High-Performance n-type SnSe Thermoelectric Polycrystal Prepared by Arc-Melting

Tin selenide (SnSe) has notable thermoelectric properties, yet stable n-type polycrystalline SnSe is difficult to synthesize. Here, polycrystalline SnSe is easily prepared by arc-melting as robust pellets, with thermoelectric properties repeatably changing to negative Seebeck .coefficient above 580 K reaching a figure of merit similar to 1.8 at 816 K. DC conductivity changes 4 orders of magnitude with temperature, whereas microwave conductivity increases only 4-fold, confirming the effects of oxidized grain boundaries. Effects of ambient oxygen exposure are probed by X-ray photoelectron spectroscopy. Neutron powder diffraction reveals 3% Sn deficiency. Inelastic neutron scattering shows phonon spectrum consistent with ab initio calculations and reported Raman spectra, but with higher-energy modes strongly softened at higher temperatures. We thereby provide insight on undoped n-type polycrystalline SnSe that reveals high-performance at high temperature, being a suitable peer material for p-type SnSe.

Towards a room-temperature polariton amplifier

Cristiano Ciuti, Benoît Marie Joseph Deveaud, Stefan Kundermann, Michele Saba

Microcavity exciton polaritons, the fundamental optical excitations of semiconductor microcavities with quantum wells inside, have been proposed as promising candidates for observing stimulated scattering, condensation and other phenomena related to the bosonic nature of excitons. Having a light mass, quantum degeneracy of polaritons can be reached at low densities and high temperatures. But the radiative time of polaritons is very short (in the picosecond range) and usually prevents an efficient thermalization and cooling of the excited cloud of polaritons. A 'coherently driven condensate', not corresponding to a thermal equilibrium, but featuring multiple occupation of single-particle states, can however be created by an external laser source resonantly exciting polaritons. Under this condition, stimulated parametric scattering of polaritons can provide huge optical gain on a weak probe pulse shined on the sample. In this work we demonstrate that this phenomenon can survive at temperatures close to room temperature and could be achieved in the future even above this limit. Clever sample designs favour the thermal robustness of polariton parametric amplification, but from the experimental data it turns out that the parameter that ultimately limits the highest temperature for polariton parametric scattering is the exciton binding energy.

2003

Polariton amplification in semiconductor microcavities

Cristiano Ciuti, Benoît Marie Joseph Deveaud, Stefan Kundermann, Michele Saba

Microcavity exciton polaritons, the fundamental optical excitations of semiconductor microcavities with quantum wells inside, have been proposed as promising candidates for observing stimulated scattering, condensation and other phenomena related to the bosonic nature of excitons. Having a light mass, quantum degeneracy of polaritons can be reached at low densities and high temperatures. But the radiative time of polaritons is very short (in the picosecond range) and usually prevents an efficient thermalization and cooling of the excited cloud of polaritons. A 'coherently-driven condensate', not corresponding to a thermal equilibrium, but featuring multiple occupation of single-particle states, can however be created by an external laser source resonantly exciting polaritons. Under this condition, stimulated parametric scattering of polaritons can provide huge optical gain on a weak probe pulse shined on the sample. In this work we demonstrate that this phenomenon can survive at temperatures close to room temperature and could be achieved in the next future even above this limit. Clever sample designs favour the thermal robustness of polariton parametric amplification, but from the experimental data it turns out that the parameter that ultimately limits the highest temperature for polariton parametric scattering is the exciton binding energy. (C) 2003 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

2003

Nitrous Oxide Abatement over Fe-Zeolite

Bryan Bromley

The use of zeolites for catalytic reactions is a field in continuous development. Since it was demonstrated that metal-zeolites are efficient catalysts for NOx abatement, decomposition of nitrous oxide (N2O) over Fe-containing zeolites has attracted great interest by the scientific community mainly due: N2O is the third most important gas contributing to global warming, its concentration in atmosphere is still on the rise and direct N2O decomposition to N2 and O2 is a sustainable alternative. N2O interaction with Fe-zeolite leads to the formation of "special" adsorbed oxygen (often called α-oxygen) with great potential for selective oxidation. Although the focus of a number of studies, the nature of the actives sites for the formation of this adsorbed oxygen is still unclear. The main objectives of this work are: 1) study the decomposition mechanism of N2O over isomorpously substituted Fe-ZSM-5 zeolite aiming on catalyst optimization and 2) optimization and further use of structured Fe-zeolite in novel micro-structured reactor. A number of refined transient kinetics methods were intensively used such as transient response, Temperature Programmed Desorption (TPD) and Temporal Analysis of Product (TAP). Density Functional Theory (DFT) and in situ IR spectroscopy studies were conducted in collaboration and our results support the following: In chapter 3, quantitative measurements have been carrier out to analyze the effect of temperature on the activation (under helium flow) and the irreversible deactivations that can happen during the pretreatment. The results obtained indicate that high temperature treatment (1273 K) results in the formation of a high amount of α-sites. The addition of a very low fraction of oxygen (2%) in the feed demonstrates that the catalyst is sensitive to its presence. Certain sites can be irreversibly destroyed, a result ascribed to the oxidation of active Fe(II) to Fe2O3 clusters which contain inactive Fe(III). Catalyst treatment at high temperature (1273 K) in He for up to 3 hours, also reduced irreversibly the concentration of α-sites. TPD measurements have shown desorption of oxygen at 3 different temperatures. Desorption at the lowest temperature (650 K) was assign to the α-oxygen recombination. The oxygen which desorbs at 700 K was associated to the oxygen from the deactivated sites. Oxygen which desorbs at the highest temperature (730 K) is originated from the surface NOx that desorbed as NO and O2. After a comparison of the concentration of the molecules accumulated, we propose that NO2 is the adsorbed specie. The mechanism of N2O decomposition on the binuclear oxo-hydroxo bridged extraframework iron core site [FeII(μ-O)(μ-OH)FeII]+ inside the ZSM-5 zeolite has been studied by combining theoretical and experimental approaches (see chapter 4). Rate parameters computed using standard statistical mechanics and transition state theory reveal that elementary catalytic steps involved into N2O decomposition are strongly dependent on the temperature. This theoretical result was contrasted with the experimentally observed steady state kinetics of the N2O decomposition and TPD experiments. As predicted by the theoretical study, the switch of the reaction order with respect to N2O pressure (from zero to one) occurs at around 800 K which confirms a change of the rate determining step from the α-oxygen recombination to α-oxygen formation. The proposed mechanism was also confirmed by O2-TD which confirmed the viability of the binuclear complex. The α-oxygen recombination at low temperature (

EPFL2010

Nitrous Oxide Abatement over Fe-Zeolite

Bryan Bromley

EPFL2010