Chun-Lin Jia

Determination of the 3D shape of a nanoscale crystal with atomic resolution from a single image

Although the overall atomic structure of a nanoscale crystal is in principle accessible by modern transmission electron microscopy, the precise determination of its surface structure is an intricate problem. Here, we show that aberration-corrected transmission electron microscopy, combined with dedicated numerical evaluation procedures, allows the three-dimensional shape of a thin MgO crystal to be determined from only one single high-resolution image. The sensitivity of the reconstruction procedure is not only sufficient to reveal the surface morphology of the crystal with atomic resolution, but also to detect the presence of adsorbed impurity atoms. The single-image approach that we introduce offers important advantages for three-dimensional studies of radiation-sensitive crystals.

Ferroelectric translational antiphase boundaries in nonpolar materials

Ferroelectric materials are heavily used in electro-mechanics and electronics. Inside the ferroelectric, domain walls separate regions in which the spontaneous polarization is differently oriented. Properties of ferroelectric domain walls can differ from those of the domains themselves, leading to new exploitable phenomena. Even more exciting is that a non-ferroelectric material may have domain boundaries that are ferroelectric. Many materials possess translational antiphase boundaries. Such boundaries could be interesting entities to carry information if they were ferroelectric. Here we show first that antiphase boundaries in antiferroelectrics may possess ferroelectricity. We then identify these boundaries in the classical antiferroelectric lead zirconate and evidence their polarity by electron microscopy using negative spherical-aberration imaging technique. Ab initio modelling confirms the polar bi-stable nature of the walls. Ferroelectric antiphase boundaries could make high-density non-volatile memory; in comparison with the magnetic domain wall memory, they do not require current for operation and are an order of magnitude thinner.

Large Energy Density, Excellent Thermal Stability, and High Cycling Endurance of Lead-Free BaZr0.2Ti0.8O3 Film Capacitors

A large energy storage density (ESD) of 30.4 J/cm3 and high energy efficiency of 81.7% under an electrical field of 3 MV/cm was achieved at room temperature by the fabrication of environmentally friendly lead-free BaZr0.2Ti0.8O3 epitaxial thin films on Nb-doped SrTiO3 (001) substrates by using a radio-frequency magnetron sputtering system. Moreover, the BZT film capacitors exhibit great thermal stability of the ESD from 16.8 J/cm3 to 14.0 J/cm3 with efficiency of beyond 67.4% and high fatigue endurance (up to 106 cycles) in a wide temperature range from room temperature to 125 °C. Compared to other BaTiO3-based energy storage capacitor materials and even Pb-based systems, BaZr0.2Ti0.8O3 thin film capacitors show either high ESD or great energy efficiency. All of these excellent results revealed that the BaZr0.2Ti0.8O3 film capacitors have huge potential in the application of modern electronics, such as locomotive and pulse power, in harsh working environments.

Néel-like domain walls in ferroelectric Pb(Zr,Ti)O 3 single crystals

In contrast to the flexible rotation of magnetization direction in ferromagnets, the spontaneous polarization in ferroelectric materials is highly confined along the symmetry-allowed directions. Accordingly, chirality at ferroelectric domain walls was treated only at the theoretical level and its real appearance is still a mystery. Here we report a Néel-like domain wall imaged by atom-resolved transmission electron microscopy in Ti-rich ferroelectric Pb(Zr1−xTix)O3 crystals, where nanometre-scale monoclinic order coexists with the tetragonal order. The formation of such domain walls is interpreted in the light of polarization discontinuity and clamping effects at phase boundaries between the nesting domains. Phase-field simulation confirms that the coexistence of both phases as encountered near the morphotropic phase boundary promotes the polarization to rotate in a continuous manner. Our results provide a further insight into the complex domain configuration in ferroelectrics, and establish a foundation towards exploring chiral domain walls in ferroelectrics.

Atomic resolution imaging of YAlO3: Ce in the chromatic and spherical aberration corrected PICO electron microscope

The application of combined chromatic and spherical aberration correction in high-resolution transmission electron microscopy enables a significant improvement of the spatial resolution down to 50 pm. We demonstrate that such a resolution can be achieved in practice at 200kV. Diffractograms of images of gold nanoparticles on amorphous carbon demonstrate corresponding information transfer. The Y atom pairs in [010] oriented yttrium orthoaluminate are successfully imaged together with the Al and the O atoms. Although the 57 pm pair separation is well demonstrated separations between 55 pm and 80 pm are measured. This observation is tentatively attributed to structural relaxations and surface reconstruction in the very thin samples used. Quantification of the resolution limiting effective image spread is achieved based on an absolute match between experimental and simulated image intensity distributions.

Surface reconstructions and related local properties of a BiFeO3 thin film

Coupling between lattice and order parameters, such as polarization in ferroelectrics and/or polarity in polar structures, has a strong impact on surface relaxation and reconstruction. However, up to now, surface structures that involve the termination of both matrix polarization and polar atomic planes have received little attention, particularly on the atomic scale. Here, we study surface structures on a BiFeO3 thin film using atomic-resolution scanning transmission electron microscopy and spectroscopy. Two types of surface structure are found, depending on the polarization of the underlying ferroelectric domain. On domains that have an upward polarization component, a layer with an Aurivillius-Bi2O2-like structural unit is observed. Dramatic changes in local properties are measured directly below the surface layer. On domains that have a downward polarization component, no reconstructions are visible. Calculations based on ab initio density functional theory reproduce the results and are used to interpret the formation of the surface structures.

Controlled Charging of Ferroelastic Domain Walls in Oxide Ferroelectrics

Conductive domain walls (DWs) in ferroic oxides as device elements are a highly attractive research topic because of their robust and agile response to electric field. Charged DWs possessing metallic-type conductivity hold the highest promises in this aspect. However, their intricate creation, low stability, and interference with nonconductive DWs hinder their investigation and the progress toward future applications. Here, we find that conversion of the nominally neutral ferroelastic 90° DWs into partially charged DWs in Pb(Zr0.1Ti0.9)O3 thin films enables easy and robust control over the DW conductivity. By employing transmission electron microscopy, conductive atomic force microscopy and phase-field simulation, our study reveals that charging of the ferroelastic DWs is controlled by mutually coupled DW bending, type of doping, polarization orientation and work-function of the adjacent electrodes. Particularly, the doping outweighs other parameters in controlling the DW conductivity. Understanding the interplay of these key parameters not only allows us to control and optimize conductivity of such ferroelastic DWs in the oxide ferroelectrics but also paves the way for utilization of DW-based nanoelectronic devices in the future.

Interface thickness optimization of lead-free oxide multilayer capacitors for high-performance energy storage

The effects of interface density and total multilayer film thickness on the dielectric properties and breakdown behavior have been revealed in this work by investigating the environment-friendly energy storage multilayer films of Ba0.7Ca0.3TiO3 (BCT) and BaZr0.2Ti0.8O3 (BZT) dielectrics. Numerical simulations based on a finite element method have given the breakdown process vividly, which agreed well with the experimental results. Moreover, not only the ultrahigh energy storage density of 51.8 J cm−3 with a great efficiency of 81.2% at room temperature but also robust thermal stability has been obtained by optimizing the interface density and total thickness. High energy density above 25.1 J cm−3 and excellent efficiency over 63.6% from room temperature to 200 °C provide a solid basis for potential applications of the multilayer systems in harsh environments.

High-performance BaZr0.35Ti0.65O3 thin film capacitors with ultrahigh energy storage density and excellent thermal stability

The ability to work at ultralow (−90 °C) or ultrahigh (200 °C) temperature with superior energy storage properties is essential for dielectric capacitors to operate in harsh environments. Here, we realized an ultrahigh recoverable energy density (Wrec) (78.7 J cm−3) and efficiency (η) (80.5%) in BaZr0.35Ti0.65O3 film capacitors through enhancing the breakdown electric field strength at room temperature. Moreover, the BaZr0.35Ti0.65O3 film capacitor exhibits great energy storage properties when measured from −150 °C to 200 °C. Wrec and η can reach the value of 41.9 J cm−3 and 66.4% under an electric strength of 4.0 MV cm−1 even at 200 °C, respectively. Especially, the variation of both Wrec and η at 200 °C during 1 × 106 cycles (ferroelectric fatigue tests) is less than 3%. All these reveal that the BZT film capacitor is a commendable material for application in equipment working in harsh environments.

Atomic-scale evidence for displacive disorder in bismuth zinc niobate pyrochlore

Pyrochlores characterized by the chemical formula A2B2O7 form an extended class of materials with interesting physical and chemical properties. The compound Bi1.5ZnNb1.5O7 is prototypical. Its excellent dielectric properties make it attractive, e.g. for capacitors, tunable microwave devices and electric-energy storage equipment. Bi1.5ZnNb1.5O7 shows an intriguing frequency-dispersive dielectric relaxation at 50u202fKu202f≤u202fTu202f≤u202f250u202fK, which has been studied intensively but is still not fully understood. In this first study on a pyrochlore by atomic-resolution transmission electron microscopy we observe the Bi atoms on A sites since, due to their low nuclear charge, the contribution of Zn atoms to the contrast of these sites is negligible. We find in our [1¯00]and [112] oriented images that the position of the atomic intensity maxima do not coincide with the projected Wyckoff positions of the basic pyrochlore lattice. This supplies atomic-scale evidence for displacive disorder on split A-type sites. The Bi atoms are sessile, only occasionally we observe in time sequences of images jumps between individual split-site positions. The apertaining jump rate of the order of 0.1-1u202fHz is by ten orders of magnitude lower than the values derived in the literature from Arrhenius plots of the low-temperature dielectric relaxation data. It is argued that these jumps are radiation induced. Therefore our observations are ruling out a contribution of Bi-atom jumps to low-temperature dielectric A sites-related relaxation. It is suggested that this relaxation is mediated by jumps of Zn atoms.