Low-energy excitations in type-II Weyl semimetal T-d-MoTe2 evidenced through optical conductivity

Molybdenum ditelluride, MoTe2, is a versatile material where the topological phase can be readily tuned by manipulating the associated structural phase transition. The fine details of the band structure of MoTe2, key to understanding its topological properties, have proven difficult to disentangle experientially due to the multiband character of the material. Through experimental optical conductivity spectra, we detect two strong low-energy interband transitions. Both are linked to excitations between spin-orbit split bands. The lowest interband transition shows a strong thermal shift, pointing to a chemical potential that dramatically decreases with temperature. With the help of ab initio calculations and a simple two-band model, we give qualitative and quantitative explanations of the main features in the temperature-dependent optical spectra up to 400 meV.

Conductivity, dielectric and piezoelectric properties of SrBi4Ti4O15

Strontium Bismuth Titanate is a very promising material for high temperature piezoelectric applications, its elevated ferroelectric phase transition (530°C), linear piezoelectric properties under low field and relatively low room temperature conductivity (compared to others Bismuth Titanates) make it very attractive for precision sensors. However, under severe conditions (low frequency, high field, high temperature or low oxygen partial pressure) some of those advantages disappear. Piezoelectric response is dominated by charge drift in general becomes unstable. Above all, at high temperature and low oxygen partial pressure, a large conductivity increase reduces the piezoelectric efficiency of the material, in this work, electrical conductivity, piezoelectric properties and dielectric permittivity of SrBIT ceramic have been investigated in conditions of high temperature, low oxygen partial pressure, low to moderate driving field and frequency. As a result of this research, a better understanding of SrBIT properties was achieved. Thanks to a careful study of SrBIT processing as a bulk ceramic, a reproducible route was established. Many basic mechanisms leading to both SrBIT crystallization and sintering have been identified. It was demonstrated that a detailed knowledge of the exact processing conditions is required in order to achieve high quality material. DC conductivity measurements were carried out as a function of temperature, oxygen partial pressure and dopant concentration. It was found that the apparent activation energy for conduction for undoped SrBIT was 1 eV between 140 and 220°C and 1.5 eV between 450 and 700°C. Decrease of the activation energy in the lower temperature range has been discussed considering grain boundary conductivity, as a transition from electronic to ionic conduction or as consequence of small polarons conduction. It was shown that lower activation energy resulted from Manganese doping (0.5 eV), this was interpreted as either growing influence of grain boundary conductivity as dopant concentration increases or as shallow hole trap formation. DC conductivity measurements and acceptor/donor doping experiments demonstrated p-type conductivity in the low temperature range (up to 220°C) as donor doping decreases conductivity, while oxygen partial pressure controlled measurements indicated n-type conductivity at higher temperature (above 700°C). An electrical impedance analysis was performed with several equivalent circuits. The aim of these models was to simulate the impedance of SrBIT. The best approximation was found with a distributed element of Havriliak-Negami type. However, as the physical justification for this circuit was not clear, the investigation of the grain, grain boundary and electrode impedances was performed with multiple discrete parallel RC elements. With temperature, grain size and oxygen activity variations, the identification of three separate contributions as grain, grain boundary and electrode was realized. The anisotropy of conductivity and permittivity was demonstrated with textured material and both DC and AC analysis. With the master curves built for the electrical modulus, it was found that the impedance probably related to Bismuth oxide layers produces an additional high frequency are. From this finding and by comparing characteristic relaxation frequencies of undoped, 2 mol.% Mn and 4 mol.% Nb SrBIT, it was determined that conductivity is higher in the ab plane direction than in the c direction within both perovskite units and Bismuth oxide layers. With conductivity measurements under controlled oxygen partial pressure, it was found that an acceptor-based (intrinsic or extrinsic) model could be used to describe the electrical conductivity under controlled oxygen partial pressure of both undoped and 2 mol.% Mn doped SrBIT. However, as neither a pO2-1/6 region (intrinsic oxygen vacancies compensated by electrons) for undoped SrBIT nor a pO2-1/4 region (oxygen vacancies compensated by singly ionized acceptors) for Mn doped SrBIT were seen, it was concluded that the acceptorcontrolled model is not sufficient for a complete description of SrBIT. For this reason and in order to include the low oxygen partial pressure behavior of undoped SrBIT, a donor-based (intrinsic) model was also considered. The source of intrinsic donors would be in that case Bi3+ cations sitting on Sr2+ sites in the perovskite sublattice. Considering Bismuth vacancies as the negative compensating species, both pO2-1/4 and pO2-independent regions could be predicted with the model. However, even if the donor-controlled model seems to better match conductivity measurements in the full PO2) range, rejecting the acceptor-based model would be an error. It is actually not demonstrated that in SrBIT the concentration of exchanged Bismuth cations is always (all temperature, pressure) larger than the natural acceptor impurity concentration. It is very likely that the cation exchange is dependent of the oxygen partial pressure. It is also not proved as suggested in the literature that direct compensation between exchanged Strontium and Bismuth exists, reducing the net donor-excess. With the acceptor-controlled model, the mass-action constants for reduction and for ionization of intrinsic carriers across the band gap were determined. The band gap of SrBIT was estimated to be 3.5 eV. The ionic conductivity of SrBIT was determined at high temperature with measurements under controlled oxygen partial pressure. It was found that the electrical conductivity of SrBIT is probably mixed (electronic and ionic) as the estimation of the transference number provided quite large values (t=0.8 at 800°C). From electronic and ionic conductivity data, mixed conduction can actually be predicted in a large temperature range (above room temperature). The piezoelectric measurements using direct effect demonstrated that it is actually possible to unlock piezoelectrically active ferroelectric domain walls and create non-linear piezoelectric properties in undoped SrBIT. This occurs above a threshold elastic field, which is thermally activated. With a piezoelectric composite, it was demonstrated that the electromechanical coupling between two different phases creates a piezoelectric relaxation. This one could be positive or negative depending on the respective properties of each composite's component. It was shown experimentally that a small temperature change is sufficient to transform a positive relaxation into a negative one. While these experiments did not provide a detailed microstructural explanation for the piezoelectric relaxation observed in 2 mol.% Mn doped SrBIT, they gave a first insight into an original phenomenological approach. Microstructure and piezoelectric properties were related with the calculation of a piezoelectric relaxation composite made of two textured samples. This demonstrated that a piezoelectric relaxation may occur just because of anisotropy. Microstructural reproduction of this coupling is actually an important feature of Aurivillius phases.

EPFL2000

Photoemission studies of thin films grown by pulsed laser deposition

Mike Abrecht

In this thesis I report on the unique novel possibilities offered by combining pulsed laser deposition (PLD) film growth of high temperature superconductors with angle integrated and angle resolved photoemission spectroscopy (PES and ARPES). The originality of the procedure rests on the in situ preparation and transfer of samples, hence by-passing the usual cumbersome cleaving or scraping practices to obtain high quality surfaces suitable for photoemission studies. Photoemission spectroscopy is one of the major experimental techniques to analyze the electronic structure that holds the key to understanding the properties of the high Tc cuprates (copper oxides) for which a complete microscopic theory still needs to materialize. In chapter 1, I introduce these complex copper oxide materials. The vast majority of ARPES measurements on the cuprate superconductors have so far been limited to the easily cleavable Bi2Sr2CaCu2O8+x (BSCCO-2212) single crystals. In chapter 2, I present the principle of an ARPES measurement, and show as an example (obtained in the "traditional way" of cleaving single crystals) a crossover in the electronic response at a special temperature T+>Tc in overdoped samples. In chapter 3, our unique laser ablation set-up, built on site at the Wisconsin Synchrotron Radiation Center (SRC), is introduced. This is followed by reports on film characterization such as transport, crystal and surface properties which enables the optimization of growth parameters. From here on to the end of the thesis, we show that instead of being a competing technique to cleaving samples, in situ growth of films appears to be a complementary one. In particular, our results show that preparing cuprates which contain oxygen chains, like Re-Ba2Cu3O6+x (RBCO-123; R=Y, Nd), for the surface sensitive ARPES measurements is very difficult due to a material intrinsic loss of oxygen near the surface. This, in turn, curbs the photoemission signal near the chemical potential due to the loss of superficial conductivity (chapter 3). Among the cuprates studied, La2-xSrxCuO4 (LSCO) and Bi2Sr2CaCu2O8+x films, however, both exhibit a sharp Fermi step in angle integrated photoemission spectra, indicating a conducting behavior at the surface. Moreover, thanks to using film samples, we were able to study ultra thin cuprates, down to about 1 unit cell (UC), and we were able to induce epitaxial strain in the samples which can remarkably enhance superconductivity. In chapter 4, combining core level, angle integrated valence band photoemission, and x-ray diffraction, we demonstrate that a structural phase transition occurs in the early growth of BSCCO-2212 films on SrTiO3 (STO) substrates, transforming the precursor Bi6O7 natural reactive buffer layer into the BSCCO-2212 structure. This is qualitatively different from the initial growth of YBCO-123 characterized by nucleation of well separated islands. Chapter 5 then presents the main success of our method: the first ever ARPES data on the low energy electronic structure of any high Tc superconductor under strain. In particular, we confirm that the Fermi surface (FS) of LSCO evolves with doping, but changes even more significantly with strain. More specifically, the FS becomes electron-like for in-plane compressed samples (for all doping values x studied, 0.1

EPFL2003

A multi-technique approach to study the microstructural properties of tin-based transparent conductive oxides

Federica Landucci

Transparent conductive oxides (TCOs) are semiconductor-like materials that exhibit high electrical conductivity and high optical transparency combined. They are adopted in various applications ranging from gas sensors, to electrochromic windows, to photovoltaic cells. Indium-based TCOs represent the industry standard. Nevertheless, indium is among the less abundant elements in the earth crust and forecasts based on its current consumption envisage an urgent need to replace it. Tin-based TCOs are a promising alternative, since their opto- electronic characteristics mimic the ones of indium-based materials. This thesis aims to investigate the link between optoelectronic and microstructural properties of tin dioxide and zinc tin oxide (ZTO) with a composition Zn0.05Sn0.30O0.65 and their stability when submitted to thermal treatments. Indeed, lots of practi- cal applications require the TCO to operate in high temperature conditions. To conduct this study, a combination of analytical techniques, such as transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX), X- ray diffraction (XRD), electron paramagnetic resonance (EPR) and differential scanning calorimetry (DSC) was employed. Amorphous SnO2 and ZTO were deposited by RF sputtering and annealed up to 1050°C in different atmospheres. The influence of annealing temperature and atmosphere were decoupled and led us to an in-depth comprehension of the mechanisms governing the optoelectronic properties of both materials. When annealed in air, between room temperature and 300°C, ZTO exhibits increased mobility and carrier concentration with respect to the as-deposited state. This increase, investigated with DSC, was ascribed to a structural relaxation that allows point defects to release electrons in conduction band. Between 300°C and 500°C atmospheric oxygen passivates oxygen vacancies, drastically decreasing the carrier concentration and therefore causing a large drop of the conductivity. EPR experiments allowed to ascribe the drop in conductivity to the decrease of carrier concentration, which occurs slightly before the phase change. At 570°C (and 930°C for the case of vacuum annealing) the phase change occurs and the ZTO crystallizes in the rutile form of SnO2. The material becomes completely insulating. When the temperature is increased to 1050°C, evaporation of zinc is observed. In order to improve the electrical conductivity of ZTO at high temperature, a doping strategy was implemented starting from DFT calculations conducted by a partner group, who screened among the entire periodic table, which elements are the best candidates to act as n-dopants for ZTO. Bromine and iodine were retained, since they were found to be the most energetically favorable to become substitutional defects for a tin site. An exploratory doping route is therefore presented and the treated samples analyzed with TEM, EDX and UV-VIS-IR spectroscopy. Finally, the structural properties of an indium-based TCO (zirconium-doped indium oxide) were investigated and used as a benchmark to propose a crystallization model for the tin-based, as well as the indium-based materials. The influence of pa- rameters such as the material thickness, annealing atmosphere and temperature and deposition pressure are discussed for both materials.

EPFL2019