Nanotermoparells: heterounions de nanowires

Projecte de recerca elaborat a partir d’una estada a la University of California a Irvine, EEUU, entre juliol del 2007 i gener del 2008. Els termoparells són actualment els sensors de temperatura més populars i més utilitzats per a un ampli rang d’aplicacions: industrials, domèstiques, etc. Aconseguir miniaturar els dispositius fins a dimensions extremadament petites obra un ampli rang de noves aplicacions per aquests dispositius, per exemple, en el camp de la tecnologia lab-on-a-chip. En aquesta investigació, el concepte de termoparell, és a dir, dos cables de diferent metall connectats per un extrem s’ha extrapolat a l’escala nanomètrica, utilitzant nanowires com a element de construcció. Aquests nanowires s’han sintetitzat a través d’un nou procediment desenvolupat en el grup d’investigació de la Universitat de California, Irvine, que ha permès treballar amb nanowires de diferents dimensions (control independent de l’alçada i amplada) i un major grau d’èxit en la fabricació d’aquests termometres. El mètode també permet dipositar aquestes nanoestructures sobre substractes no conductors de manera controlable, simplificant notablement tot el procés de fabricació. L’obtenció d’aquests dispositius ha permès demostrar que, a part de ser bons sensors de temperatura a nivell macroscòpic (fonts de calor ambientals), també permet la determinació de temperatura a nivell microscòpic (fonts de calor focalitzada, com és el cas de feixos làser). Per a la seva caracterització ha estat necessari l’ús de tecnologia puntera (làsers, amplificadors, microscopis de forces atòmiques) i inclòs el disseny de nous dispositius. Aquests nanotermoparells presenten propietats extraordinàries, com una gran sensitivitat, gran velocitat de resposta a estímuls tèrmics, i un comportament estable vers l’ús i el temps.

Silver space-time trellis-coded modulation

Silver Code (SilC) was originally discovered in [1–4] for 2×2 multiple-input multiple-output (MIMO) transmission. It has non-vanishing minimum determinant 1/7, slightly lower than Golden code, but is fast-decodable, i.e., it allows reduced-complexity maximum likelihood decoding [5–7]. In this paper, we present a multidimensional trellis-coded modulation scheme for MIMO systems [11] based on set partitioning of the Silver Code, named Silver Space-Time Trellis Coded Modulation (SST-TCM). This lattice set partitioning is designed specifically to increase the minimum determinant. The branches of the outer trellis code are labeled with these partitions. Viterbi algorithm is applied for trellis decoding, while the branch metrics are computed by using a sphere-decoding algorithm. It is shown that the proposed SST-TCM performs very closely to the Golden Space-Time Trellis Coded Modulation (GST-TCM) scheme, yetwith a much reduced decoding complexity thanks to its fast-decoding property.

Influence of the (111) twinning on the formation of diamond cubic/diamond hexagonal heterostructures in Cu-catalyzed Si nanowires

The occurrence of heterostructures of cubic silicon/hexagonal silicon as disks defined along the nanowire (111) growth direction is reviewed in detail for Si nanowires obtained using Cu as catalyst. Detailed measurements on the structural properties of both semiconductor phases and their interface are presented. We observe that during growth, lamellar twinning on the cubic phase along the (111) direction is generated. Consecutive presence of twins along the (111) growth direction was found to be correlated with the origin of the local formation of the hexagonal Si segments along the nanowires, which define quantum wells of hexagonal Si diamond. Finally, we evaluate and comment on the consequences of the twins and wurtzite in the final electronic properties of the wires with the help of the predicted energy band diagram.

Size-dependent recombination dynamics in ZnO nanowires.

A deep understanding of the recombination dynamics of ZnO nanowires NWs is a natural step for a precise design of on-demand nanostructures based on this material system. In this work we investigate the influence of finite-size on the recombination dynamics of the neutral bound exciton around 3.365 eV for ZnO NWs with different diameters. We demonstrate that the lifetime of this excitonic transition decreases with increasing the surface-to-volume ratio due to a surface induced recombination process. Furthermore, we have observed two broad transitions around 3.341 and 3.314 eV, which were identified as surface states by studying the dependence of their life time and intensitiy with the NWs dimensions.

Enhancement of the photoelectrochemical properties of Cl-doped ZnO nanowires by tuning their coaxial doping profile

Arrays of vertically aligned ZnO:Cl/ZnO core-shell nanowires were used to demonstrate that the control of the coaxial doping profile in homojunction nanostructures can improve their surface charge carrier transfer while conserving potentially excellent transport properties. It is experimentally shown that the presence of a ZnO shell enhances the photoelectrochemical properties of ZnO:Cl nanowires up to a factor 5. Likewise, the ZnO shell promotes the visible photoluminescence band in highly conducting ZnO:Cl nanowires. These lines of evidence are associated with the increase of the nanowires" surface depletion layer

Defect study of SnO2 nanostructures by cathodoluminescence analysis: Application to nanowires

Defects in SnO2 nanowires have been studied by cathodoluminescence, and the obtained spectra have been compared with those measured on SnO2 nanocrystals of different sizes in order to reveal information about point defects not determined by other characterization techniques. Dependence of the luminescence bands on the thermal treatment temperatures and pre-treatment conditions have been determined pointing out their possible relation, due to the used treatment conditions, with the oxygen vacancy concentration. To explain these cathodoluminescence spectra and their behavior, a model based on first-principles calculations of the surface oxygen vacancies in the different crystallographic directions is proposed for corroborating the existence of surface state bands localized at energy values compatible with the found cathodoluminescence bands and with the gas sensing mechanisms. CL bands centered at 1.90 and 2.20 eV are attributed to the surface oxygen vacancies 100° coordinated with tin atoms, whereas CL bands centered at 2.37 and 2.75 eV are related to the surface oxygen vacancies 130° coordinated. This combined process of cathodoluminescence and ab initio calculations is shown to be a powerful tool for nanowire defect analysis.

The effects of electron-hole separation on the photoconductivity of individual metal oxide nanowires

The responses of individual ZnO nanowires to UV light demonstrate that the persistent photoconductivity (PPC) state is directly related to the electron¿hole separation near the surface. Our results demonstrate that the electrical transport in these nanomaterials is influenced by the surface in two different ways. On the one hand, the effective mobility and the density of free carriers are determined by recombination mechanisms assisted by the oxidizing molecules in air. This phenomenon can also be blocked by surface passivation. On the other hand, the surface built-in potential separates the photogenerated electron¿hole pairs and accumulates holes at the surface. After illumination, the charge separation makes the electron¿hole recombination difficult and originates PPC. This effect is quickly reverted after increasing either the probing current (self-heating by Joule dissipation) or the oxygen content in air (favouring the surface recombination mechanisms). The model for PPC in individual nanowires presented here illustrates the intrinsic potential of metal oxide nanowires to develop optoelectronic devices or optochemical sensors with better and new performances.

Composition, nanostructure, and optical properties of silver and silver-copper lusters

Lusters are composite thin layers of coinage metal nanoparticles in glass displaying peculiar optical properties and obtained by a process involving ionic exchange, diffusion, and crystallization. In particular, the origin of the high reflectance (golden-shine) shown by those layers has been subject of some discussion. It has been attributed to either the presence of larger particles, thinner multiple layers or higher volume fraction of nanoparticles. The object of this paper is to clarify this for which a set of laboratory designed lusters are analysed by Rutherford backscattering spectroscopy, transmission electron microscopy, x-ray diffraction, and ultraviolet-visible spectroscopy. Model calculations and numerical simulations using the finite difference time domain method were also performed to evaluate the optical properties. Finally, the correlation between synthesis conditions, nanostructure, and optical properties is obtained for these materials.

Si3N4 single-crystal nanowires grown from silicon micro- and nanoparticles near the threshold of passive oxidation

A simple and most promising oxide-assisted catalyst-free method is used to prepare silicon nitride nanowires that give rise to high yield in a short time. After a brief analysis of the state of the art, we reveal the crucial role played by the oxygen partial pressure: when oxygen partial pressure is slightly below the threshold of passive oxidation, a high yield inhibiting the formation of any silica layer covering the nanowires occurs and thanks to the synthesis temperature one can control nanowire dimensions

Spatial mapping of exciton lifetimes in single ZnO nanowires

We investigate the spatial dependence of the exciton lifetimes in single ZnO nanowires. We have found that the free exciton and bound exciton lifetimes exhibit a maximum at the center of nanowires, while they decrease by 30% towards the tips. This dependence is explained by considering the cavity-like properties of the nanowires in combination with the Purcell effect. We show that the lifetime of the bound-excitons scales with the localization energy to the power of 3/2, which validates the model of Rashba and Gurgenishvili at the nanoscale.

Electrochemical synthesis of mesoporous CoPt nanowires for methanol oxidation

A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane"s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter) dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

Ecology of Armillaria species on silver fir (Abies alba) in the Spanish Pyrenees

We describe the distribution and the ecology of three Armillaria species observed in silver fir (Abies alba) forests of the Pyrenees. We surveyed the presence and abundance of Armillaria above and belowground in 29 stands. Isolates were identified by the PCR-RFLP pattern of the IGS-1 region of their ribosomal DNA. We measured several ecological and management parameters of each stand in order to describe Armillaria infected sites. Armillaria cepistipes was the most abundant of three species observed. Armillaria gallica was dominant in soils with a higher pH and at lower elevations. Armillaria ostoyae seemed to be more frequent in stands where A. alba recently increased its dominance relative to other forest tree species. Thinning activities correlated with an increased abundance of Armillaria belowground. In 83% of the stands the same Armillaria species was observed above and belowground. It seems that in a conifer forest, A. cepistipes can be more frequent than A. ostoyae, a virulent conifer pathogen. Since logging is related to a higher abundance of Armillaria in the soil, the particular Armillaria species present in a given stand could be considered an additional site factor when making management decisions.

A comparative study of silver amalgam and compomer as retrograde filling materials in periapical surgery

Objective: A comparative study is made of the histological effects of silver amalgam versus compomer (Dyract®) 90 days after placement as retrograde filling materials in experimental animals. Method: Six Beagle dogs were used, with total pulpectomy and orthograde material filling followed by periapical surgery of the 6 upper and 6 lower incisors (for a total of 72 teeth). Thirty-six teeth corresponded to the right side and were filled with the control material (silver amalgam), while the 36 teeth on the left side were filled with the compomer study material (Dyract®). After three months the animals were sacrificed and the histological study was carried out, with evaluation of bone formation, inflammation, and the tissue in contact with the filler material. The results obtained were subjected to a descriptive and comparative statistical analysis (chi-square test). Results: The samples retrogradely filled with compomer showed significantly greater percentage inflammation (76.19% versus 26.66% in the control group). On the other hand, a large proportion of samples with root cement growth were found in the compomer group. Filler material expulsion was also significantly more common when compomer was used. Conclusions: the comparative study of the histological findings showed greater inflammation but also greater root cement growth in the compomer group versus the controls

Spatial mapping of exciton lifetimes in single ZnO nanowires

We investigate the spatial dependence of the exciton lifetimes in single ZnO nanowires. We have found that the free exciton and bound exciton lifetimes exhibit a maximum at the center of nanowires, while they decrease by 30% towards the tips. This dependence is explained by considering the cavity-like properties of the nanowires in combination with the Purcell effect. We show that the lifetime of the bound-excitons scales with the localization energy to the power of 3/2, which validates the model of Rashba and Gurgenishvili at the nanoscale.

Electrochemical synthesis of mesoporous CoPt nanowires for methanol oxidation

A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane"s channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter) dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.