Indirect excitation of Er3+ ions in silicon nitride films prepared by reactive evaporation

International audienceEr-doped silicon nitride films were obtained by reactive evaporation of silicon under a flow of nitrogen ions and were annealed at temperatures up to 1300°C. Samples were studied by infrared absorption and Raman spectrometries and by transmission electron microscopy. The 1.54 m Er-related photoluminescence ͑PL͒ was studied in relation with the structure with pump excitation at 488 and 325 nm. Steady-state PL, PL excitation spectroscopy, and time-resolved PL were performed. The results demonstrate that Er 3+ ions are indirectly excited both via silicon nanocrystals and via localized states in the silicon nitride matrix. Er-doped silicon-based materials have attracted much attention in the scientific community because of their potential use for optoelectronics. 1 Indeed, Er 3+ ions can emit sharp luminescence at 1.54 m, which is the commonly used wavelength for optical communications. The Er sensitization has been widely studied in Si rich SiO 2 layers. In silica containing silicon nanocrystals ͑Si-nc͒, the Er-related photolu-minescence is strongly improved due to a strong energy transfer from Si-nc to Er 3+ ions. 2-4 The Er 3+ ions can then be indirectly excited by Si-nc which have an absorption cross section several orders of magnitude higher than that of direct Er excitation. While SiN x is a particularly interesting host matrix for electrically pumped light-emitting devices, the Er excitation mechanism in silicon nitride films is still not clear. Similarly to the SiO x based samples, the sensitization of Er 3+ ions by Si nanoparticules has been reported in SiN x samples prepared by plasma enhanced chemical vapour deposition ͑PECVD͒ 5 or by magnetron sputtering. 6 However, some works have also demonstrated that indirect excitation of Er 3+ ions could occur via electronic states localized in the SiN x band tail states. 7,8 In this letter, we study the Er-related PL at 1.54 m in Er-doped silicon nitride thin films prepared by an ion-beam-assisted evaporation technique. The evolutions of the structure and of the PL properties with the annealing treatments are studied. It is demonstrated that the Er excitation is indirect and that Si-nc is able to improve the PL intensity. It is also shown that another indirect excitation path presumably exists in the amorphous SiN x matrix. Silicon was evaporated from an electron beam gun with a deposition rate equal to 0.1 nm/s. The 200 nm thick films were deposited on silicon substrates maintained at 100°C. The nitrogen ions were provided by an electron cyclotron resonance microwave plasma source. The nitrogen flow was regulated by maintaining the total pressure in the evaporation chamber at 2 ϫ 10 −5 Torr. The Er doping was performed from an effusion cell. Rutherford backscattering spectrom-etry was used to analyze the chemical content of the film. The Si, N, O, and Er atomic concentrations are equal to 47%, 48%, 5%, and 0.3%, respectively. The oxygen content is due to the low density of the layer and to exposure to the air. This concentration corresponds to a 12 at. % Si excess compared to the Si 3 N 4 equilibrium stoichiometry. The Fourier transform infrared ͑FTIR͒ experiments were carried out with a spectrometer with a resolution of 2 cm −1. Raman measurements were carried out with a mutichannel spectrometer equipped with a 1800 grooves mm −1 grating. The samples were excited by the 514 nm line from an argon laser. Transmission electron microscopy was performed with a 200 keV microscope. For the steady-state PL experiments, the samples were excited by a 30 mW He-Cd laser using the 325 nm line or by a 60 mW laser diode emitting at 488 nm. For the PL excitation ͑PLE͒ experiments, the samples were excited by an optical parametric oscillator laser. The PL signal was measured by a photomultiplier tube cooled at 190 K. For the time-resolved PL experiments, the samples were pumped by the 355 nm line of a frequency-tripled YAG:Nd laser. The laser pulse frequency, energy, and duration were typically equal to 10 Hz, 50 J, and 20 ns, respectively. The time response of the detection system was better than 1 s. Figure 1͑a͒ shows the FTIR spectra of the films for as-deposited sample and samples annealed at 1000 and 1100°C. The spectrum shows a very intense band at around 850 cm −1 , characteristic of the asymmetric stretching vibration of the SiN bonds. 9 The spectra are not significantly modified for annealing temperatures lower than 1000°C since only a 6 cm −1 shift occurs to higher wavenumbers. For higher annealing temperature, the peaks shift again a few cm −1 and a shoulder appears at high wavenumbers, demonstrating a modification of the SiN bonds, which could be correlated to the precipitation of Si-nc. 1

The vibrational spectrum of CaCO3 aragonite: A combined experimental and quantum-mechanical investigation

The vibrational properties of CaCO3 aragonite have been investigated both theoretically, by using a quantum mechanical approach (all electron Gaussian type basis set and B3LYP HF-DFT hybrid functional, as implemented in the CRYSTAL code) and experimentally, by collecting polarized infrared (IR) reflectance and Raman spectra. The combined use of theory and experiment permits on the one hand to analyze the many subtle features of the measured spectra, on the other hand to evidentiate limits and deficiencies of both approaches. The full set of TO and LO IR active modes, their intensities, the dielectric tensor (in its static and high frequency components), and the optical indices have been determined, as well as the Raman frequencies. Tools such as isotopic substitution and graphical animation of the modes are available, that complement the analysis of the spectrum

Periodic Density Functional Theory Investigation of the Uranyl Ion Sorption on Three Mineral Surfaces: A Comparative Study

Canister integrity and radionuclides retention is of prime importance for assessing the long term safety of nuclear waste stored in engineered geologic depositories. A comparative investigation of the interaction of uranyl ion with three different mineral surfaces has thus been undertaken in order to point out the influence of surface composition on the adsorption mechanism(s). Periodic DFT calculations using plane waves basis sets with the GGA formalism were performed on the TiO2(110), Al(OH)3(001) and Ni(111) surfaces. This study has clearly shown that three parameters play an important role in the uranyl adsorption mechanism: the solvent (H2O) distribution at the interface, the nature of the adsorption site and finally, the surface atoms’ protonation state

Rôle de la structure chimique du donneur sur l'efficacité des réactions de transfert de charge photoinduit.

Cette thèse concerne la compréhension du rôle de la structure chimique du donneur d'électron sur l'efficacité des réactions de transfert de charge photoinduit en solution. Sont abordés le transfert d'électron total (TE) et la formation de complexes à l'état excité ou "exciplexes". Le chapitre 1 rappelle les bases théoriques du transfert d'électron. La notion de TE non-adiabatique est présentée via la théorie de Marcus. D'autres modèles, basés sur un TE adiabatique, sont également décrits en détails. Le chapitre 2 confronte ces théories à un jeu de données expérimentales qui permet d'envisager une possible prédominance des théories adiabatiques en condition de libre diffusion des espèces. De plus, il est montré que l'utilisation d'amines aliphatiques comme donneurs réduit le couplage électronique avec l'accepteur et conduit à formuler une version quantitative du principe de réactivité-sélectivité grâce à une relation thermodynamique originale entre le facteur d'adiabaticité et le potentiel de réduction de l'accepteur. Le chapitre 3 aborde la caractérisation expérimentale de l'exciplexe. Il montre que la structure du donneur définit la géométrie du complexe créé et influence considérablement l'efficacité de la réaction dans la région endergonique. Ce résultat permet alors d'unifier les deux visions phénoménologiques contradictoires de la littérature. Le chapitre 4 utilise les données du chapitre précédent pour les confronter aux deux modèles théoriques d'exciplexes de la littérature. Les hypothèses de ces deux modèles sont étudiées en détails, et une troisième théorie est formulée, qui rend mieux compte des résultats expérimentaux. Enfin, le chapitre 5 est une application des notions précédentes à la photoréd-uction des cétones aromatiques. La photoréduction par les amines aliphatiques conduit à la réactivité par transfert d'électron des radicaux. La photoréduction par des phénols substitués apporte le concept d'exciplexe à liaison hydrogène.MULHOUSE-SCD Sciences (682242102) / SudocSudocFranceF

Le syndrome de West

REIMS-BU Santé (514542104) / SudocSudocFranceF