A. Cantarero

Probing Nanoscale Ferroelectricity by Ultraviolet Raman Spectroscopy

We demonstrated that ultraviolet Raman spectroscopy is an effective technique to measure the transition temperature (Tc) in ferroelectric ultrathin films and superlattices. We showed that one-unit-cell-thick BaTiO3 layers in BaTiO3/SrTiO3 superlattices are not only ferroelectric (with Tc as high as 250 kelvin) but also polarize the quantum paraelectric SrTiO3 layers adjacent to them. Tc was tuned by ∼500 kelvin by varying the thicknesses of the BaTiO3 and SrTiO3 layers, revealing the essential roles of electrical and mechanical boundary conditions for nanoscale ferroelectricity.

Review on Polymers for Thermoelectric Applications

In this review, we report the state-of-the-art of polymers in thermoelectricity. Classically, a number of inorganic compounds have been considered as the best thermoelectric materials. Since the prediction of the improvement of the figure of merit by means of electronic confinement in 1993, it has been improved by a factor of 3–4. In the mean time, organic materials, in particular intrinsically conducting polymers, had been considered as competitors of classical thermoelectrics, since their figure of merit has been improved several orders of magnitude in the last few years. We review here the evolution of the figure of merit or the power factor during the last years, and the best candidates to compete with inorganic materials. We also outline the best polymers to substitute classical thermoelectric materials and the advantages they present in comparison with inorganic systems.

Enhanced thermoelectric performance of PEDOT with different counter-ions optimized by chemical reduction

This work reports on the synthesis of the intrinsically conducting polymer poly(3,4-ethylenedioxythiophene) (PEDOT) doped with several counter-ions, ClO4, PF6 and bis(trifluoromethylsulfonyl)imide (BTFMSI), by electro-polymerization and its thermoelectric properties. We show that, depending on the counter-ion size, the thermoelectric efficiency of PEDOT can be increased up to two orders of magnitude. A further chemical reduction with hydrazine optimizes the power factor (PF). By changing the counter-ions, we were able to increase the electrical conductivity (σ) of PEDOT by a factor of three, while the Seebeck coefficient remains at the same order of magnitude in the three polymers. The best thermoelectric efficiency has been observed in PEDOT:BTFMSI. From the measurement of the Seebeck coefficient and σ, a PF of 147 μW m−1 K−2 has been deduced, while the measured thermal conductivity is κ = 0.19 W m−1 K−1, resulting in a ZT ∼ 0.22 at room temperature, one of the highest values reported in the literature for polymers. The increase in σ with the change of the counter-ion is mainly due to the stretching of the polymer chains. In this work, we provide a chemical route to further improve ZT in polymers and demonstrate a method of synthesis based on the electro-polymerization on gold. After removing the gold layer, a very thin semiconducting polymer film can be isolated.

Thermoelectric properties of atomically thin silicene and germanene nanostructures

The thermoelectric properties in one- and two-dimensional silicon and germanium structures have been investigated using first-principle density functional techniques and linear response for the thermal and electrical transport. We have considered here the two-dimensional silicene and germanene, together with nano-ribbons of different widths. For the nano-ribbons, we have also investigated the possibility of nano-structuring these systems by mixing silicon and germanium. We found that the figure of merit at room temperature of these systems is remarkably high, up to 2.5.

Electronic structure, optical properties, and lattice dynamics in atomically thin indium selenide flakes

The progressive stacking of chalcogenide single layers gives rise to two-dimensional semiconducting materials with tunable properties that can be exploited for new field-effect transistors and photonic devices. Yet the properties of some members of the chalcogenide family remain unexplored. Indium selenide (InSe) is attractive for applications due to its direct bandgap in the near infrared, controllable p- and n-type doping and high chemical stability. Here, we reveal the lattice dynamics, optical and electronic properties of atomically thin InSe flakes prepared by micromechanical cleavage. Raman active modes stiffen or soften in the flakes depending on which electronic bonds are excited. A progressive blue-shift of the photoluminescence peaks is observed for decreasing flake thickness (as large as 0.2 eV for three single layers). First-principles calculations predict an even larger increase in the bandgap, 0.40 eV, for three single layers, and as much as 1.1 eV for a single layer. These results are promising from the point of view of the versatility of this material for optoelectronic applications at the nanometer scale and compatible with Si and III-V technologies.

Thermoelectric properties of atomic-thin silicene and germanene nano-structures

The thermoelectric properties in one- and two-dimensional silicon and germanium structures have been investigated using first-principle density functional techniques and linear response for the thermal and electrical transport. We have considered here the two-dimensional silicene and germanene, together with nano-ribbons of different widths. For the nano-ribbons, we have also investigated the possibility of nano-structuring these systems by mixing silicon and germanium. We found that the figure of merit at room temperature of these systems is remarkably high, up to 2.5.

Electron-phonon effects on the direct band gap in semiconductors: LCAO calculations

Abstract Using a perturbative treatment of the electron–phonon interaction, we have studied the effect of phonons on the direct band gap of conventional semiconductors. Our calculations are performed in the framework of the tight-binding linear combination of atomic orbitals (LCAO) approach. Within this scheme we have calculated the temperature and isotopic mass dependence of the lowest direct band gap of several semiconductors with diamond and zincblende structure. Our results reproduce the overall trend of available experimental data for the band gap as a function of temperature, as well as give correctly the mass dependence of the band gap on isotopic. A calculation of conduction band intervalley deformation potentials is also reported. Finally, calculated Debye–Waller factors are compared with X-ray and EXAFS experimental results.

From kinetic to collective behavior in thermal transport on semiconductors and semiconductor nanostructures

We present a model which deepens into the role that normal scattering has on the thermal conductivity in semiconductor bulk, micro, and nanoscale samples. Thermal conductivity as a function of the temperature undergoes a smooth transition from a kinetic to a collective regime that depends on the importance of normal scattering events. We demonstrate that in this transition, the key point to fit experimental data is changing the way to perform the average on the scattering rates. We apply the model to bulk Si with different isotopic compositions obtaining an accurate fit. Then we calculate the thermal conductivity of Si thin films and nanowires by only introducing the effective size as additional parameter. The model provides a better prediction of the thermal conductivity behavior valid for all temperatures and sizes above 30 nm with a single expression. Avoiding the introduction of confinement or quantum effects, the model permits to establish the limit of classical theories in the study of the thermal conductivity in nanoscopic systems.

F-centre luminescence in nanocrystalline CeO2

Nanocrystalline CeO2 powders were synthesized by two cost-effective methods: the self-propagating room temperature (SPRT) method and the precipitation method. Differently prepared samples exhibited different temperature-dependent photoluminescence (PL) in the ultraviolet and visible regions. The PL signals originated from different kinds of oxygen-deficient defect centres with or without trapped electrons (F0, F+ or F++ centres). The temperature-dependent PL spectra were measured using different excitation lines, below (457, 488 and 514?nm) or comparable (325?nm) to the ceria optical band gap energy, in order to investigate the positions of intragap localized defect states. Evidence for the presence of F+ centres was supported by the signals observed in electron paramagnetic resonance (EPR) measurements. Based on PL and EPR measurements it was shown that F+ centres dominate in the CeO2 sample synthesized by the SPRT method, whereas F0 centres are the major defects in the CeO2 sample synthesized by the precipitation method. The luminescence from F++ states, as shallow trap states, was registered in both samples. Energy level positions of these defect states in the ceria band gap were proposed.

Photoluminescence study of excitons in homoepitaxial GaN

High-resolution photoluminescence spectra have been measured in high-quality homoepitaxial GaN grown on a free-standing GaN substrate with lower residual strain than in previous work. Unusually strong and well-resolved excitonic lines were observed. Based on free- and bound exciton transitions some important GaN parameters are derived. The Arrhenius plot of the free A exciton recombination yields a binding energy of 24.7 meV. Based on this datum, an accurate value for the band-gap energy, EG(4.3 K) = 3.506 eV, can be given. From the donor bound excitons and their “two-electron” satellites, the exciton localization energy and donor ionization energy are deduced. Finally, estimates of the electron and hole masses have been obtained within the effective mass approximation.