Classical and Quantum Critical Phenomena in the Dipolar Antiferromagnet LiErF4

The collective behavior of systems consisting of interacting dipoles is a subject of considerable studies. The anisotropic nature of such interactions opens an arena to explore fundamental questions in correlated electron physics, ranging from quantum entanglement, phase transitions, spin glass states to disorder and fluctuations. LiHoF4 is a textbook example of a ferromagnetic Ising-dipolar model, offering a simple and well-understood Hamiltonian. The system undergoes a quantum phase transition (QPT) in a field transverse to the easy axis, which induces quantum fluctuations between the ground state doublet. Dilution of Ho sites with non-magnetic Yttrium ions lowers only the transition temperature (Tc), and eventually lead to spin-glass state. While Tc decreases in a linear fashion, as expected from simple mean-field (MF) calculation, critical field decreases much faster. The behavior upon dilution has been pointed out to be related to randomness and off-diagonal dipolar interactions. In chapter 5 of this thesis I quantify the deviation of experimental results from neutron scattering studies from MF prediction, with the aim that this analysis can be used in future theoretical efforts towards a quantitative description. The aim of this thesis, however, deals with LiErF4 which is an unexplored planar dipolar antiferromagnetic member of LiReF4 family, with TN ≃ 370 mK. The system undergoes a QPT in an applied field H∥c = 4.0±0.1 kOe, confirmed by a softening of the characteristic excitations at Hc. A combined neutron scattering, specific heat, and magnetic susceptibility study reveals a novel non-MF critical scaling of the classical phase transition, belonging to the 2DXY /h4 universality class. In accord with this, the quantum phase transition at Hc exhibits a three-dimensional classical behavior. The effective dimensional reduction may be a consequence of the intrinsic anisotropic nature of the dipolar interaction. Four-fold anisotropy and degeneracy breaking could be due to the "order-by-disorder" phenomena, which could open a gap in dispersion of the magnetic excitations.

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

Neutron spectroscopy in the layered quantum magnet SrCu₂(BO₃)₂ and in transition metal phosphorus trisulfides (MPS₃)

Diane Virginie Marie Lançon

Collective magnetic excitations are a fascinating aspect of condensed matter physics, where neutron scattering can provide valuable insight into the magnetic properties of physical realisations of model systems. This thesis focuses on the excitation spectra of layered quantum magnets in the case of the frustrated quantum magnet SrCu

_2

(BO

_3

)

_2

and the family of quasi-2D antiferromagnets MPS

_3

, with M a transition metal. \begin{itemize}[topsep=2pt,itemsep=-0.7ex] \item SrCu

_2

(BO

_3

)

_2

is a physical realisation of the two-dimensional Shastry-Sutherland theoretical model, constructed as orthogonal dimers with the product of singlets on the strong antiferromagnetic

J

bond as an exact ground state. The spin interactions for such a particular geometry induces strong frustration which leads to unconventional magnetism and exotic phases of matter. This work is concerned with a series of aspects of the magnetic excitations in this compound. The excitation spectra as a function of field, temperature and pressure are measured using neutron time-of-flight spectroscopy. The experimental results show that correlations, bound magnons and finite temperature properties are highly unconventional and these results are compared with existing theories on frustrated model systems. In addition, predicted topological properties of SrCu

_2

(BO

_3

)

_2

in an applied field are confirmed experimentally. \item The transition metal phosphorus trisulfides (MPS

_3

) are a family of quasi two-dimensional materials on a honeycomb lattice with weakly bound magnetic planes. This work focuses mainly on the exchange interactions and critical properties of FePS

_3

, which is largely anisotropic with the S=2 Fe

^{2+}

moments pointing normal to the

(a,b)

plane. Inelastic neutron scattering on single crystals is used to measure the spin wave dispersion, providing new insight on the strength of the coupling interactions and anisotropies and showing that FePS

_3

is a good two-dimensional model antiferromagnet. Similar experiments on powdered samples of NiPS

_3

show low-Q dispersive spin waves with a small spin-gap. Critical properties of FePS

_3

close to the Néel temperature are further discussed, as the magnetic nature of the measured quasi-elastic scattering is confirmed. Based on magnetization measurements in high pulsed fields, a possible tricritical point in the 40-50T range is proposed. \end{itemize} The work presented in this thesis has been carried out in a collaboration between the Institut Laue Langevin in Grenoble and the Laboratory for Quantum Magnetism of the EPFL.

EPFL2017

Etude par microscopie électronique à transmission à haute résolution de l'élargissement thermique des parois de domaines ferroélectriques dans un système de premier ordre

The macroscopic properties of ferroelectric materials depend directly on the domain configuration and the structure of the domain boundaries. For this reason, their study is of great scientific and technological interest. Several models have been developed to describe the properties of domain walls (structure, thickness, stress at the interface, mobility, …). However, few quantitative experimental observations of ferroelectric domain walls at an atomic scale have been reported, and even less results exist at higher temperatures. The ferroelectric domain-wall thickness is an important parameter whose behavior as a function of temperature is directly related to the order of the phase transition. In a second-order system, the temperature dependence of the domain-wall thickness follows a power law L ~ (Tc - T)-ω where ω is the critical exponent characterizing the divergence of L near the critical temperature Tc The predictions concerning the numerical value of are different depending on the theoretical model considered. Nevertheless, the majority of ferroelectric materials are known to undergo a first-order transition. In these systems the domain-wall thickness increases when the transition temperature is approached, but without diverging as for a second-order phase transition. The major objective of this work was to measure this broadening predicted by the theory for the first time at the approach of the phase transition temperature. We have shown that high resolution transmission electron microscopy is powerful technique for the study of ferroelectric domain walls not only at room temperature but also at higher temperatures. This method allows a direct and local observation of interfaces at an atomic scale which is a considerable advantage over diffraction techniques (X-ray, neutron, electron) and most of the other electron microscopy methods. However, the requirements of this method concerning the performance of the optical system of the microscope, the quality of the specimen and its stability in the column are very high, and today high resolution microscopy at high temperature remains a major challenge. The domain-wall thickness is obtained from the measurement of the crystal lattice distortion near the interface using two different numerical techniques of image analysis. The first method is based on the accurate determination of the center of bright peaks which appear on high resolution images for a judicious choice of the experimental parameters (delocalization and crystal thickness) and which represent the crystal lattice nodes. The second technique consists in selecting a circular region of the power spectrum around a reflection peak, centering the Fourier space on this reflection and performing the inverse Fourier transform. The information about the local displacement of atomic planes corresponding to the selected reflection is extracted form the phase component of the obtained complex image. Both techniques have been successfully applied to the measurement of the thickness of the 90° ferroelectric domain walls in PbTiO3 single crystals. This perovskite presents a first order phase transition at Tc = 492.2°C. which corresponds to the transformation of the crystal from the high-temperature paraelectric cubic phase to the low-temperature ferroelectric tetragonal phase. For the first time, the thermal broadening of domain walls has been measured quantitatively using HRTEM. The results are compared with the predictions made by phenomenological theories. We find that the domain wall thickness increases continuously from 0.7 nm at room temperature up to 5.5 nm near the transition temperature. Our results are consistent with those obtained by other authors at room temperature and those of a very recent study performed at higher temperatures using weak-beam microscopy. The measured domain-wall broadening is greater than the one predicted by a three-dimensional Ginzburg-Landau model where the polarization which is the primary order parameter is coupled to the elastic strain which plays the role of secondary order parameter. Our results are better described by a one-dimensional Ginzburg-Landau model without secondary order parameter. In this case the gradient coupling coefficient κ of the Ginzburg-Landau free energy is found to be 1.3 · 10-10 m3F-1. The methods developed for the measurement of the domain-wall thickness can by applied not only to other first-order ferroelectric crystals but also to ferroelectric systems presenting a second-order phase transition thus allowing the determination of the critical exponent ω. Characteristics only present in 2-D systems could also be detected by studying very thin specimens. Moreover, the same techniques can be adapted to the study of domain walls in purely ferroelastic materials.

EPFL2000