Ferroelectric oxide materials have offered a tantalizing potential for applications since the discovery of ferroelectric perovskites more than 50 years ago. Their switchable electric polarization is ideal for use in devices for memory storage and integrated microelectronics, but progress has long been hampered by difficulties in materials processing. Recent breakthroughs in the synthesis of complex oxides have brought the field to an entirely new level, in which complex artificial oxide structures can be realized with an atomic-level precision comparable to that well known for semiconductor heterostructures. Not only can the necessary high-quality ferroelectric films now be grown for new device capabilities, but ferroelectrics can be combined with other functional oxides, such as high-temperature superconductors and magnetic oxides, to create multifunctional materials and devices. Moreover, the shrinking of the relevant lengths to the nanoscale produces new physical phenomena. Real-space characterization and manipulation of the structure and properties at atomic scales involves new kinds of local probes and a key role for first-principles theory.

http://science.sciencemag.org/content/sci/303/5657/488.full.pdf

Ferroelectricity at the Nanoscale: Local Polarization in Oxide Thin Films and Heterostructures

This review paper summarizes recent advances in the quickly developing field of nanoscale ferroelectrics, analyses its current status and considers potential future developments. The paper presents a brief survey of the fabrication methods of ferroelectric nanostructures and investigation of the size effects by means of scanning probe microscopy. One of the focuses of the review will be the study of kinetics of nanoscale ferroelectric switching in inhomogeneous electrical and elastic fields. Another emphasis will be made on tailoring the electrical and mechanical properties of ferroelectrics with a viewpoint of fabrication of nanoscale domain structures.

/pdf/nanoscale-ferroelectrics-processing-characterization-and-3waqb910lb.pdf

Nanoscale ferroelectrics: processing, characterization and future trends

Electrostatic force microscopy and scanning surface potential microscopy are applied to study force gradient and surface potential on ${\mathrm{BaTiO}}_{3}(100)$ surface. Surface potential evolution during a ferroelectric/paraelectric phase transition and the potential distribution near moving domain walls allow the relationship between potential polarity and polarization orientation. Results indicate that polarization bound charge is completely screened on this surface and domain potential is reverse to that expected from domain polarity. Surface potential is attributed to the formation of double layer due to the complete screening of polarization charge. The absolute value of the measured potential difference between domains of opposite polarity suggests that surface adsorbates play a governing role in potential formation mechanism, though intrinsic screening by free carriers is not completely excluded.

Local potential and polarization screening on ferroelectric surfaces

Piezoresponse force microscopy (PFM) has emerged as a powerful and versatile tool for probing nanoscale phenomena in ferroelectric materials on the nanometer and micrometer scales. In this review, we summarize the fundamentals and recent advances in PFM, and describe the nanoscale electromechanical properties of several important ferroelectric ceramic materials widely used in memory and microelectromechanical systems applications. Probing static and dynamic polarization behavior of individual grains in PZT films and ceramics is discussed. Switching spectroscopy PFM is introduced as a useful tool for studying defects and interfaces in ceramic materials. The results on local switching and domain pinning behavior, as well as nanoscale fatigue and imprint mapping are presented. Probing domain structures and polarization dynamics in polycrystalline relaxors (PMN-PT, PLZT, doped BaTiO 3 ) are briefly outlined. Finally, applications of PFM to dimensionally confined ferro-electrics are demonstrated. The potential of PFM for studying local electromechanical phenomena in polycrystalline ferroelectrics where defects and other inhomogeneities are essential for the interpretation of their macroscopic properties is illustrated.

Electromechanical Imaging and Spectroscopy of Ferroelectric and Piezoelectric Materials: State of the Art and Prospects for the Future

Ferroelectric materials have remained one of the major focal points of condensed matter physics and materials science for over 50 years. In the last 20 years, the development of voltage-modulated scanning probe microscopy techniques, exemplified by Piezoresponse force microscopy (PFM) and associated time- and voltage spectroscopies, opened a pathway to explore these materials on a single-digit nanometer level. Consequently, domain structures and walls and polarization dynamics can now be imaged in real space. More generally, PFM has allowed studying electromechanical coupling in a broad variety of materials ranging from ionics to biological systems. It can also be anticipated that the recent Nobel prize [“The Nobel Prize in Chemistry 2016,” http://www.nobelprize.org/nobel_prizes/chemistry/laureates/2016/ (Nobel Media, 2016)] in molecular electromechanical machines will result in rapid growth in interest in PFM as a method to probe their behavior on single device and device assembly levels. However, the br...

Ferroelectric or non-ferroelectric: Why so many materials exhibit "ferroelectricity" on the nanoscale

We report on the recent investigations of the surface of ferroelectric crystals with scanning force microscopy. In situ investigations are demonstrated for temperatures T even above the transition temperature Tc for triglycine‐sulphate (TGS) and barium‐titanate (BaTiO3) (Tc,TGS=49 °C, Tc,BaTiO3=126 °C. We directly observed transition from the ferroelectric into the paraelectric phase. Our inspection of the ferroelectric crystals TGS and BaTiO3 allowed the simultaneous investigation of topographic surface features and ferroelectric domain structure in these crystals. Ferroelectric domains are clearly discernible in the noncontact mode as well as the friction force mode of imaging. The domain wall width in TGS was measured to be smaller than 8 nm. Furthermore, contact force microscopy indicated the domain wall to be atomically flat, exhibiting no surface step. While image contrast in noncontact scanning force microscopy pictures is found to be a convolution of both topographic and ferroelectric forces on TG...

Deconvolution of topographic and ferroelectric contrast by noncontact and friction force microscopy

We report on the recent investigations of the surface of ferroelectric crystals with scanning force microscopy. Our inspection of the ferroelectric crystals triglycine-sulphate (TGS) and Barium-titanate (BaTiO3) allowed the simultaneous investigation of topographic surface features and ferroelectric domain structure in these crystals. Ferroelectric domains are clearly discernible in the non-contact mode as well as the friction force mode of imaging. In-situ investigations are demonstrated for temperatures T above the transition temperature Tc for TGS and BaTiO3 (Tc , TGS = 49°C, Tc , BaTiO3 = 126°C). We directly observed transition from the ferroelectric into the paraelectric phase. Upon cooling, new domains were formed indicating no memory effect, i.e. new domains grew on other spots than before heating. Further, a significantly different type of surface decoration was found for positively and negatively charged surface domains in TGS. This allows the in-situ observation of both domain wall moti...

Scanning force microscopy of ferroelectric crystals

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Deconvolution of topographic and ferroelectric contrast by noncontact and friction force microscopy

Scanning force microscopy of ferroelectric crystals