Road Map for Nanocrystal Based Infrared Photodetectors

Infrared (IR) sensors based on epitaxially grown semiconductors face two main challenges which are their prohibitive cost and the difficulty to rise the operating temperature. The quest for alternative technologies which will tackle these two difficulties requires the development of new IR active materials. Over the past decade, significant progresses have been achieved. In this perspective, we summarize the current state of the art relative to nanocrystal based IR sensing and stress the main materials, devices and industrial challenges which will have to be addressed over the 5 next years

Field effect transistor and photo transistor of narrow band gap nanocrystal arrays using ionic glasses

International audienceGating of nanocrystal films is currently driven by two approaches: either the use of a dielectric such as SiO2 or the use of electrolyte. SiO2 allows fast bias sweeping over a broad range of temperatures but requires a large operating bias. Electrolyte, thanks to a large capacitance, leads to significantly reduce operating bias but is limited to slow speed and quasi room temperature operation. None of these operating conditions are optimal for narrow band gap nanocrystal-based phototransistors for which the need of a large capacitance gate has to be combined with low temperature operation. Here we explore the use of a LaF3 ionic glass as a high capacitance gating alternative. We demonstrate for the first time the use of such ionic glasses to gate thin films made of HgTe and PbS nanocrystals. This gating strategy allows operation in the 180 to 300 K range of temperatures with capacitance as high as 1 µF·cm-2. We unveil the unique property of ionic glass gate to enable unprecedented tunability of both magnitude and dynamics of the photocurrent, thanks to high charge doping capability within an operating temperature window relevant for infrared photodetection. We demonstrate that by carefully choosing the operating gate bias, the signal to noise ratio can be improved by a factor 100 and the time response accelerated by a factor 6. Moreover, the good transparency of LaF3 substrate allows back side illumination in the infrared which is highly valuable for the design of phototransistor

Transport and Phototransport in ITO Nanocrystals with Short to Long-Wave Infrared Absorption

Nanocrystals are often described as an interesting strategy for the design of low-cost optoelectronic devices especially in the infrared range. However the driving materials reaching infrared absorption are generally heavy metalcontaining (Pb and Hg) with a high toxicity. An alternative strategy to achieve infrared transition is the use of doped semiconductors presenting intraband or plasmonic transition in the short, mid and long-wave infrared. This strategy may offer more flexibility regarding the range of possible candidate materials. In particular, significant progresses have been achieved for the synthesis of doped oxides and for the control of their doping magnitude. Among them, tin doped indium oxide (ITO) is the one providing the broadest spectral tunability. Here we test the potential of such ITO nanoparticles for photoconduction in the infrared. We demonstrate that In2O3 nanoparticles presents an intraband absorption in the mid infrared range which is transformed into a plasmonic feature as doping is introduced. We have determined the cross section associated with the plasmonic transition to be in the 1-3x10-13 cm2 range. We have observed that the nanocrystals can be made conductive and photoconductive due to a ligand exchange using a short carboxylic acid, leading to a dark conduction with n-type character. We bring further evidence that the observed photoresponse in the infrared is the result of a bolometric effect

Optical spectroscopy and electronic microscopy of Ag-In and Ag-Fe nanoparticles under controlled environment, in the presence of reactive gases

Les nanoparticules (NPs) bimétalliques présentent des propriétés catalytiques très intéressantes qui justifient leur utilisation dans des procédés industriels de catalyse hétérogène. Leur structure (chimique, géométrique, électronique) est néanmoins susceptible d’évoluer dans des conditions environnementales réelles et modifier leurs propriétés. L’objectif de cette thèse pluridisciplinaire est de suivre la réactivité de ces NPs en atmosphère réactive contrôlée. Pour cela, on a développé un dispositif de spectroscopie in situ à modulation spatiale afin de suivre l’évolution de la structure sur une grande population de NPs via l’étude de leur résonance du plasmon de surface (RPS) localisée. Ces observations ont été couplées avec une approche locale (NPs individuelles) par microscopie électronique à transmission environnemental (MET-E). La MET-E a permis de révéler des effets de composition et d’environnement sur la structure chimique de NPs Ag-In. Des alliages stables pauvres en indium se forment, puis une coquille d’oxyde d’indium dont l’épaisseur augmente avec la concentration atomique d’indium. D’autre part, des domaines de structures stables (coeur@coquille, Janus, système réduit) ont été mis en évidence selon les conditions locales de température et de pression d’hydrogène. Enfin, l’oxydo-réduction de NPs Ag-Fe a été suivie in situ via l’étude de leur RPS. La MET, la plasmonique environnementale et les nombreuses simulations (réponse optique, simulations Monte-Carlo) suggèrent une ségrégation du fer et de l’argent avec une surface enrichie en argent. L’oxydation semble induire la diffusion du fer en surface, directement suivie de la formation de magnétite (Fe3O4)Bimetallic nanoparticles (NPs) are known to present interesting catalytic properties justifying their use in several industrial processes in the domain of heterogeneous catalysis. However, their (chemical, geometrical, electronical) structure may evolve under realistic reactive atmosphere, involving a modification of their properties. In this multidisciplinary work, the aim is focused on the surface reactivity monitoring of these NPs under controlled gaseous environment. For this purpose, we developed an in situ spectrophotometer based on spatial modulation to monitor the structure evolution of a large assembly of NPs through the study of their localized surface plasmon resonance (LSPR). This global approach has been coupled with a more local approach by environmental transmission electronic microscopy (E-TEM). E-TEM observations have shown both composition and environmental effects on the chemical structure of Ag-In NPs. This structure evolves from a stable low-enriched indium alloy to a core@shell configuration with a shell composed of indium oxide as the indium atomic concentration increases. Furthermore, stable structure (core@shell, Janus, reduced system) domains were evidenced under reducing atmosphere, depending on the temperature and hydrogen pressure. Lastly, Ag-Fe NP oxido-reduction was monitored on the new setup through LSPR modifications. MET observations, environmental plasmonics and simulations (optical response, Monte-Carlo simulations) suggest that these metals are initially segregated, with an enriched-silver surface. The exposure to an oxidative atmosphere seems to induce the diffusion of iron onto the surface, followed by the formation of magnetite (Fe3O4

Spectroscopie optique et microscopie électronique environnementale de nanoparticules Ag-In et Ag-Fe en présence de gaz réactifs

Bimetallic nanoparticles (NPs) are known to present interesting catalytic properties justifying their use in several industrial processes in the domain of heterogeneous catalysis. However, their (chemical, geometrical, electronical) structure may evolve under realistic reactive atmosphere, involving a modification of their properties. In this multidisciplinary work, the aim is focused on the surface reactivity monitoring of these NPs under controlled gaseous environment. For this purpose, we developed an in situ spectrophotometer based on spatial modulation to monitor the structure evolution of a large assembly of NPs through the study of their localized surface plasmon resonance (LSPR). This global approach has been coupled with a more local approach by environmental transmission electronic microscopy (E-TEM). E-TEM observations have shown both composition and environmental effects on the chemical structure of Ag-In NPs. This structure evolves from a stable low-enriched indium alloy to a core@shell configuration with a shell composed of indium oxide as the indium atomic concentration increases. Furthermore, stable structure (core@shell, Janus, reduced system) domains were evidenced under reducing atmosphere, depending on the temperature and hydrogen pressure. Lastly, Ag-Fe NP oxido-reduction was monitored on the new setup through LSPR modifications. MET observations, environmental plasmonics and simulations (optical response, Monte-Carlo simulations) suggest that these metals are initially segregated, with an enriched-silver surface. The exposure to an oxidative atmosphere seems to induce the diffusion of iron onto the surface, followed by the formation of magnetite (Fe3O4)Les nanoparticules (NPs) bimétalliques présentent des propriétés catalytiques très intéressantes qui justifient leur utilisation dans des procédés industriels de catalyse hétérogène. Leur structure (chimique, géométrique, électronique) est néanmoins susceptible d’évoluer dans des conditions environnementales réelles et modifier leurs propriétés. L’objectif de cette thèse pluridisciplinaire est de suivre la réactivité de ces NPs en atmosphère réactive contrôlée. Pour cela, on a développé un dispositif de spectroscopie in situ à modulation spatiale afin de suivre l’évolution de la structure sur une grande population de NPs via l’étude de leur résonance du plasmon de surface (RPS) localisée. Ces observations ont été couplées avec une approche locale (NPs individuelles) par microscopie électronique à transmission environnemental (MET-E). La MET-E a permis de révéler des effets de composition et d’environnement sur la structure chimique de NPs Ag-In. Des alliages stables pauvres en indium se forment, puis une coquille d’oxyde d’indium dont l’épaisseur augmente avec la concentration atomique d’indium. D’autre part, des domaines de structures stables (coeur@coquille, Janus, système réduit) ont été mis en évidence selon les conditions locales de température et de pression d’hydrogène. Enfin, l’oxydo-réduction de NPs Ag-Fe a été suivie in situ via l’étude de leur RPS. La MET, la plasmonique environnementale et les nombreuses simulations (réponse optique, simulations Monte-Carlo) suggèrent une ségrégation du fer et de l’argent avec une surface enrichie en argent. L’oxydation semble induire la diffusion du fer en surface, directement suivie de la formation de magnétite (Fe3O4

Contact laws between nanoparticles: the elasticity of a nanopowder

International audienceStudies of the mechanical contact between nanometer-scale particles provide fundamental insights into the mechanical properties of materials and the validity of contact laws at the nanoscale which are still under debate for contact surfaces approaching atomic dimensions. Using in situ Brillouin light scattering under high pressure, we show that effective medium theories successfully predict the macroscopic sound velocities in nanopowders if one takes into account the cementation of the contacts Our measurements suggest the relevance of the continuum approach and effective medium theories to describe the contact between nanoparticles of diameters as small as 4 nm, i.e. with radii of contact of a few angstroms. In particular, we demonstrate that the mechanical properties of nanopowders strongly depend on the surface state of the nanoparticles. The presence of molecular adsorbates modifies significantly the contact laws

Fano Transparency in Rounded Nanocube Dimers Induced by Gap Plasmon Coupling

International audienceHomodimers of noble metal nanocubes form model plasmonic systems where the localized plasmon resonances sustained by each particle not only hybridize but also coexist with excitations of a different nature: surface plasmon polaritons confined within the Fabry−Perot cavity delimited by facing cube surfaces (i.e., gap plasmons). Destructive interference in the strong coupling between one of these highly localized modes and the highly radiating longitudinal dipolar plasmon of the dimer is responsible for the formation of a Fano resonance profile and the opening of a spectral window of anomalous transparency for the exciting light. We report on the clear experimental evidence of this effect in the case of 50 nm silver and 160 nm gold nanocube dimers studied by spatial modulation spectroscopy at the single particle level. A numerical study based on a plasmon mode analysis leads us to unambiguously identify the main cavity mode involved in this process and especially the major role played by its symmetry. The Fano depletion dip is red-shifted when the gap size is decreasing. It is also blue-shifted and all the more pronounced that the cube edge rounding is large. Combining nanopatch antenna and plasmon hybridization descriptions, we quantify the key role of the face-to-face distance and the cube edge morphology on the spectral profile of the transparency dip. T he optical excitation of localized surface plasmon resonances (LSPR) in single metallic nanoparticles or multicomponent nanostructures is responsible for efficient resonant far-field scattering and near-field concentration of light. 1,2 Such nanoantennas offer the opportunity to manipulate light at scales much shorter than the wavelength by making the best use of the LSPR sensitivity to variations in particle shape, size, chemical composition, and dielectric environment. 3,4 The electrostatic coupling between several plasmonic subunits is an additional tool for tailoring the optical response over a wide spectral range. 5,6 In this respect, much attention is paid to analogues of Fano resonances in classical electrostatics and especially those arising from the coupling between a " dark " plasmonic mode (weak dipole moment and narrow line width) and a degenerate mode that is highly radiative over a much broader spectral range (" bright " mode, large dipole moment). On either side of the resonance, the rapid phase shift of the " dark " mode polarizability relative to that of the bright mode and the exciting field may induce constructive or destructive interference in the net far field scattering process. They result in the formation of a dip in the broad spectral band of the far field scattered light with a typical dissymmetric profile and a narrow width related to the " dark " resonance lifetime. 7−11 Fano resonances open sharp and transparent windows in the plasmonic response of metallic nanostructures. 12−14 Their high sensitivity to relative changes in the nanostructure dielectric environment can be efficiently exploited for chemical and biological sensing. 15,16 Most of the studies in this field deal with noble metal nanoantennas built from the assembly and coupling of subunits of various size, shape, and orientation: oligomers of colloidal particles (DNA assembled, 17,18 heterodimers 19) and predominantly objects engraved by electron-beam lithography. 20−22 This method offers considerable flexibility for designing the spectral response of intricate structures with an advantageous symmetry breaking. 13,23 In the far field, they act as wide ban

Size effects of the magnetic anisotropy of fcc cobalt nanoparticles embedded in copper

Cobalt nanoparticles embedded in copper matrices show strong size effects in the magnetic anisotropy with a non-monotonous dependence on the particle diameter. In this article we discuss quantitative values of the magnetic anisotropy in the frame of two models: in small clusters the surface anisotropy contribution dominates whereas larger particles ( >3 nm diameter) have an elliptic shape leading to increased shape anisotropy. The crystalline structure of the particles is shown to be face-centered cubic, justifying that the magneto-crystalline anisotropy can be neglected