scholarly journals Atomic scale symmetry and polar nanoclusters in the paraelectric phase of ferroelectric materials

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Andreja Bencan ◽  
Emad Oveisi ◽  
Sina Hashemizadeh ◽  
Vignaswaran K. Veerapandiyan ◽  
Takuya Hoshina ◽  
...  

AbstractThe nature of the “forbidden” local- and long-range polar order in nominally non-polar paraelectric phases of ferroelectric materials has been an open question since the discovery of ferroelectricity in oxide perovskites, ABO3. A currently considered model suggests locally correlated displacements of B-site atoms along a subset of <111> cubic directions. Such off-site displacements have been confirmed experimentally; however, being essentially dynamic in nature they cannot account for the static nature of the symmetry-forbidden polarization implied by the macroscopic experiments. Here, in an atomically resolved study by aberration-corrected scanning transmission electron microscopy complemented by Raman spectroscopy, we reveal, directly visualize and quantitatively describe static, 2–4 nm large polar nanoclusters in the nominally non-polar cubic phases of (Ba,Sr)TiO3 and BaTiO3. These results have implications on understanding of the atomic-scale structure of disordered materials, the origin of precursor states in ferroelectrics, and may help answering ambiguities on the dynamic-versus-static nature of nano-sized clusters.

2020 ◽  
Vol 3 (1) ◽  
Author(s):  
Kalani Moore ◽  
Michele Conroy ◽  
Eoghan N. O’Connell ◽  
Charlotte Cochard ◽  
Jennifer Mackel ◽  
...  

AbstractCharged domain walls (DWs) in ferroelectric materials are an area of intense research. Microscale strain has been identified as a method of inducing arrays of twin walls to meet at right angles, forming needlepoint domains which exhibit novel material properties. Atomic scale characterisation of the features exhibiting these exciting behaviours was inaccessible with the piezoresponse force microscopy resolution of previous work. Here we use aberration corrected scanning transmission electron microscopy to observe short, stepped, highly charged DWs at the tip of the needle points in ferroelectric PbTiO3. Reverse Ti4+ shift polarisation mapping confirms the head-to-head polarisation in adjacent domains. Strain mapping reveals large deviations from the bulk and a wider DW with a high Pb2+ vacancy concentration. The extra screening charge is found to stabilise the DW perpendicular to the opposing polarisation vectors and thus constitutes the most highly charged DW possible in PbTiO3. This feature at the needle point junction is a 5 nm × 2 nm channel running through the sample and is likely to have useful conducting properties. We envisage that similar junctions can be formed in other ferroelastic materials and yield exciting phenomena for future research.


Author(s):  
J. L. Lee ◽  
C. A. Weiss ◽  
R. A. Buhrman ◽  
J. Silcox

BaF2 thin films are being investigated as candidates for use in YBa2Cu3O7-x (YBCO) / BaF2 thin film multilayer systems, given the favorable dielectric properties of BaF2. In this study, the microstructural and chemical compatibility of BaF2 thin films with YBCO thin films is examined using transmission electron microscopy and microanalysis. The specimen was prepared by using laser ablation to first deposit an approximately 2500 Å thick (0 0 1) YBCO thin film onto a (0 0 1) MgO substrate. An approximately 7500 Å thick (0 0 1) BaF2 thin film was subsequendy thermally evaporated onto the YBCO film.Images from a VG HB501A UHV scanning transmission electron microscope (STEM) operating at 100 kV show that the thickness of the BaF2 film is rather uniform, with the BaF2/YBCO interface being quite flat. Relatively few intrinsic defects, such as hillocks and depressions, were evident in the BaF2 film. Moreover, the hillocks and depressions appear to be faceted along {111} planes, suggesting that the surface is smooth and well-ordered on an atomic scale and that an island growth mechanism is involved in the evolution of the BaF2 film.


2014 ◽  
Vol 20 (6) ◽  
pp. 1782-1790 ◽  
Author(s):  
Ping Lu ◽  
Eric Romero ◽  
Shinbuhm Lee ◽  
Judith L. MacManus-Driscoll ◽  
Quanxi Jia

AbstractWe report our effort to quantify atomic-scale chemical maps obtained by collecting energy-dispersive X-ray spectra (EDS) using scanning transmission electron microscopy (STEM) (STEM-EDS). With thin specimen conditions and localized EDS scattering potential, the X-ray counts from atomic columns can be properly counted by fitting Gaussian peaks at the atomic columns, and can then be used for site-by-site chemical quantification. The effects of specimen thickness and X-ray energy on the Gaussian peak width are investigated using SrTiO3 (STO) as a model specimen. The relationship between the peak width and spatial resolution of an EDS map is also studied. Furthermore, the method developed by this work is applied to study cation occupancy in a Sm-doped STO thin film and antiphase boundaries (APBs) present within the STO film. We find that Sm atoms occupy both Sr and Ti sites but preferably the Sr sites, and Sm atoms are relatively depleted at the APBs likely owing to the effect of strain.


2009 ◽  
Vol 24 (8) ◽  
pp. 2596-2604 ◽  
Author(s):  
Sašo Šturm ◽  
Makoto Shiojiri ◽  
Miran Čeh

The microstructure in AO-excess SrTiO3 (A = Sr2+, Ca2+, Ba2+) ceramics is strongly affected by the formation of Ruddlesden-Popper fault–rich (RP fault) lamellae, which are coherently intergrown with the matrix of the perovskite grains. We studied the structure and chemistry of RP faults by applying quantitative high-resolution transmission electron microscopy and high-angle annular dark-field scanning transmission electron microscopy analyses. We showed that the Sr2+ and Ca2+ dopant ions form RP faults during the initial stage of sintering. The final microstructure showed preferentially grown RP fault lamellae embedded in the central part of the anisotropic perovskite grains. In contrast, the dopant Ba2+ ions preferably substituted for Sr2+ in the SrTiO3 matrix by forming a BaxSr1−xTiO3 solid solution. The surplus of Sr2+ ions was compensated structurally in the later stages of sintering by the formation of SrO-rich RP faults. The resulting microstructure showed RP fault lamellae located at the surface of equiaxed BaxSr1-xTiO3 perovskite grains.


2013 ◽  
Vol 19 (S2) ◽  
pp. 1238-1239
Author(s):  
G. Nicotra ◽  
Q.M. Ramasse ◽  
I. Deretzis ◽  
C. Bongiorno ◽  
C. Spinella ◽  
...  

Extended abstract of a paper presented at Microscopy and Microanalysis 2013 in Indianapolis, Indiana, USA, August 4 – August 8, 2013.


Science ◽  
2020 ◽  
Vol 370 (6516) ◽  
pp. eabb5940 ◽  
Author(s):  
Mathias Uller Rothmann ◽  
Judy S. Kim ◽  
Juliane Borchert ◽  
Kilian B. Lohmann ◽  
Colum M. O’Leary ◽  
...  

Hybrid organic-inorganic perovskites have high potential as materials for solar energy applications, but their microscopic properties are still not well understood. Atomic-resolution scanning transmission electron microscopy has provided invaluable insights for many crystalline solar cell materials, and we used this method to successfully image formamidinium lead triiodide [CH(NH2)2PbI3] thin films with a low dose of electron irradiation. Such images reveal a highly ordered atomic arrangement of sharp grain boundaries and coherent perovskite/PbI2 interfaces, with a striking absence of long-range disorder in the crystal. We found that beam-induced degradation of the perovskite leads to an initial loss of formamidinium [CH(NH2)2+] ions, leaving behind a partially unoccupied perovskite lattice, which explains the unusual regenerative properties of these materials. We further observed aligned point defects and climb-dissociated dislocations. Our findings thus provide an atomic-level understanding of technologically important lead halide perovskites.


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