster and nanostructure synthesis by conventional pulsed laser ablation

We describe the basic principles of nanoparticle synthesis by conventional pulsed laser ablation. The generalization of the Zeldovich and Raizer theory of condensation has been performed for inhomogeneous laser-induced plume where the rates of nucleation as well as the condensation times are different for different parts of the plume. The theoretical development and analysis of the experimental results are given for condensation, expansion and properties of silicon nanoclusters.

Thiophene-based push–pull chromophores for small molecule organic solar cells (SMOSCs)

The last decade has witnessed rapid progress in organic photovoltaics boosted by the design and synthesis of novel π-conjugated small donor–acceptor molecules (mainly thiophene-based chromophores) and by the control and optimization of both device processing and fabrication. Although some important progress has been reached, current challenges remain to further improve their efficiency, durability and cost-effectiveness in order to compete with silicon-based solar cells. This review will provide the scientific community with both general and in depth information on the structure–property relationships related to the photocurrent efficiencies comprising detailed I/V characteristics. It will highlight guidelines for designing new efficient and emerging alternatives to conjugated polymers on the basis of thiophenic chromophores representing, to date, the most widely used class of organic materials for such a purpose as well as important information on device processing or fabrication factors that could influence their performances.

Surface enhanced Raman spectroscopy of organic molecules deposited on gold sputtered substrates

Aggregates of Au nanoparticles have been extremely easily obtained on glass substrates by physical sputtering under primary vacuum. With such a protocol, we demonstrate that it is possible to control the surface plasmon band absorption. Surface enhanced Raman spectroscopy (SERS) experiments were performed with methylene blue, zinc octacarboxyphthalocyanine, 4-aminothiophenol and cysteamine. The correlation between the absorption band and the wavelength giving the highest SERS intensity is clearly observed for methylene blue, in accordance with the electromagnetic enhancement theory. For the other molecules, effects of the chemical enhancement are also observed. In addition, we noticed a strong influence of the nature of the adsorbed molecule on the enhancement factor for a given wavelength. The origin of this feature is discussed in terms of resonant effects or multipolar surface plasmon modes.

Size dependent photoluminescence from Si nanoclusters produced by laser ablation

We report a photoluminescence study of silicon nanoclusters deposited by laser ablation. This technique allows to obtain clusters with a reduced size dispersion. Taking advantage of that as well as of the possibility to tune selectively the cluster size relatively to the preparation parameters, we are able to make a fine correlation between the emission band and the corresponding emitting size. The photoluminescence band can be tuned in a wide spectral region spreading from the near ultraviolet to the near infrared depending on preparation conditions. The correlation with atomic force microscopy measurements provides a size dependence of the luminescence which is fully consistent with the quantum confinement interpretation. To our knowledge, we present here the first observation of a wide spectral range tuning of the emission bands of nanocrystalline silicon by using a dry technique compatible with clean vacuum processing.

Single and binary self-assembled monolayers of phenyl- and pentafluorophenyl-based silane species, and their phase separation with octadecyltrichlorosilane.

In this paper, we first present the study of the formation of phenyltrichlorosilane film and self-assembled monolayers of phenylalkyltrichlorosilane (PATCl), pentafluoro-phenylalkyltrichlorosilane (PFATCl), and a mixture of the two, on silicon covered by its native oxide. These monolayers are shown to grow in two steps with characteristic time constants. The first step is characterized by a similar time constant of growth for all the studied trichlorosilane molecules and attributed to chemisorption. The second step corresponds to the arrangement between molecules, accelerated by the presence of the short alkyl chain (3-4 carbon atoms), and by mixing phenyl and pentafluoro-phenyl terminal moieties, which is accounted for by hydrogen bonding CH···FC and/or attractive quadrupolar interactions within a face-to-face phenyl/pentafluoro-phenyl alternating stack arrangement. Such results should allow improvement of intermolecular stacking within conjugated molecular domains, which is particularly important for molecular electronic devices. In the second part, we studied how PATCl, PFATCl, and their mixture phase separate with octadecyltrichlorosilane (OTS) molecules in various ratios. The way to improve phase separation was studied modifying aromatic ring to ring as well as aromatic-aliphatic interactions. OTS island size and coverage are shown to be smaller with the aromatic phase that involves stronger ring to ring interactions, i.e., attractive interactions between the phenyl species by mixing phenyl and pentafluoro-phenyl rings. The best phase separation is obtained with PFATCl as the aromatic molecule. If nanoislands of aromatic molecules could not be observed in these experiments, we show that they are attainable by mixing OTS and aromatic small organotriethoxysilanes whose grafting kinetics is slower. These results pave the way to the control improvement of the composition and nanostructuration of SAMs, essential for their further use within molecular devices.

Insight into electronic mechanisms of nanosecond-laser ablation of silicon

We present experimental and theoretical studies of nanosecond ArF excimer laser desorption and ablation of silicon with insight into material removal mechanisms. The experimental studies involve a comprehensive analysis of the laser-induced plume dynamics and measurements of the charge gained by the target during irradiation time. At low laser fluences, well below the melting threshold, high-energy ions with a narrow energy distribution are observed. When the fluence is increased, a thermal component of the plume is formed superimposing on the nonthermal ions, which are still abundant. The origin of these ions is discussed on the basis of two modeling approaches, thermal and electronic, and we analyze the dynamics of silicon target excitation, heating, melting, and ablation. An electronic model is developed that provides insight into the charge-carrier transport in the target. We demonstrate that, contrary to a commonly accepted opinion, a complete thermalization between the electron and lattice subsystems is not reached during the nanosecond-laser pulse action. Moreover, the charging effects can retard the melting process and have an effect on the overall target behavior and laser-induced plume dynamics.

A Surface Enhanced Raman Spectroscopy study of aminothiophenol and aminothiophenol-C60 self-assembled monolayers: evolution of Raman modes with experimental parameters

P-aminothiophenol (PATP) is a well-known molecule for the preparation of self-assembled monolayers on gold via its thiol functional group. After adsorption, it has been demonstrated that this molecule is anchored to gold through its thiol group, and standing nearly upright at the surface with the amino functional group on top. This molecule has been extensively studied by surface enhanced Raman spectroscopy but its exact SERS spectrum remains unclear. Here, we demonstrate that it can be strongly affected by at least two experimental parameters: laser power and layer density. Those features are discussed in terms of a dimerization of the PATP molecules. The free amino group affords the adsorption of other molecules such as C(60). In this case, a complex multilayer system is formed and the question of its precise characterisation remains a key point. In this article, we demonstrate that surface enhanced Raman spectroscopy combined with x ray photoelectron spectroscopy can bring very important information about the organization of such a self-assembled multilayer on gold. In our study, the strong evolution of Raman modes after C(60) adsorption suggests a change in the organization of aminothiophenol molecules during C(60) adsorption. These changes, also observed when the aminothiophenol layer is annealed in toluene, do not prevent the adsorption of C(60) molecules.

Solvent induced aggregation of protoporphyrin and octacarboxylphthalocyanine of zinc deposited on gold surface

In this paper, we studied the influence of solvent on the morphology of zinc protoporphyrin and zinc octacarboxylphthalocyanine films transferred onto gold surface by dipping. In these films, carboxylic acid groups borne in periphery of macrocycles allow anchoring to gold via ionic interaction. First, we followed by UV-Visible absorption spectroscopy the solvation state of these conjugated macrocycles in pure DMF, in pure ethanol and in various ethanol/DMF mixtures. We show that the increase in ethanol proportion promotes interactions between macrocycles. Second, molecular layers of macrocycles spontaneously adsorbed from these various solutions onto gold surface were analyzed by ellipsometry, water contact angle measurements, UV-Visible absorption spectroscopy and atomic force microscopy. Results evidenced the layers were mainly composed of grains whose size of a few nanometers was directly related to the solvation conditions of molecules. In addition, Q band splitting was observed in the absorption spectrum of zinc octacarboxylphthalocyanine grain films which indicates specific organization of those molecules. Therefore solvent is shown to have a profound influence on the nanostructuration of as-prepared macrocycle layers on gold surface by promoting pre-organization in solution, and its composition enables to better control the morphology of those films by tuning the solubilization of macrocycles.

Pulsed Laser Deposition of Si Nanocluster Films

The studies of light emission from Si-related materials have attracted attention in the past several years because of the potential applications for optoelectronic devices. Reactive laser ablation of Si targets by ArF* excimer laser (wavelength 193 nm, pulse width 15 ns (FWHM)) was performed in He, Ar or O{sub 2} 0.05--1 Torr atmospheres and led to Si-SiO{sub x} nanocluster thin film formation within laser-induced plasma plume. Optical spectroscopy and optical Time-of-Flight (TOF) measurements were carried out during ablation-deposition experiments. A number of large weak emission bands in blue and green-yellow spectral branches were observed both in inert gases and in oxygen ambient atmospheres and attributed to the emission from excited nanoparticles in the plasma plume. TOF measurements proved a different spatio-temporal evolution of this emission compare to the emission of monoatomic particles. The films exhibit photoluminescence bands in the UV region (around 290 nm and between 310--370 nm), in the blue (between 240 and 500 nm), and in the green-yellow (at 520--560 nm). The relative intensities of the luminescence bands depend on the average cluster size, which is determined by preparation conditions (nature and pressure of the ambient gas, laser fluence).