Relaxor ferroelectrics were discovered almost 50 years ago among the complex oxides with perovskite structure. In recent years this field of research has experienced a revival of interest. In this paper we review the progress achieved. We consider the crystal structure including quenched compositional disorder and polar nanoregions (PNR), the phase transitions including compositional order-disorder transition, transition to nonergodic (probably spherical cluster glass) state and to ferroelectric phase. We discuss the lattice dynamics and the peculiar (especially dielectric) relaxation in relaxors. Modern theoretical models for the mechanisms of PNR formation and freezing into nonergodic glassy state are also presented.

Recent progress in relaxor ferroelectrics with perovskite structure

We report that crystalline phases with ferroelectric behavior can be formed in thin films of SiO2 doped hafnium oxide. Films with a thickness of 10 nm and with less than 4 mol. % of SiO2 crystallize in a monoclinic/tetragonal phase mixture. We observed that the formation of the monoclinic phase is inhibited if crystallization occurs under mechanical encapsulation and an orthorhombic phase is obtained. This phase shows a distinct piezoelectric response, while polarization measurements exhibit a remanent polarization above 10 μC/cm2 at a coercive field of 1 MV/cm, suggesting that this phase is ferroelectric. Ferroelectric hafnium oxide is ideally suited for ferroelectric field effect transistors and capacitors due to its excellent compatibility to silicon technology.

Ferroelectricity in hafnium oxide thin films

The transition metal oxides ZrO2 and HfO2 as well as their solid solution are widely researched and, like most binary oxides, are expected to exhibit centrosymmetric crystal structure and therewith linear dielectric characteristics. For this reason, those oxides, even though successfully introduced into microelectronics, were never considered to be more than simple dielectrics possessing limited functionality. Here we report the discovery of a field-driven ferroelectric phase transition in pure, sub 10 nm ZrO2 thin films and a composition- and temperature-dependent transition to a stable ferroelectric phase in the HfO2–ZrO2 mixed oxide. These unusual findings are attributed to a size-driven tetragonal to orthorhombic phase transition that in thin films, similar to the anticipated tetragonal to monoclinic transition, is lowered to room temperature. A structural investigation revealed the orthorhombic phase to be of space group Pbc21, whose noncentrosymmetric nature is deemed responsible for the spontaneous...

Ferroelectricity in Simple Binary ZrO2 and HfO2

Incipient ferroelectricity is known to occur in perovskites such as SrTiO3, KTaO3, and CaTiO3. For the first time it is shown that the intensively researched HfO2 thin films (16 nm) also possess ferroelectric properties when aluminium is incorporated into the host lattice. Polarization measurements on Al:HfO2 based metal–insulator–metal capacitors show an antiferroelectric-to-ferroelectric phase transition depending on annealing conditions and aluminium content. Structural investigation of the electrically characterized capacitors by grazing incidence X-ray diffraction is presented in order to gain further insight on the potential origin of ferroelectricity. The non-centrosymmetry of the elementary cell, which is essential for ferroelectricity, is assumed to originate from an orthorhombic phase of space group Pbc21 stabilized for low Al doping in HfO2. The ferroelectric properties of the modified HfO2 thin films yield high potential for various ferroelectric, piezoelectric, and pyroelectric applications. Furthermore, due to the extensive knowledge accumulated by various research groups regarding the HfO2 dielectric, an immediate relevance of ferroelectric hafnium oxide thin films is anticipated by the authors.

Incipient Ferroelectricity in Al-Doped HfO2 Thin Films

The state of the art of thin-film pyroelectric infrared (IR) detectors is reviewed covering device physics, material performance, micro-fabrication and device examples. Emphasis is given to special issues related to thin films, such as small heat capacities and the substrate influence on the pyroelectric properties. For the latter, an overview of the hitherto reported values is given. Examples of micromachined IR detectors based on pyroelectric thin films are described. The ultimate limit of micromachined thermal IR detectors is estimated for uncooled operation. It is concluded that the best pyroelectric thin films achieved to date are in principle sufficiently good to approach this limit, meaning that the present performance of pyroelectric thin-film focal plane arrays can still be improved by more than a factor of 10. A comparison of the different principles for IR detection shows that pyroelectricity is indeed one of the most competitive principles for uncooled IR detection. The major obstacle hindering quick industrialization is the fabrication complexity.

https://iopscience.iop.org/article/10.1088/0034-4885/64/10/203/pdf

Micromachined infrared detectors based on pyroelectric thin films

A zero-field spontaneous relaxor-ferroelectric transition is reported in Pb(Sc0.5Ta0.5)O3 (PST). This behavior is different from that of other relaxors, where such transitions occur only under the field. A highly disordered PST that has the wide relaxation spectrum typical of relaxors is shown to transform spontaneously into a macroscopic ferroelectric state. Introduction of defects (lead vacancies) into the material impedes the transition resulting in the usual relaxor behavior. Dielectric properties of PST, with and without defects, are analyzed. For the interpretation of the observed properties, a model invoking an additional nonpolar phase is proposed. This model does not imply a freezing in the system. At the low-frequency limit, it is possible to account for the Vogel-Fulcher (VF) law for the temperature of the maximum of the dielectric constant, using only the commonly accepted assumption of an exponentially wide relaxation time spectrum that shrinks on heating. The presented approach interprets the observed proximity between the ferroelectric phase transition temperature and that of the freezing temperature obtained from the VF relation.

F. Chu

Papers

The Spontaneous Relaxor-Ferroelectric Transition of Pb(Sc0.5ta0.5)O3