In-line Electron Holography Research Articles

Multiphase cooperation for multilevel strain accommodation in a single-crystalline BiFeO3 thin film

Abstract The functionalities and diverse metastable phases of multiferroic BiFeO3 (BFO) thin films depend on the misfit strain. Although mixed-phase-induced strain relaxation in multiphase BFO thin films is well known, it is unclear whether a single-crystalline BFO thin film can accommodate misfit strain without the involvement of its polymorphs. Thus, understanding the strain relaxation behavior is key to elucidating the lattice strain–property relationship. In this study, a correlative strain analysis based on dark-field inline electron holography (DIH) and quantitative scanning transmission electron microscopy (STEM) was performed to reveal the structural mechanism for strain accommodation of a single-crystalline BFO thin film. The nanoscale DIH strain analysis results indicated a random combination of multiple strain states that acted as a primary strain relief, forming irregularly strained nanodomains. The STEM-based bond length measurement of the corresponding strained nanodomains revealed a unique strain accommodation behavior achieved by a statistical combination of multiple modes of distorted structures on the unit-cell scale. The globally integrated strain for each nanodomain was estimated to be close to -1.5%, irrespective of the nanoscale strain states, which was consistent with the fully strained BFO film on the SrTiO3 substrate. Density functional theory calculations suggested that strain accommodation by the combination of metastable phases was energetically favored in relation to single-phase-mediated relaxation. This discovery allows a comprehensive understanding of strain accommodation behavior in ferroelectric oxide films, such as BFO, with various low-symmetry polymorphs.

Feld-induced modulation of two-dimensional electron gas at LaAlO3/SrTiO3 interface by polar distortion of LaAlO3

Since the discovery of two-dimensional electron gas at the LaAlO3/SrTiO3 interface, its intriguing physical properties have garnered significant interests for device applications. Yet, understanding its response to electrical stimuli remains incomplete. Our in-situ transmission electron microscopy analysis of a LaAlO3/SrTiO3 two-dimensional electron gas device under electrical bias reveals key insights. Inline electron holography visualized the field-induced modulation of two-dimensional electron gas at the interface, while electron energy loss spectroscopy showed negligible electromigration of oxygen vacancies. Instead, atom-resolved imaging indicated that electric fields trigger polar distortion in the LaAlO3 layer, affecting two-dimensional electron gas modulation. This study refutes the previously hypothesized role of oxygen vacancies, underscoring the lattice flexibility of LaAlO3 and its varied polar distortions under electric fields as central to two-dimensional electron gas dynamics. These findings open pathways for advanced oxide nanoelectronics, exploiting the interplay of polar and nonpolar distortions in LaAlO3.

Direct Imaging of Radiation-Sensitive Organic Polymer-Based Nanocrystals at Sub-Ångström Resolution.

Seeing the atomic configuration of single organic nanoparticles at a sub-Å spatial resolution by transmission electron microscopy has been so far prevented by the high sensitivity of soft matter to radiation damage. This difficulty is related to the need to irradiate the particle with a total dose of a few electrons/Å2, not compatible with the electron beam density necessary to search the low-contrast nanoparticle, to control its drift, finely adjust the electron-optical conditions and particle orientation, and finally acquire an effective atomic-resolution image. On the other hand, the capability to study individual pristine nanoparticles, such as proteins, active pharmaceutical ingredients, and polymers, with peculiar sensitivity to the variation in the local structure, defects, and strain, would provide advancements in many fields, including materials science, medicine, biology, and pharmacology. Here, we report the direct sub-ångström-resolution imaging at room temperature of pristine unstained crystalline polymer-based nanoparticles. This result is obtained by combining low-dose in-line electron holography and phase-contrast imaging on state-of-the-art equipment, providing an effective tool for the quantitative sub-ångström imaging of soft matter.

In-line and Off-axis Electron Holography for the Study of Biological.

In-line and Off-axis Electron Holography for the Study of Biological.

In-plane charged domain walls with memristive behaviour in a ferroelectric film.

Domain-wall nanoelectronics is considered to be a new paradigm for non-volatile memory and logic technologies in which domain walls, rather than domains, serve as an active element. Especially interesting are charged domain walls in ferroelectric structures, which have subnanometre thicknesses and exhibit non-trivial electronic and transport properties that are useful for various nanoelectronics applications1-3. The ability to deterministically create and manipulate charged domain walls is essential to realize their functional properties in electronic devices. Here we report a strategy for the controllable creation and manipulation of in-plane charged domain walls in BiFeO3 ferroelectric films a few nanometres thick. By using an in situ biasing technique within a scanning transmission electron microscope, an unconventional layer-by-layer switching mechanism is detected in which ferroelectric domain growth occurs in the direction parallel to an applied electric field. Based on atomically resolved electron energy-loss spectroscopy, in situ charge mapping by in-line electron holography and theoretical calculations, we show that oxygen vacancies accumulating at the charged domain walls are responsible for the domain-wall stability and motion. Voltage control of the in-plane domain-wall position within a BiFeO3 film gives rise to multiple non-volatile resistance states, thus demonstrating the key functional property of being a memristor a few unit cells thick. These results promote a better understanding of ferroelectric switching behaviour and provide a new strategy for creating unit-cell-scale devices.

Synergistic use of gradient flipping and phase prediction for inline electron holography

Inline holography in the transmission electron microscope is a versatile technique which provides real-space phase information that can be used for the correction of imaging aberrations, as well as for measuring electric and magnetic fields and strain distributions. It is able to recover high-spatial-frequency contributions of the phase effectively but suffers from the weak transfer of low-spatial-frequency information, as well as from incoherent scattering. Here, we combine gradient flipping and phase prediction in an iterative flux-preserving focal series reconstruction algorithm with incoherent background subtraction that gives extensive access to the missing low spatial frequencies. A procedure for optimizing the reconstruction parameters is presented, and results from Fe-filled C nanospheres, and MgO cubes are compared with phase images obtained using off-axis holography.

Oxide Two-Dimensional Electron Gas with High Mobility at Room-Temperature.

The prospect of 2‐dimensional electron gases (2DEGs) possessing high mobility at room temperature in wide‐bandgap perovskite stannates is enticing for oxide electronics, particularly to realize transparent and high‐electron mobility transistors. Nonetheless only a small number of studies to date report 2DEGs in BaSnO3‐based heterostructures. Here, 2DEG formation at the LaScO3/BaSnO3 (LSO/BSO) interface with a room‐temperature mobility of 60 cm2 V−1 s−1 at a carrier concentration of 1.7 × 1013 cm–2 is reported. This is an order of magnitude higher mobility at room temperature than achieved in SrTiO3‐based 2DEGs. This is achieved by combining a thick BSO buffer layer with an ex situ high‐temperature treatment, which not only reduces the dislocation density but also produces a SnO2‐terminated atomically flat surface, followed by the growth of an overlying BSO/LSO interface. Using weak beam dark‐field transmission electron microscopy imaging and in‐line electron holography technique, a reduction of the threading dislocation density is revealed, and direct evidence for the spatial confinement of a 2DEG at the BSO/LSO interface is provided. This work opens a new pathway to explore the exciting physics of stannate‐based 2DEGs at application‐relevant temperatures for oxide nanoelectronics.

Quantifying the data quality of focal series for inline electron holography

Inline electron holography, the recovery of amplitude and phase of an electron wave function having passed through a thin specimen from a focal series recorded in a transmission electron microscope is being applied in many labs worldwide. At medium range magnification (i.e. typically ≥0.8 nm where the lattice of small unit cell crystals such as silicon is not resolved), where the defocus needs to be varied over a rather large range of several hundred nm or even μm, the retrieval of low spatial frequency information is severely affected by the choice of experimental parameters as well as the way of data normalization. Methods to quantitatively analyze the reliability of phase maps obtained by inline electron holography are presented, and data recorded and processed in different ways are compared. While, even under optimized conditions, the phase reconstructed from an experimental focal series still lacks very low spatial frequency components, regularization schemes exist and are demonstrated to effectively hide artifacts associated with this lack of information.

Analysis of Local Charges at Hetero-interfaces by Electron Holography – A Comparative Study of Different Techniques

Interface charges confined within a few nanometers of hetero-interface can be characterized by measuring the phase shift of the transmitted beam using different electron holography techniques. However, reliable measurement of the electrostatic potential arising from the interface charges is challenging as the mean inner potential difference (ΔV0) between two adjoining materials as well as local variation of the sample thickness affect the phase shift. In the present study, we show how electron holography can be used to characterize the confined charges at an oxide hetero-interface and evaluate the applicability of different techniques for this purpose. The model system chosen for this study is a LaAlO3/SrTiO3 (LAO/STO) (111) hetero-interface featuring a two-dimensional electron gas (2DEG), where the ΔV0 between LAO and STO is about 2 eV, which is unignorably large and dominates the net potential variation across the interface. For transmission electron microscopy specimens prepared by focused ion beam we applied three different variants of electron holography techniques: off-axis, inline and hybrid electron holography; and compare the results obtained by these approaches in terms of the information transfer in the spatial frequency domain, and the signal-to-noise ratio of the electric field and charge density maps. To correctly assess the information pertinent to the interface-confined charges, we calculate the electrostatic potential and electric field distribution based on a charge model with taking account of the ΔV0 between LAO and STO and compared the calculated profiles with the experimental results after calibrating the local thickness variation across the LAO/STO interface. The results show that hybrid electron holography recovers the information across a wide range of spatial frequencies, and as a result, delivers the most reliable charge density information, albeit convoluted with the unavoidable effects arising from ΔV0.

Low-energy in-line electron holographic imaging of vitreous ice-embedded small biomolecules using a modified scanning electron microscope

Cryo-electron microscopy (cryo-EM) has become the method of choice in the field of structural biology, owing to its unique ability to deduce structures of vitreous ice-embedded, hydrated biomolecules over a wide range of structural resolutions. As cryo-transmission electron microscopes (cryo-TEM) become increasingly specialised for high, near-atomic resolution studies, operational complexity and associated costs serve as significant barriers to widespread usability and adoptability. To facilitate the expansion and accessibility of the cryo-EM method, an efficient, user-friendly means of imaging vitreous ice-embedded biomolecules has been called for. In this study, we present a solution to this issue by integrating cryo-EM capabilities into a commercial scanning electron microscope (SEM). Utilising the principle of low-energy in-line electron holography, our newly developed hybrid microscope permits low-to-moderate resolution imaging of vitreous ice-embedded biomolecules without the need for any form of sample staining or chemical fixation. Operating at 20 kV, the microscope takes advantage of the ease-of-use of SEM-based imaging and phase contrast imaging of low-energy electron holography. This study represents the first reported successful application of low-energy in-line electron holographic imaging to vitreous ice-embedded small biomolecules, the effectiveness of which is demonstrated here with three morphologically distinct specimens.

Exploration of Bragg in-line electron holography as a possible tool for crystal structure determination

Exploration of Bragg in-line electron holography as a possible tool for crystal structure determination

Cavities Imaged by In-Line Electron Holography in Irradiated Aluminium Alloy

Cavities Imaged by In-Line Electron Holography in Irradiated Aluminium Alloy

(Invited) Multiple Heterojunction in Single Titanium Dioxide Nanomaterials for Photocatalysis and Photoelectrochemical Cells

Despite a longstanding controversy surrounding TiO2 materials, TiO2 polymorphs with heterojunctions composed of anatase and rutile outperform individual polymorphs because of the type-II energetic band alignment at the heterojunction interface. Improvement in photocatalysis has also been achieved via black TiO2 with a thin disorder layer surrounding ordered TiO2. However, localization of this disorder layer in a conventional single TiO2 nanoparticle with the heterojunction composed of anatase and rutile has remained a big challenge. Here we report the selective positioning of a disorder layer of controlled thicknesses between the anatase and rutile phases by a conceptually different synthetic route to access highly efficient novel metal-free photocatalysis for H2 production. The presence of localized disorder layer within a single TiO2 nanoparticle was confirmed for the first time by high-resolution transmission electron microscopy (TEM) with electron energy-loss spectroscopy (EELS) and inline electron holography. Multiple heterojunctions in single TiO2 nanoparticles composed of crystalline anatase/disordered rutile/ordered rutile layers give the nanoparticles superior electron/hole separation efficiency and novel metal-free surface reactivity, which concomitantly yields an H2 production rate that is ~11 times higher than that of Pt decorated conventional anatase and rutile single heterojunction TiO2 systems.

Quantitative counting of Zn and O atoms by atomic resolution off-axis and in-line electron holography

We present quantitative counting of Zn and O atoms in zinc oxide epitaxial thin film by different routes; reconstruction of phase from the side and central bands of atomic resolution off-axis and in-line electron holography. Results show that the reconstructed phase from both the side and the central bands and the corresponding number of Zn (Z = 30) and O (Z = 8) atoms are in close agreement with the systematic increase in the number of atoms for a sample area less than the extinction distance. However, complete disagreement is observed for the sample area more than the extinction distance. On the other hand, the reconstructed phase obtained via in-line holography shows no systematic change with thickness for the same sample. Phase detection limits and the atomic model used to count the atoms are discussed.

Investigation of the electrostatic potential of a grain boundary in Y-substituted BaZrO3 using inline electron holography.

We apply inline electron holography to investigate the electrostatic potential across an individual BaZr0.9Y0.1O3 grain boundary. With holography, we measure a grain boundary potential of -1.3 V. Electron energy loss spectroscopy analyses indicate that barium vacancies at the grain boundary are the main contributors to the potential well in this sample. Furthermore, geometric phase analysis and density functional theory calculations suggest that reduced atomic density at the grain boundary also contributes to the experimentally measured potential well.

Towards quantitative mapping of the charge distribution along a nanowire by in-line electron holography

Mapping the charge distribution in nano scale systems still is a difficult task, but is important to provide fundamental insights into the properties of materials. We demonstrate how in-line holography in transmission electron microscopy can be used to extract the charge distribution in the nanowire in a quantitative way. This technique can realize a fast acquisition of delicate charge variations. By taking advantage of the possibilities of in-situ electron microscopy, variations of the external field can be used to modulate the charge distribution. Because of the fast response to charge variations, this method provides an efficient probing tool for detecting dynamic charge redistribution.

Multiple Heterojunction in Single Titanium Dioxide Nanoparticles for Novel Metal-Free Photocatalysis.

Despite a longstanding controversy surrounding TiO2 materials, TiO2 polymorphs with heterojunctions composed of anatase and rutile outperform individual polymorphs because of the type-II energetic band alignment at the heterojunction interface. Improvement in photocatalysis has also been achieved via black TiO2 with a thin disorder layer surrounding ordered TiO2. However, localization of this disorder layer in a conventional single TiO2 nanoparticle with the heterojunction composed of anatase and rutile has remained a big challenge. Here, we report the selective positioning of a disorder layer of controlled thicknesses between the anatase and rutile phases by a conceptually different synthetic route to access highly efficient novel metal-free photocatalysis for H2 production. The presence of a localized disorder layer within a single TiO2 nanoparticle was confirmed for the first time by high-resolution transmission electron microscopy with electron energy-loss spectroscopy and inline electron holography. Multiple heterojunctions in single TiO2 nanoparticles composed of crystalline anatase/disordered rutile/ordered rutile layers give the nanoparticles superior electron/hole separation efficiency and novel metal-free surface reactivity, which concomitantly yields an H2 production rate that is ∼11-times higher than that of Pt-decorated conventional anatase and rutile single heterojunction TiO2 systems.

Induction Mapping of the 3D-Modulated Spin Texture of Skyrmions in Thin Helimagnets.

Envisaged applications of Skyrmions in magnetic memory and logic devices crucially depend on the stability and mobility of these topologically nontrivial magnetic textures in thin films. We present for the first time quantitative maps of the magnetic induction that provide evidence for a 3D modulation of the Skyrmionic spin texture. The projected in-plane magnetic induction maps as determined from in-line and off-axis electron holography carry the clear signature of Bloch Skyrmions. However, the magnitude of this induction is much smaller than the values expected for homogeneous Bloch Skyrmions that extend throughout the thickness of the film. This finding can only be understood if the underlying spin textures are modulated along the out-of-plane z direction. The projection of (the in-plane magnetic induction of) helices is further found to exhibit thickness-dependent lateral shifts, which show that this z modulation is accompanied by an (in-plane) modulation along the x and y directions.

Multiple-Heterojunction in Single Titanium Dioxide Nanoparticle for Novel Metal-Free Photocatalysis

Despite longstanding controversy, TiO2 polymorphs heterojunction composed of anatase and rutile outperform the individual ones because of the energetic type-II band alignment at the heterojunction interface. Apart from the conventional polymorphs interface, the surface disordered TiO2 has been drawing interest and considered as an unpredictable strategy while is regarded as a fact for dramatically enhancing photocatalytic activity. However, introduction and localization of the disordered layer within conventional TiO2 nanoparticles with the heterojunction has remained a big challenge. Here we report a selective positioning of a disordered layer with different thickness ranges in between the anatase and rutile phases by a conceptually different synthetic route for highly efficient novel metal-free photocatalytic H2 production (denoted as DE-P25). With two step disorder engineering: Phase selective disordering of rutile TiO2 and thermal annealing process at temperature lower than phase transformation, the multiple heterojunction in DE-P25 single nanoparticle with the disordered layer of 2~3 nm could be synthesized which is confirmed by high resolution-TEM, electron energy loss spectroscopy (EELS) and inline electron holography mapping for the first time. EELS Ti-L2,3 spectrum geometry of DE-P25 showed distinctive oxygen-deficient variation between the two crystals which corresponds with the drastic decrease of potential and negative charge density within the disordered layer due to localized unpaired electrons. PL decay profiles exhibiting ultra-fast charge migration of DE-P25 indicate that the rutile phase incorporated with the disordered layer in the TiO2 nanoparticle induces dominant direct excition formation and reduces the self-trap of charge carriers, thus suppressing the electron/hole recombination, which perfectly coincides with the holography mapping analysis. This multiple heterojunction in single TiO2 nanoparticles composed of crystalline anatase/disordered rutile/ordered rutile demonstrate not only superior interfacial charge separation efficiency, but also novel-metal free surface reactivity, which synergistically yields ~140 times higher H2 production rate than conventional anatase and rutile single heterojunction system. Figure 1

Development of a SEM-based low-energy in-line electron holography microscope for individual particle imaging

A new SEM-based in-line electron holography microscope has been under development. The microscope utilizes conventional SEM and BF-STEM functionality to allow for rapid searching of the specimen of interest, seamless interchange between SEM, BF-STEM and holographic imaging modes, and makes use of coherent low-energy in-line electron holography to obtain low-dose, high-contrast images of light element materials. We report here an overview of the instrumentation and first experimental results on gold nano-particles and carbon nano-fibers for system performance tests. Reconstructed images obtained from the holographic imaging mode of the new microscope show substantial image contrast and resolution compared to those acquired by SEM and BF-STEM modes, demonstrating the feasibility of high-contrast imaging via low-energy in-line electron holography. The prospect of utilizing the new microscope to image purified biological specimens at the individual particle level is discussed and electron optical issues and challenges to further improve resolution and contrast are considered.