Search

The formation of complex hierarchical nanostructures has attracted a lot of attention from both the fundamental science and potential applications point of view. Spherulite structures with radial fibrillar branches have been found in various solids; however, their growth mechanisms remain poorly understood. Here, we report real time imaging of the formation of two-dimensional (2D) iron oxide spherulite nanostructures in a liquid cell using transmission electron microscopy (TEM). By tracking the growth trajectories, we show the characteristics of the reaction front and growth kinetics. Our observations reveal that the tip of a growing branch splits as the width exceeds certain sizes (5.5–8.5 nm). The radius of a spherulite nanostructure increases linearly with time at the early stage, transitioning to nonlinear growth at the later stage. Furthermore, a thin layer of solid is accumulated at the tip and nanoparticles from secondary nucleation also appear at the growing front which later develop into fibrillar branches. The spherulite nanostructure is polycrystalline with the co-existence of ferrihydrite and Fe3O4 through-out the growth. A growth model is further established, which provides rational explanations on the linear growth at the early stage and the nonlinearity at the later stage of growth.

Formation mechanisms of dendrite structures have been extensively explored theoretically, and many theoretical predictions have been validated for micro- or macroscale dendrites. However, it is challenging to determine whether classical dendrite growth theories are applicable at the nanoscale due to the lack of detailed information on the nanodendrite growth dynamics. Here, we study iron oxide nanodendrite formation using liquid cell transmission electron microscopy (TEM). We observe "seaweed"-like iron oxide nanodendrites growing predominantly in two dimensions on the membrane of a liquid cell. By tracking the trajectories of their morphology development with high spatial and temporal resolution, it is possible to explore the relationship between the tip curvature and growth rate, tip splitting mechanisms, and the effects of precursor diffusion and depletion on the morphology evolution. We show that the growth of iron oxide nanodendrites is remarkably consistent with the existing theoretical predictions on dendritic morphology evolution during growth, despite occurring at the nanoscale.

The successful integration of the strain-driven nanoscale phase boundary of BiFeO3 onto a silicon substrate is demonstrated with extraordinary ferroelectricity and ferromagnetism. The detailed strain history is delineated through a reciprocal space mapping technique. We have found that a distorted monoclinic phase forms prior to a tetragonal-like phase, a phenomenon which may correlates with the thermal strain induced during the growth process.

We report transition metal oxide nanocrystal formation in a liquid cell using transmission electron microscopy (TEM). The growth of M–Fe–oxide (M = Ni, Mn, Co, or Zn) nanoparticles from a growth solution of metal acetylacetonates dissolved in oleylamine, oleic acid, and benzyl ether was studied. Nickel iron oxide nanocrystals with spinel structure were obtained under electron beam irradiation of the Ni–Fe growth solution, whereas iron oxide nanocrystals were achieved with Mn remaining in the Mn–Fe growth solution. Similarly, we achieved cobalt iron oxide nanocrystals in the Co–Fe precursor solution, while iron oxide nanoparticles were obtained in the Zn–Fe solution. By tracking nanoparticle size evolution as a function of time along the Ni–Fe–oxide nanoparticle growth trajectories, we found the growth kinetics follow a Lifshitz–Slyozov–Wagner (LSW) model suggesting surface reaction-limited growth. Ex situ characterization shows elemental distribution and structural and valence state of the different nanop...

We report an in situ study of Fe3Pt-Fe2O3 core-shell nanoparticle growth using liquid cell transmission electron microscopy. By controlling the Fe-to-Pt ratio in the precursor solution, we achieved the growth of nanoparticles with the formation of an iron-platinum alloy core followed by an iron oxide shell in the electron beam-induced reactions. There was no substantial change in the growth kinetics of the iron oxide shell after the Fe-Pt alloy core stopped growing. The core growth was arrested by depletion of the Pt precursor. Heteroepitaxy of Fe3Pt [101] (core)||α-Fe2O3 [111] (shell) was observed in most of the nanoparticles, while a polycrystalline iron oxide shell is developed eventually for strain relaxation. Our studies suggest that Pt atoms catalyze the reduction of Fe ions to form the Fe3Pt alloy core, and when Pt is depleted, a direct precipitation of iron oxide results in the core-shell nanostructure formation.

Great attention is paid to that stimulus response of materials, which is a prerequisite for energy harvesting applications. Driven by advances in nanotechnology, the atomic motions, involved in phase transitions and associated with stimulus responses, require detailed investigation on the nanoscale. Recently, strain engineering of BiFeO 3 (BFO) has become the subject of broad research interest due to its promising potential in energy conversion applications, such as piezoelectric, pyroelectric and shape memory effect (SME) devices. In this study, an excellent pyroelectric response is associated with reversible phase transitions in mixed-phase BFO films using thermal stimuli. Using an in situ high-resolution transmission electron microscope (HRTEM), we observed that phase transition between rhombohedral-like (R-like) and tetragonal-like (T-like) BFO involved the migration of the phase boundary, which is a prerequisite for the growth of the T-like phase and requires an intermediate phase. Moreover, the origin of the phase transition is attributed to competition between thermodynamic stability and substrate-induced strain, as suggested by phase-field simulations. The results provide a fundamental understanding of the atomic processes that underlie the stimulus response of the strained BFO films and demonstrate the potential of this extraordinary material for novel energy harvesting applications.

Strain engineering of epitaxial ferroelectrics has emerged as a powerful method to tailor the electromechanical response of these materials, although the effect of strain at the atomic scale and the interplay between lattice displacements and electronic structure changes are not yet fully understood. Here, using a combination of scanning transmission electron microscopy (STEM) and density functional theory (DFT), we systematically probe the role of epitaxial strain in mixed phase bismuth ferrite thin films. Electron energy loss O K and Fe L2,3 edge spectra acquired across the rhombohedral (R)–tetragonal (T) phase boundary reveal progressive, and systematic, changes in electronic structure going from one phase to the other. The comparison of the acquired spectra with theoretical simulations using DFT suggests a breakage in the structural symmetry across the boundary due to the simultaneous presence of increasing epitaxial strain and off-axial symmetry in the T phase. This implies that the imposed epitaxial strain plays a significant role in not only changing the crystal-field geometry, but also the bonding environment surrounding the central iron cation at the interface thus providing new insights and a possible link to understand how the imposed strain could perturb magnetic ordering in the T phase BFO.

Self-assembled vertical heteroepitaxial nanostructures (VHN) in the complex oxide field have fascinated scientists for decades because they provide degrees of freedom to explore in condensed matter physics and design-coupled multifunctionlities. Recently, of particular interest is the perovskite-spinel-based VHN, covering a wide spectrum of promising applications. In this review, fabrication of VHN, their growth mechanism, control, and resulting novel multifunctionalities are discussed thoroughly, providing researchers a comprehensive blueprint to construct promising VHN. Following the fabrication section, the state-of-the-art design concepts for multifunctionalities are proposed and reviewed by suitable examples. By summarizing the outlook of this field, we are excitedly expecting this field to rise with significant contributions ranging from scientific value to practical applications in the foreseeable future.

We study the lithiation of a Au electrode in an electrochemical liquid cell using transmission electron microscopy (TEM). The commercial liquid electrolyte for lithium ion batteries (1 M lithium hexafluorophosphate LiPF6 dissolved in 1 : 1 (v/v) ethylene carbonate (EC) and diethyl carbonate (DEC)) was used. Three distinct types of morphology change during the reaction, including gradual dissolution, explosive reaction and local expansion/shrinkage, are observed. It is expected that significant stress is generated from lattice expansion during lithium–gold alloy formation. There is vigorous bubble formation from electrolyte decomposition, likely due to the catalytic effect of Au, while the bubble generation is less severe with titanium electrodes. There is an increase of current in response to electron beam irradiation, and electron beam effects on the observed electrochemical reaction are discussed.

Complex oxide heterointerfaces, which play host to an incredible variety of interface physical phenomena, are of great current interest in introducing new functionalities to systems. Here, coherent super-tetragonal BiFeO3/LaAlO3 and rhombohedral BiFeO3/LaAlO3 heterointerfaces are investigated by using a combination of high-angle annular dark-field (HAADF) imaging and annular bright-field (ABF) imaging in a spherical aberration (Cs) corrected scanning transmission electron microscope (STEM), and first-principles calculations. The complicated ferroelectric polarization pinning and relaxation that occurs at both interfaces is revealed with atomic resolution, with a dramatic change in structure of BiFeO3, from cubic to super-tetragonal-like. The results enable a detailed explanation to be given of how non-bulk phase structures are stabilized in thin films of this material.

We report the study of Mg cathodic electrochemical deposition on Ti and Au electrode using a multimodal approach by examining the sample area in-situ using liquid cell transmission electron microscopy (TEM), scanning transmission X-ray microscopy (STXM) and X-ray absorption spectroscopy (XAS). Magnesium Aluminum Chloride Complex was synthesized and utilized as electrolyte, where non-reversible features during in situ charging-discharging cycles were observed. During charging, a uniform Mg film was deposited on the electrode, which is consistent with the intrinsic non-dendritic nature of Mg deposition in Mg ion batteries. The Mg thin film was not dissolvable during the following discharge process. We found that such Mg thin film is hexacoordinated Mg compounds by in-situ STXM and XAS. This study provides insights on the non-reversibility issue and failure mechanism of Mg ion batteries. Also, our method provides a novel generic method to understand the in situ battery chemistry without any further sample processing, which can preserve the original nature of battery materials or electrodeposited materials. This multimodal in situ imaging and spectroscopy provides many opportunities to attack complex problems that span orders of magnitude in length and time scale, which can be applied to a broad range of the energy storage systems.

Recent advances in thin-fi lm engineering leads to a new type of mixed-phase system in BiFeO 3 (BFO) epitaxial fi lms driven by substrate strain. [ 1 ] Single-phase multiferroic BFO had attracted great interests due to its robust ferroelectric and antiferromagnetic orderings at room temperatures. [ 2–11 ] Under a strong compressive strain ( > 4%), the stable crystal structure of BFO transformed from the rhombohedral-like monoclinics (R) to tetragonal-like monoclinics (T), [ 12 , 13 ] and with suitable strain relaxation through thickness, the coexistence of R-BFO and T-BFO phases can be obtained in the same fi lm. [ 1 , 14–18 ]

Development of magnetoelectric, electromechanical, and photovoltaic devices based on mixed-phase rhombohedral-tetragonal (R-T) BiFeO(3) (BFO) systems is possible only if the control of the engineered R phase variants is realized. Accordingly, we explore the mechanism of a bias induced phase transformation in this system. Single point spectroscopy demonstrates that the T → R transition is activated at lower voltages compared to T → -T polarization switching. With phase field modeling, the transition is shown to be electrically driven. We further demonstrate that symmetry of formed R-phase rosettes can be broken by a proximal probe motion, allowing controlled creation of R variants with defined orientation. This approach opens a pathway to designing next-generation magnetoelectronic and data storage devices in the nanoscale.

In this study magnetic force microscopy (MFM), piezoresponse force microscopy (PFM), and the newly developed piezomagnetic force microscopy (PmFM) techniques are used to probe the ferroelectric and ferromagnetic properties of BiFeO3-LiMn2O4 (BFO-LMO) heterostructures at nano-scale. The PmFM technique is also used to probe the ferromagnetic properties of CoFe2O4 (CFO) as a case study. The PFM and PmFM mappings of the BFO-LMO heterostructures clearly distinguish the BFO matrix and LMO nanopillars while the MFM mapping is ambiguous. The relatively high piezomagnetic response of BFO matrix is believed to be due to the Mn doping while the piezoelectric-like response of LMO nanopillars is due to the ionic activities and the vertical geometry of its heterostructure. Lastly, limitations of the PmFM technique are discussed.Copyright © 2014 by ASME

We report direct visualization of electrochemical lithiation and delithiation of Au anodes in a commercial LiPF6/EC/DEC electrolyte for lithium ion batteries using transmission electron microscopy (TEM). The inhomogeneous lithiation, lithium metal dendritic growth, electrolyte decomposition, and solid-electrolyte interface (SEI) formation are observed in situ. These results shed lights on strategies of improving electrode design for reducing short-circuit failure and improving the performance of lithium ion batteries.

The origin of giant electromechanical response in a mixed-phase rhombohedral-tetragonal BiFeO${}_{3}$ thin film is probed using subcoercive scanning probe microscopy based multiple-harmonic measurements. Significant contributions to the strain arise from a second-order harmonic response localized at the phase boundaries. Strain and dissipation data, backed by thermodynamic calculations, suggest that the source of the enhanced electromechanical response is the motion of phase boundaries. These findings elucidate the key role of labile phase boundaries, both natural and artificial, in achieving thin films with giant electromechanical properties.

Hybrid nanoparticles (NPs) composed of multiple components offer new opportunities for next-generation materials. In this study, a paradigm for the noble metal/ternary complex oxide hybrid NPs is reported by adopting pulsed laser ablation in liquids. As model hybrids, gold-spinel heterodimer (Au-CoFe2O4) and gold-pervoskite heterodimer (Au-SrTiO3) NPs are investigated. This work has demonstrated the diverse playgroup of NP conjugation enlarged by complex oxides.

We report a study on the thermodynamic stability and structure analysis of the epitaxial BiFeO3 (BFO) thin films grown on YAlO3 (YAO) substrate. First we observe a phase transition of MC-MA-T occurs in thin sample (, 18 pages, 6 figures, submitted to Journal of Applied Physics

We report a detailed study on the strain-driven phase transition between the tetragonal-like and rhombohedral-like phases in epitaxial BiFeO${}_{3}$ (BFO) thin films which focuses on their structural nature, thermodynamic stability, and ferroelectric/piezoelectric properties. We first show that the tetragonal-like phase, which has a large c/a ratio (\ensuremath{\sim}1.2), in the compressively strained BFO is thermodynamically more favorable at high temperature and high strain state (small thickness). We also report a phase transition between two monoclinic phases at 150 \ifmmode^\circ\else\textdegree\fi{}C. The two monoclinic phases are differentiated by their $c$-axis parameters and tilting angles: The low-temperature phase (M${}_{\mathrm{C}}$) has a $c$-axis parameter of 4.64 \AA{} and a tilting angle (\ensuremath{\beta} $=$ 88.5\ifmmode^\circ\else\textdegree\fi{}) along the $a$ axis, while the high-temperature phase (M${}_{\mathrm{A}}$) has a $c$-axis parameter of 4.66 \AA{} and a tilting angle (\ensuremath{\beta} $=$ 86.8\ifmmode^\circ\else\textdegree\fi{}) along both of the $a$ and $b$ axes. We further show that samples undergoing the M${}_{\mathrm{C}}$--M${}_{\mathrm{A}}$ phase transition exhibit ferroelectric polarization rotation and piezoelectric enhancement. Our findings directly unveil the close links between structural changes, polarization rotation, and large piezoelectricity at morphotropic phase boundaries in BiFeO${}_{3}$.

Development of magnetoelectric, electromechanical, and photovoltaic devices based on mixed-phase rhombohedral-tetragonal (R-T) BiFeO(3) (BFO) systems is possible only if the control of the engineered R phase variants is realized. Accordingly, we explore the mechanism of a bias induced phase transformation in this system. Single point spectroscopy demonstrates that the T → R transition is activated at lower voltages compared to T → -T polarization switching. With phase field modeling, the transition is shown to be electrically driven. We further demonstrate that symmetry of formed R-phase rosettes can be broken by a proximal probe motion, allowing controlled creation of R variants with defined orientation. This approach opens a pathway to designing next-generation magnetoelectronic and data storage devices in the nanoscale.

Strong spin-lattice coupling in condensed matter gives rise to intriguing physical phenomena such as colossal magnetoresistance and giant magnetoelectric effects. The phenomenological hallmark of such a strong spin-lattice coupling is the manifestation of a large anomaly in the crystal structure at the magnetic transition temperature. Here we report that the magnetic Neel temperature of the multiferroic compound BiFeO(3) is suppressed to around room temperature by heteroepitaxial misfit strain. Remarkably, the ferroelectric state undergoes a first-order transition to another ferroelectric state simultaneously with the magnetic transition temperature. Our findings provide a unique example of a concurrent magnetic and ferroelectric transition at the same temperature among proper ferroelectrics, taking a step toward room temperature magnetoelectric applications.

Magnetoelectrics and multiferroics present exciting opportunities for electric-field control of magnetism. However, there are few room-temperature ferromagnetic-ferroelectrics. Among the various types of multiferroics the bismuth ferrite system has received much attention primarily because both the ferroelectric and the antiferromagnetic orders are quite robust at room temperature. Here we demonstrate the emergence of an enhanced spontaneous magnetization in a strain-driven rhombohedral and super-tetragonal mixed phase of BiFeO₃. Using X-ray magnetic circular dichroism-based photoemission electron microscopy coupled with macroscopic magnetic measurements, we find that the spontaneous magnetization of the rhombohedral phase is significantly enhanced above the canted antiferromagnetic moment in the bulk phase, as a consequence of a piezomagnetic coupling to the adjacent tetragonal-like phase and the epitaxial constraint. Reversible electric-field control and manipulation of this magnetic moment at room temperature is also shown.

We present a detailed study on the magnetic coercivity of Co/CoO-MgO core-shell systems, which exhibits a large exchange bias due to an increase of the uncompensated spin density at the interface between the CoO shell and the metallic Co core by replacing Co by Mg within the CoO shell. We find a large magnetic coercivity of 7120 Oe around the electrical percolation threshold of the Co/CoO core/shell particles, while samples with a smaller or larger Co metal volume fraction show a considerably smaller coercivity. Thus, this study may lead to a route to improving the magnetic properties of artificial magnetic material in view of potential applications.

As the advance of technology, devices with multi-function have dictated the material design. Complex oxide materials, having the spatial variation of electron charge and lattice degree of freedom at interface, have attracted wide attention because of their various properties. Recently, strained bismuth ferrite (BiFeO3, BFO) thin film is the most promising multifunctional material due to its spontaneous magnetic, ferroelectric and unique electromechanical properties at room temperature. In this study, we have investigated the temperature-dependent structural and strain-driven phase transition in epitaxial BFO thin films deposited on LaAlO3 substrates. Atomic force microscopy (AFM) and X-ray diffraction spectroscopy (XRD) demonstrated that the tetragonal-like phase (T-phase) and rhombohedral-like phase (R-phase) were involved in the strain BFO thin films. High-resolution transmission electron microscopy (HRTEM) images show that the T-phase BFO has a large c-axis parameter of ~4.65 Å, whereas R-phase BFO has a relatively small c-axis parameter of ~4.05 Å. We further find that the tilt angle between R/T phases is about 4.65° along the a-axis. Using in-situ TEM, we observed that the BFO thin film exhibited R→T phase transition with increasing temperature. Upon increasing the temperature from room temperature to 200℃, we found a significant increase in the width of T-phase region with the broader morphology phase boundary (MPB). Interestingly, upon further increasing the temperature to 250~300℃, the MPB disappears gradually with the change of tilt angle. Eventually, only T-phase BFO would be preserved at high temperature. Our study directly demonstrates the detail of structural changes with temperature effect, which may provide important information for material design and promising multifunctional applications in future technology.

Cation intermixing at functional oxide interfaces remains a highly controversial area directly relevant to interface-driven nanoelectronic device properties. Here, we systematically explore the cation intermixing in epitaxial (001) oriented multiferroic bismuth ferrite (BFO) grown on a (001) lanthanum aluminate (LAO) substrate. Aberration corrected dedicated scanning transmission electron microscopy and electron energy loss spectroscopy reveal that the interface is not chemically sharp, but with an intermixing of ∼2 nm. The driving force for this process is identified as misfit-driven elastic strain. Landau-Ginzburg-Devonshire-based phenomenological theory was combined with the Sheldon and Shenoy formula in order to understand the influence of boundary conditions and depolarizing fields arising from misfit strain between the LAO substrate and BFO film. The theory predicts the presence of a strong potential gradient at the interface, which decays on moving into the bulk of the film. This potential gradient...

not Available.

Trilayer heterostructures consisting of a ferroelectric bismuth ferrite (BFO) film sandwiched between ferromagnetic lanthanum strontium manganese oxide (LSMO) films were fabricated using pulsed laser deposition. Both BFO thicknesses (20 nm, 5 nm) and cooling rates were varied to investigate the role of processing parameters on the chemistry of the interfaces. The interfaces were investigated using a dedicated aberration corrected scanning transmission electron microscope (STEM) operated at 100 kV via STEM-high angle annular dark field (STEM-HAADF) and STEM-electron energy loss spectroscopy (STEM-EELS) modes. Combined analysis through STEM-HAADF and STEM-EELS revealed the formation of lattice distortion in certain regions of the BFO layer for the ∼5 nm film. Piezoresponse force microscopy (PFM) studies of the ∼5 nm BFO sample revealed weak ferroelectric domain switching. Stacking fault defects with mixed valence manganese (Mn-B site cation) were formed in the top LSMO layer when the heterostructure was coo...

The magnetoelectric coupling in multiferroic materials is promising for a wide range of applications, yet manipulating magnetic ordering by electric field proves elusive to obtain and difficult to control. In this paper, we explore the prospect of controlling magnetic ordering in misfit strained bismuth ferrite (BiFeO(3), BFO) films, combining theoretical analysis, numerical simulations, and experimental characterizations. Electric field induced transformation from a tetragonal phase to a distorted rhombohedral one in strain engineered BFO films has been identified by thermodynamic analysis, and realized by scanning probe microscopy (SPM) experiment. By breaking the rotational symmetry of a tip-induced electric field as suggested by phase field simulation, the morphology of distorted rhombohedral variants has been delicately controlled and regulated. Such capabilities enable nanoscale control of magnetoelectric coupling in strain engineered BFO films that is difficult to achieve otherwise, as demonstrated by phase field simulations.