Pressure-tuned Transport Properties of Novel Iron-based Superconductors and Topological Insulators

The majority of interactions in solids strongly depend on the interatomic distances. The application of pressure changes the lattice parameters and modifies the electronic and the phononic energy spectra of a material avoiding some of the undesirable effects induced by chemical doping, like lattice disorder, impurity phases and phase separations. Layered materials are particularly affected by the application of pressure because their anisotropic structure eases the contraction of the lattice along specific crystallographic directions. In this thesis I study the effect of pressure on the transport properties of two new layered materials: L4Fe2As2Te(1-x)O4 (L = Pr, Sm, Gd) superconductors and beta-Bi4I4 topological insulator. The discovery of Fe-based superconductors (Fe-SCs) provided a new material base for studying the mechanism of high temperature superconductivity. These materials present unexpectedly high critical temperatures (Tc ) despite the presence of magnetic atoms. The parent compounds of Fe-SCs are semimetals with an antiferromagnetic ground state in which the itinerant electrons form a periodic modulation of spin density called spin density wave (SDW). By changing the structural properties or by adding/removing carriers the SDW order can be suppressed and superconductivity emerges. Our group recently succeeded in synthesizing a new family of Fe-SCs that presents Tc up to 45 K upon optimum chemical doping and substitution. I performed a systematic study of the upper critical field and the pressure-dependent electrical resistivity of single crystals of Pr4Fe2As2Te(1-x)O4 and Sm4Fe2As2Te(1-x)O(4-y)Fy . Hall coefficient and magnetoresistance of Pr4Fe2As2Te(1-x)O4 revealed electrons as the dominant type of charge carriers. The results can be successfully fitted by a two-band model that allows the estimation of the temperature dependent electron and hole densities and mobilities. In view of the exceptionally high structural anisotropy of this new class of Fe-SCs I investigated the electronic anisotropy of Sm4Fe2As2Te(1-x)O(4-y)Fy by means of microfabrication techniques. The results show a ratio between the out-of-plane and in-plane electrical resistivities that is the highest reported so far in Fe-SCs. Topological insulators (TIs) form another class of materials that is currently attracting a lot of attention both for fundamental physics and potential applications. In TIs metallic surface states coexist with an insulating bulk. Most of the TIs known so far are either three-dimensional strongly bonded bulk materials or layered van der Waals crystals. Beta-Bi4I4 is a material composed of quasi-one-dimensional molecular chains that was theoretically predicted, and only recently experimentally verified, to be a novel strong topological insulator. Due to its particular structure, beta-Bi4I4 offers the possibility to study the interplay between different ground states like topological insulating phase, charge-density-wave and superconductivity. Here I present, for the first time, a study of the thermoelectric properties of beta-Bi4I4 single crystals. Electrical resistivity, Seebeck coefficient, thermal conductivity and Hall coefficient measurements reveal a possible charge density-wave-order (CDW) at low temperature. According to resistivity and thermoelectric power measurements, pressure suppresses the CDW order. Resistivity measurements performed in a diamond anvil cell up to 20 GPa demonstrate that superconductivity is induced in beta-Bi4I4 for pressure above 10 GPa. Preliminary X-ray diffraction measurements by synchrotron radiation, performed on the sample recovered at ambient pressure after the experiment, reveal that a new Bi-I phase is formed at high pressure. The possibility that the topological insulator state could coexist with superconductivity in beta-Bi4I4 is certainly a fascinating option but it remains for now an open question.

Thermopower as a Unique Tool to Probe Quantum Phase Transitions

Stevan Arsenijevic

In my thesis, transport measurements such as resistivity and, more importantly, thermopower S, were used to explore the phase diagram of bad metals. Bad metals are electronically correlated systems whose ground state lies close to a quantum phase transition. By tuning the control parameters, such as temperature (T ), magnetic field (B), hydrostatic pressure (p) or chemical substitution (x), we can induce phase transitions between the various electronic, magnetic and structural phases. Here, the thermopower is presented as a unique tool for probing quantum phase transition because it is a measure of the entropy of conducting electrons. The main part of the thesis is dedicated to the study of Fe-based superconductors (FeSC) discovered in 2008. Their parent compound has an antiferromagnetic (AF) ground state, where the itinerant electrons form a spin-density wave (SDW), a periodic modulation of spin density. This coincides or is preceded by a structural, tetragonal-to-orthorhombic transition. The nesting between the electron and hole Fermi surface is believed to be the driving mechanism for the SDW state. By changing the structural or chemical properties the AF ground state of FeSC is suppressed, giving way to superconductivity (SC). The remaining antiferromagnetic fluctuations above the transition can provide a glue for SC pairing. Here, the analysis of the thermopower S/T of BaFe1−xCoxAs2 (BFCA) in the x-T phase diagram shows the signatures of the spin fluctuation which have a dome-like dependence and follow the trend of superconducting Tc . The logarithmic increase of S/T upon decreasing T is ascribed to the proximity of the spin-density-wave quantum critical point. It can be understood as an increase of entropy due to the incommensurate AF spin fluctuations. We can ascribe the high values of thermopower in BFCA at intermediate- and room-temperatures to the influence of low-T quantum criticality. To probe the response of the electronic system in FeSC to structural changes, we performed measurements under pressure of the parent compound BaFe2As2 (BFA), the SC electron-doped BFCA, and hole-doped Ba1−xKxFe2As2 (BKFA). In the parent compound pressure suppresses the structural/SDW transition, similar to the effect of doping. For doped systems, in order to describe the behavior of thermopower in the high-T range (above 100K) we used a semi-metallic two-band model which was fitted to the data in order to extract the pressure dependence of the band parameters. In both doping cases the effect of pressure was similar, an increase of the band overlap and of the effective number of charge carriers. With this model we can explain the high-T , x and p dependence of thermopower in both electron- and hole-doped BFA. In a structurally simpler Fe-chalcogenide Fe1+yTe1−xSex compound, the excess of Fe has a Kondo-like influence on the charge carriers which dramatically changes the physics of the normal state. To probe the normal state, pressure, doping, magnetic Fe-excess concentration (y) and temperature were used as control parameters. At low-T a characteristic upturn of resistivity (ρmag ) is observed, followed by an increase of thermopower (Smag ), which we identify as the magnetic contribution caused by the spin-flip scattering events. Increasing the y resulted in an increase of ρmag , and a decrease of Smag , which is in agreement with the behavior of canonical Kondo-systems. Pressure suppresses the magnetic contribution to transport, thus increasing the itinerancy of the system. MnSi is another system in which the sensitivity of thermopower to entropy brings new information related to the complex magnetic structure. Pressure was used to drive the system from a helically ordered, canonical Fermi-liquid (FL) phase with T 2-resistivity to the intrinsically disordered, non-Fermi-liquid (NFL) phase above pc with T3/2-dependence. Our contour plot of S/T demonstrated how powerful the thermopower technique is, by reproducing the whole previously established T -p phase diagram. At the phase transition from the magnetically-ordered FL phase to the disordered NFL, the thermopower is dramatically enhanced. We bring useful information about the mysterious partial order (PO) phase inside the NFL phase, previously detected only by neutron scattering. The fluctuating helices scenario can describe the observed increase of entropy/thermopower in the PO phase. At ambient pressure, close to the helical transition of MnSi, a moderate magnetic field can stabilize the skyrmion lattice - the lattice of topological magnetic whirls, vortices. We observe a signature of the skyrmion lattice as a minute drop in thermopower. It is located exactly in the same region of the T − B phase diagram where an increase in magnetoresistance and Hall effect was reported previously. This feature originates from the additional scattering of conducting electrons on magnetic vortices, while the change in S is dominated by the decrease of entropy as the stable skyrmion lattice is formed. Overall, resistivity was used to confirm the established phase diagram, while thermopower, as an interesting and not sufficiently understood technique, was used to probe the sensitive changes of the charge carriers at the Fermi surface. We explored various phases showing how useful thermopower is to probe the entropy of electronic system on the verge of quantum phase transition.

EPFL2012

Tailoring thermal properties of functional materials

Xavier François Mettan

Thermal conductivity (k) plays an essential role in functional devices. In some cases, high value is required to transfer heat efficiently. In others, low k assists in maintaining a temperature gradient necessary for device operation. It is profitable to design materials where one can tune k in a broad range according to its function. Beyond functionality, k is a fundamental property of matter, and a fantastic probe to assess vibrational dynamics and electronic structure in condensed matter. In conjunction with other transport properties such as electrical resistivity and thermoelectric power, k promotes a deeper understanding of the electronic and vibrational structure of materials. In the present Thesis, careful experimental determination of the transport coefficients of a variety of systems over a broad temperature range (4-300 K) let me unveil subtle interactions between phonons and/or electrons. The insights gained from an accurate interpretation of these properties empowers us to engineer and fine-tune the functionality of materials for applications. I first investigate the thermoelectric properties of nickel-based high-entropy alloys (HEAs), believed to host unconventional effects arising from the high level of site-disorder in their crystalline structure. Anomalous resistivity with a low temperature coefficient validates the disordered nature of HEAs. The Seebeck coefficient, reported for the first time for HEAs, is surprisingly low. In the quest to understand transport in HEA, I have discovered that iron-nickel alloys exhibit a promising thermoelectric figure of merit (ZT) of 0.1 at room temperature. One way to further increase ZT is to decrease k (in FeNi alloys or other materials) by texturing the material. Aluminium foams are systems of choice to observe the effect of a modified structure on the thermoelectric properties. Tailoring of the bubbles' size is demonstrated by applying an external acoustic force in the foaming process. Moreover, the influence of the macro- and micro- structure of the foams on thermoelectric properties is discussed. The best example for tuning k by texturing it is anatase titanium dioxide (TiO2). k was varied over three orders of magnitude by adjusting its oxygen contents and by texturing it into a foam, aerogel-like structure. We identified a new, strong diffusion mechanism of heat by polarons, created as a consequence of oxygen vacancies. Furthermore, anatase nanowires organized into foams result in an unprecedented low k = 0.014 W/Km at room-temperature. Doping this anatase foam heralds promising applications, in particular in thermoelectricity. An oxide which has an intrinsically nanoporous structure reminding that of a foam, is Mayenite (Ca12Al14O33). The thermal conductivity of such system is verified to be intrinsically low. The peculiar cage structure could host atomic of molecular species to tune its electrical conductivity, with bright prospects for thermoelectric applications. Finally, the thermoelectric properties of hybrid halide perovskites, cheap and easy-to-synthesise compounds, were studied. Three materials of this family have ultra-low k, due to the vibrational degrees of freedom of their organic cations. Notably, a tin-based organic-inorganic compound delivers ZT = 0.13 at room temperature. The thermoelectric conversion efficiency of this material was measured directly and is believed to yield promising thermoelectric applications.

EPFL2019

Normal state transport properties of novel superconductors

Balazs Sipos

The discovery of high temperature superconductivity in the cuprates in 1986 has boosted the research in strongly correlated materials. One strong motivation was and stays the understanding the high-Tc phenomenon with the hope that one can ultimately engineer new materials with even higher Tc. Besides the in-depth investigation of cuprates, there is a strong tendency in the solid state community to find new superconductors, which by themselves are interesting for applications, or by their properties they can contribute to the understanding of the high-Tc phenomenon. The program of my doctoral thesis was three-fold: i) to address one important issue in the cuprate superconductors, that of the role of homogeneity in the underdoped part of the phase diagram; ii) what is the effect of disorder in MgB2 superconductor, which has high potentials for applications; iii) to discover new superconductors in the family of transition metal dichalcogenides. All these materials are in some sense unconventional superconductors. The cuprates by their high Tc and the symmetry of the order parameter, MgB2 by its two-band superconductivity and Tc of 39 K, and the dichalcogenides by the appearance of superconductivity on the background of competing interactions. Measurements of transport properties, such as resistivity and thermoelectric power, were used to get insight in the behavior of these materials. Besides temperature as variable, I applied high pressure, extreme magnetic fields and controlled disorder introduced by fast electron irradiation. In the first part I present the pressure dependent study of two members of the transition metal dichalcogenides having 1T structure, 1T-TiSe2 and 1T-TaS2, where superconductivity was never observed in a pristine sample. 1T-TiSe2 has a CDW phase below 220 K which origin, weather it is driven by an excitonic mechanism or by a Jahn-Teller distortion, is an ongoing question. By applying pressure I showed that the pristine sample is superconducting in the pressure range of 2.0–4.0 GPa. This range remarkably coincides with the short range fluctuating CDW before its disappearance at the upper pressure value. If CDW is due to excitonic interactions than our observations suggest that it can be at the origin of superconductivity, as well. The second dichalcogenide is the 1T-TaS2, where a Mott-insulator phase appears on the top of a commensurate CDW. By applying pressure I was able to melt that Mott-phase, and reveal that the material is superconducting above 2.5 GPa with Tc of 5.9 K. Unexpectedly, superconductivity is born from a nonmetallic phase, and stays remarkably stable up to the highest applied pressure of 24 GPa. In the second part I tried to give my contribution to the field of high-Tc superconductors. I carefully selected few high quality underdoped Bi2Sr2PrxCa1-xCu2O8-δ sample, to address the nature of the low temperature ground state by applying high magnetic field. Although former measurements by other groups showed that at high underdoping, the ground state is an insulator, I found that a sample with as low Tc as 15 K exhibits metallic behavior up to 60 T. Furthermore, I showed that a inhomogeneous distribution of the doping atoms can completely mask the intrinsic normal state of a high-Tc superconductor. In the last part of my thesis I focused on the two-band superconductor MgB2 by studying the scattering between the bands by the means of the Matthiessen's rule. I made a systematic study of the influence of defects created by fast electron irradiation, and found that the the Matthiessen's rule is satisfied for the defect concentration range I induced. I further compare the influence of defects on the critical temperature and the residual resistivity in MgB2 with superconductors with various order parameters, and found that the decrease-rate of Tc in our system is within the range of a response of a superconductor with an s-wave order parameter.

EPFL2008