Study of static and dynamical properties of complex antiferroelectrics materials

The aim of this dissertation is the investigation of the static and dynamical properties of the complex antiferroelectric materials using Effective Hamiltonian method and First principles calculations. In chapter 3, a novel elemental interatomic coupling in perovskite materials which bilinearly couples the antiferroelectric displacements of cations with the rotations of the oxygen octahedra. This new coupling explains a very complex crystal structure of prototypical antiferroelectric PbZrO3. My explanation provides a unified description of many other complex antipolar crystal structures in variety of perovskite materials, including the occurrence of incommensurate phases in some of them. In chapter 4, results and analysis of atomistic simulations explaining the dynamics of antiferroelectric distortions in BiFeO3 (BFO) bulk under hydrostatic pressure are reported. This system undergoes a phase transition on cooling from paraelectric Pm3 ̄m state at high temperatures to an intermediate P4/mbm phase followed by Pnma state at low temperatures. On the basis of my calculations, I prepared an analytical model of these phase transitions. The model developed can be easily applied to predict dynamics of antipolar cation motion in improper ferroelectrics. I found out that the antipolar modes do not soften themselves in the high temperature regime but they soften in the intermediate and Pnma phases, due to trilinear energetic coupling term. In chap- ter 5, the finite temperature behavior of the polar, antipolar, and antiferrodistortive phonons in a prototypical hybrid improper ferroelectric (BiFeO3)1/(NdFeO3)1 1:1 superlattice is studied. In the low-temperature phase, a spontaneous polarization appears due to trilinear coupling of structural and antiferroelectric (ferrroelectric) modes. In chapter 6, results of first-principles calculations to investigate and analyze properties of (001) thin films made of the most complex perovskite system, namely NaNbO3, are presented.Ferroelectric, antiferroelectric and antiferrodistortive properties of this thin film are reported and discussed, as a function of misfit strain

A new look at the temperature-dependent properties of the antiferroelectric model PbZrO3: an effective Hamiltonian study

A novel atomistic effective Hamiltonian scheme, incorporating an original and simple bilinear energetic coupling, is developed and used to investigate the temperature dependent physical properties of the prototype antiferroelectric PbZrO3 (PZO) system. This scheme reproduces very well the known experimental hallmarks of the complex Pbam orthorhombic phase at low temperatures and the cubic paraelectric state of Pm 3m symmetry at high temperatures. Unexpectedly, it further predicts a novel intermediate state also of Pbam symmetry, but in which anti-phase oxygen octahedral tiltings have vanished with respect to the Pbam ground state. Interestingly, such new state exhibits a large dielectric response and thermal expansion that remarkably agree with previous experimental observations and the x-ray experiments we performed. We also conducted direct first-principles calculations at 0K which further support such low energy phase. Within this fresh framework, a re-examination of the properties of PZO is thus called for.Comment: 21 pages, 4 figures. This paper is submitted to Physical Review

Energetic Couplings in Ferroics

International audienceFerroics include diverse degrees of freedom (such as structural distortions and magnetic moments) among which cross couplings occur, rendering a large variety of interesting phenomena. Determining such couplings, based on symmetry analysis, is not only important to interpret observed phenomena but can also result in novel predictions to be then experimentally checked. Often, such energetic couplings are difficult to construct without a deep knowledge of group theoretical symmetry principles. In the present review, a crash course towards the derivation of energetic couplings, without using much the group theoretical language, is provided. Rather, the present approach relies on a graphical technique and suitable symbolic language, which naturally yields some known couplings (resulting in, e.g., spin/dipole canting, magnetically driven polarization and antipolar/antiferroelectric states). This review also reports and discusses other symmetry-allowed energetic terms, including some leading to the occurrence of an electric polarization in a variety of materials, and "exotic" ones that generate complex phases and phenomena in, e.g., nanostructures and heterostructures

Temperature-dependent properties of the antiferroelectric model PbZrO 3 : An effective Hamiltonian study

International audienceA novel atomistic effective Hamiltonian scheme, incorporating an original and simple bilinear energetic coupling, is developed and used to investigate the temperature dependent physical properties of the prototype antiferroelectric PbZrO 3 (PZO) system. This scheme reproduces very well the known experimental hallmarks of the complex Pbam orthorhombic phase at low temperatures and the cubic paraelectric state of Pm 3m symmetry at high temperatures. Unexpectedly, it further predicts a novel intermediate state also of Pbam symmetry, but in which anti-phase oxygen octahedral tiltings have vanished with respect to the Pbam ground state. Interestingly, such new state exhibits a large dielectric response and thermal expansion that remarkably agree with previous experimental observations and the x-ray experiments we performed. We also conducted direct first-principles calculations at 0K which further support such low energy phase. Within this fresh framework, a re-examination of the properties of PZO is thus called for

Ferroelectric phase transitions in epitaxial antiferroelectric PbZrO3 thin films

International audienceThe archetypical antiferroelectric, PbZrO3, is currently attracting a lot of interest, but no consensus can be clearly established on the nature of its ground state as well as on the influence of external stimuli over its physical properties. Here, the antiferroelectric state of 45-nm-thick epitaxial thin films of PbZrO3 is established by observing the characteristic structural periodicity of antiparallel dipoles at the atomic scale, combined with clear double hysteresis of the polarization-electric field response related to antiferroelectric–to–ferroelectric phase transitions. Surprisingly, while the antiferroelectric state is identified as the ground state, temperature-dependent measurements show that a transition to a ferroelectric-like state appears in a large temperature window (100 K). Atomistic simulations further confirm the existence, and provides the origin, of such ferroelectric state in the films. Electric-field-induced ferroelectric transitions are also detected by the divergence of the piezoresponse force microscopy response. Using this technique, we further reveal the signature of a ferroelectric ground state for 4-nm-thick PbZrO3 films. Compared with bulk crystals, these results suggest a more complex competition between ferroelectric and antiferroelectric phases in epitaxial thin films of PbZrO3

Size‐Induced Ferroelectricity in Antiferroelectric Oxide Membranes

International audienceDespite extensive studies on size effects in ferroelectrics, how structures and properties evolve in antiferroelectrics with reduced dimensions still remains elusive. Given the enormous potential of utilizing antiferroelectrics for high‐energy‐density storage applications, understanding their size effects will provide key information for optimizing device performances at small scales. Here, the fundamental intrinsic size dependence of antiferroelectricity in lead‐free NaNbO3 membranes is investigated. Via a wide range of experimental and theoretical approaches, an intriguing antiferroelectric‐to‐ferroelectric transition upon reducing membrane thickness is probed. This size effect leads to a ferroelectric single‐phase below 40 nm, as well as a mixed‐phase state with ferroelectric and antiferroelectric orders coexisting above this critical thickness. Furthermore, it is shown that the antiferroelectric and ferroelectric orders are electrically switchable. First‐principle calculations further reveal that the observed transition is driven by the structural distortion arising from the membrane surface. This work provides direct experimental evidence for intrinsic size‐driven scaling in antiferroelectrics and demonstrates enormous potential of utilizing size effects to drive emergent properties in environmentally benign lead‐free oxides with the membrane platform

Size‐Induced Ferroelectricity in Antiferroelectric Oxide Membranes

Despite extensive studies on size effects in ferroelectrics, how structures and properties evolve in antiferroelectrics with reduced dimensions still remains elusive. Given the enormous potential of utilizing antiferroelectrics for high-energy-density storage applications, understanding their size effects will provide key information for optimizing device performances at small scales. Here, the fundamental intrinsic size dependence of antiferroelectricity in lead-free NaNbO3 membranes is investigated. Via a wide range of experimental and theoretical approaches, an intriguing antiferroelectric-to-ferroelectric transition upon reducing membrane thickness is probed. This size effect leads to a ferroelectric single-phase below 40 nm, as well as a mixed-phase state with ferroelectric and antiferroelectric orders coexisting above this critical thickness. Furthermore, it is shown that the antiferroelectric and ferroelectric orders are electrically switchable. First-principle calculations further reveal that the observed transition is driven by the structural distortion arising from the membrane surface. This work provides direct experimental evidence for intrinsic size-driven scaling in antiferroelectrics and demonstrates enormous potential of utilizing size effects to drive emergent properties in environmentally benign lead-free oxides with the membrane platform