Chemical Conversions within the Mo-Ga-C System: Layered Solids with Variable Ga Content.

Layered carbides are fascinating compounds due to their enormous structural and chemical diversity, as well as their potential to possess useful and tunable functional properties. Their preparation, however, is challenging and forces synthesis scientists to develop creative and innovative strategies to access high-quality materials. One unique compound among carbides is Mo2Ga2C. Its structure is related to the large and steadily growing family of 211 MAX phases that crystallize in a hexagonal structure (space group P63/mmc) with alternating layers of edge-sharing M6X octahedra and layers of the A-element. Mo2Ga2C also crystallizes in the same space group, with the difference that the A-element layer is occupied by two A-elements, here Ga, that sit right on top of each other (hence named "221" compound). Here, we propose that the Ga content in this compound is variable between 2:2, 2:1, and 2: ≤1 (and 2:0) Mo/Ga ratios. We demonstrate that one Ga layer can be selectively removed from Mo2Ga2C without jeopardizing the hexagonal P63/mmc structure. This is realized by chemical treatment of the 221 phase Mo2Ga2C with a Lewis acid, leading to the "conventional" 211 MAX phase Mo2GaC. Upon further reaction with CuCl2, more Ga is removed and replaced with Cu (instead of fully exfoliating into the Ga-free Mo2CTx MXene), leading to Mo2Ga1-xCuxC still crystallizing with space group P63/mmc, however, with a significantly larger c-lattice parameter. Furthermore, 211 Mo2GaC can be reacted with Ga to recover the initial 221 Mo2Ga2C. All three reaction pathways have not been reported previously and are supported by powder X-ray diffraction (PXRD), electron microscopy, X-ray spectroscopy, and density functional theory (DFT) calculations.

Quantitative measurement of nanoscale electrostatic potentials and charges using off-axis electron holography: Developments and opportunities.

Off-axis electron holography has evolved into a powerful electron-microscopy-based technique for characterizing electromagnetic fields with nanometer-scale resolution. In this paper, we present a review of the application of off-axis electron holography to the quantitative measurement of electrostatic potentials and charge density distributions. We begin with a short overview of the theoretical and experimental basis of the technique. Practical aspects of phase imaging, sample preparation and microscope operation are outlined briefly. Applications of off-axis electron holography to a wide range of materials are then described in more detail. Finally, challenges and future opportunities for electron holography investigations of electrostatic fields and charge density distributions are presented.

Large positive linear magnetoresistance in the two-dimensional t 2g electron gas at the EuO/SrTiO3 interface.

The development of novel nano-oxide spintronic devices would benefit greatly from interfacing with emergent phenomena at oxide interfaces. In this paper, we integrate highly spin-split ferromagnetic semiconductor EuO onto perovskite SrTiO3 (001). A careful deposition of Eu metal by molecular beam epitaxy results in EuO growth via oxygen out-diffusion from SrTiO3. This in turn leaves behind a highly conductive interfacial layer through generation of oxygen vacancies. Below the Curie temperature of 70 K of EuO, this spin-polarized two-dimensional t 2g electron gas at the EuO/SrTiO3 interface displays very large positive linear magnetoresistance (MR). Soft x-ray angle-resolved photoemission spectroscopy (SX-ARPES) reveals the t 2g nature of the carriers. First principles calculations strongly suggest that Zeeman splitting, caused by proximity magnetism and oxygen vacancies in SrTiO3, is responsible for the MR. This system offers an as-yet-unexplored route to pursue proximity-induced effects in the oxide two-dimensional t 2g electron gas.

Above 400-K robust perpendicular ferromagnetic phase in a topological insulator.

The quantum anomalous Hall effect (QAHE) that emerges under broken time-reversal symmetry in topological insulators (TIs) exhibits many fascinating physical properties for potential applications in nanoelectronics and spintronics. However, in transition metal-doped TIs, the only experimentally demonstrated QAHE system to date, the QAHE is lost at practically relevant temperatures. This constraint is imposed by the relatively low Curie temperature (Tc) and inherent spin disorder associated with the random magnetic dopants. We demonstrate drastically enhanced Tc by exchange coupling TIs to Tm3Fe5O12, a high-Tc magnetic insulator with perpendicular magnetic anisotropy. Signatures showing that the TI surface states acquire robust ferromagnetism are revealed by distinct squared anomalous Hall hysteresis loops at 400 K. Point-contact Andreev reflection spectroscopy confirms that the TI surface is spin-polarized. The greatly enhanced Tc, absence of spin disorder, and perpendicular anisotropy are all essential to the occurrence of the QAHE at high temperatures.

Direct Mapping of Charge Distribution during Lithiation of Ge Nanowires Using Off-Axis Electron Holography.

The successful operation of rechargeable batteries relies on reliable insertion/extraction of ions into/from the electrodes. The battery performance and the response of the electrodes to such ion insertion and extraction are directly related to the spatial distribution of the charge and its dynamic evolution. However, it remains unclear how charge is distributed in the electrodes during normal battery operation. In this work, we have used off-axis electron holography to measure charge distribution during lithium ion insertion into a Ge nanowire (NW) under dynamic operating conditions. We discovered that the surface region of the Ge core is negatively charged during the core-shell lithiation of the Ge NW, which is counterbalanced by positive charge on the inner surface of the lithiated LixGe shell. The remainder of the lithiated LixGe shell is free from net charge, consistent with its metallic characteristics. The present work provides a vivid picture of charge distribution and dynamic evolution during Ge NW lithiation and should form the basis for tackling the response of these and related materials under real electrochemical conditions.

Determination of Mean Inner Potential and Inelastic Mean Free Path of ZnTe Using Off-Axis Electron Holography and Dynamical Effects Affecting Phase Determination.

The mean inner potential (MIP) and inelastic mean free path (IMFP) of undoped ZnTe are determined using a combination of off-axis electron holography and convergent beam electron diffraction. The ZnTe MIP is measured to be 13.7±0.6 V, agreeing with previously reported simulations, and the IMFP at 200 keV is determined to be 46±2 nm for a collection angle of 0.75 mrad. Dynamical effects affecting holographic phase imaging as a function of incident beam direction for several common semiconductors are systematically studied and compared using Bloch wave simulations. These simulation results emphasize the need for careful choice of specimen orientation when carrying out quantitative electron holography studies in order to avoid erroneous phase measurements.

Carrier density modulation in a germanium heterostructure by ferroelectric switching.

The development of non-volatile logic through direct coupling of spontaneous ferroelectric polarization with semiconductor charge carriers is nontrivial, with many issues, including epitaxial ferroelectric growth, demonstration of ferroelectric switching and measurable semiconductor modulation. Here we report a true ferroelectric field effect-carrier density modulation in an underlying Ge(001) substrate by switching of the ferroelectric polarization in epitaxial c-axis-oriented BaTiO3 grown by molecular beam epitaxy. Using the density functional theory, we demonstrate that switching of BaTiO3 polarization results in a large electric potential change in Ge. Aberration-corrected electron microscopy confirms BaTiO3 tetragonality and the absence of any low-permittivity interlayer at the interface with Ge. The non-volatile, switchable nature of the single-domain out-of-plane ferroelectric polarization of BaTiO3 is confirmed using piezoelectric force microscopy. The effect of the polarization switching on the conductivity of the underlying Ge is measured using microwave impedance microscopy, clearly demonstrating a ferroelectric field effect.

Determination of polarization-fields across polytype interfaces in InAs nanopillars.

Polarization fields within InAs nanopillars with zincblende(ZB)/wurtzite(WZ) polytype stacking are quantified. The displacement of charged ions inside individual tetrahedra of WZ regions is measured at the atomic scale. The variations of spontaneous polarization along the interface normal are related to strain at interfaces of different polytypes. Thus, direct correlation between local atomic structure and electric properties is demonstrated.

Atomic configurations at InAs partial dislocation cores associated with Z-shape faulted dipoles.

The atomic arrangements of two types of InAs dislocation cores associated by a Z-shape faulted dipole are observed directly by aberration-corrected high-angle annular-dark-field imaging. Single unpaired columns of different atoms in a matrix of dumbbells are clearly resolved, with observable variations of bonding lengths due to excess Coulomb force from bare ions at the dislocation core. The corresponding geometric phase analysis provides confirmation that the dislocation cores serve as origins of strain field inversion while stacking faults maintain the existing strain status.

Exploring aberration-corrected electron microscopy for compound semiconductors.

The development of aberration-corrected electron microscopes (ACEMs) has made it possible to resolve individual atomic columns ('dumbbells') with correct interatomic spacings in elemental and compound semiconductors. Thus, the latest generations of ACEMs should become powerful instruments for determining detailed structural arrangements at defects and interfaces in these materials. This paper provides a short overview of off-line ('software') and on-line ('hardware') ACEM techniques, with particular reference to characterization of elemental and compound semiconductors. Exploratory probe-corrected studies of ZnTe/InP and ZnTe/GaAs epitaxial heterostructures and interfacial defects are also described. Finally, some of the associated problems and future prospects are briefly discussed.

Polarization-induced charge distribution at homogeneous zincblende/wurtzite heterostructural junctions in ZnSe nanobelts.

Homogeneous heterostructural wurtzite (WZ)/zincblende (ZB) junctions are successfully fabricated in ZnSe nanobelts. Polarity continuity across the ZB/WZ interface is demonstrated. The saw-tooth-like potential profile induced by spontaneous polarization across the WZ/ZB/WZ interfaces is identified directly at the nanoscale. The polarization-induced charge distribution across the homogeneous heterostructural interfaces is proposed as a viable alternative approach towards charge tailoring in semiconductor nanostructures.

Observation of hole accumulation in Ge/Si core/shell nanowires using off-axis electron holography.

Hole accumulation in Ge/Si core/shell nanowires (NWs) has been observed and quantified using off-axis electron holography and other electron microscopy techniques. The epitaxial [110]-oriented Ge/Si core/shell NWs were grown on Si (111) substrates by chemical vapor deposition through the vapor-liquid-solid growth mechanism. High-angle annular-dark-field scanning transmission electron microscopy images and off-axis electron holograms were obtained from specific NWs. The excess phase shifts measured by electron holography across the NWs indicated the presence of holes inside the Ge cores. Calculations based on a simplified coaxial cylindrical model gave hole densities of (0.4 ± 0.2) /nm(3) in the core regions.

Phase-shifting electron holography for atomic image reconstruction.

Phase-shifting electron holography was used to reconstruct the object-wave function of high-spatial-frequency specimens of HgCdTe, and the requirements for precise measurements were investigated. Fresnel fringes due to the electrostatic biprism caused serious calculation errors during the phase-shifting reconstruction. Uniform interference fringes, obtained by adjusting the biprism voltage to cancel out the Fresnel fringes, were needed to minimize these errors. High-resolution holograms of a HgCdTe single crystal were recorded with coarse interference fringes and a high visibility of 65% and then used to reconstruct the atomic-scale object wave. Although the spatial resolution (0.25 nm) of the transmission electron microscope was worse than the separation (0.16 nm) between Hg (or Cd) and Te columns, the crystal polarity was determined from the aberration-corrected object wave.

Determination of the inelastic mean-free-path and mean inner potential for AlAs and GaAs using off-axis electron holography and convergent beam electron diffraction.

The mean-free-paths for inelastic scattering of high-energy electrons (200 keV) for AlAs and GaAs have been determined based on a comparison of thicknesses as measured by electron holography and convergent-beam electron diffraction. The measured values are 77 +/- 4 nm and 67 +/- 4 nm for AlAs and GaAs, respectively. Using these values, the mean inner potentials of AlAs and GaAs were then determined, from a total of 15 separate experimental measurements, to be 12.1 +/- 0.7 V and 14.0 +/- 0.6 V, respectively. These latter measurements show good agreement with recent theoretical calculations within experimental error.

Crystal habits and magnetic microstructures of magnetosomes in coccoid magnetotactic bacteria

Nós relatamos a aplicação de holografia não-axial e microscopia eletrônica de alta resolução para estudar os hábitos cristalinos de magnetossomos e a microestrutura magnética de dois morfotipos de cocos de bactérias magnetotáticas coletadas em uma lagoa salobra em Itaipu, Brasil. Itaipu-1, o organismo cocóide maior, contémduas cadeias separadas de magnetossomos atipicamente grandes; os cristais dos magnetossomos possuem projeções aproximadamente quadradas, comprimentos deaté 250 nm e são ligeiramente alongados na direção [111] (razão largura/comprimento de aproximadamente 0.9).Os cristais dos magnetossomos em Itaipu-3 possuemcomprimentos até 120 nm, maior alongamento na direção [111] (largura/comprimento ~ 0.6), e proeminentes facetas nas extremidades. Os resultados mostram que os hábitos cristalinos dos magnetossomos em Itaipu-1 eItaipu-3 são relacionados, diferindo apenas nos tamanhos relativos das suas faces cristalinas. Em ambos os casos, os cristais são alinhados com seus eixos de alongamento [111] paralelos à direção da cadeia. Em Itaipu-1, mas não em Itaipu-3, o posicionamento cristalográfico, perpendicular à direção [111], de cristais sucessivos na cadeia de magnetossomos parece estar sobre controlebiológico. Enquanto os magnetossomos grandes em Itaipu-1 são monodomínios magnéticos metaestáveis, em Itaipu-3 eles são monodomínios magnéticos permanentes como na maioria das bactérias.

Crystal habits and magnetic microstructures of magnetosomes in coccoid magnetotactic bacteria.

We report on the application of off-axis electron holography and high-resolution TEM to study the crystal habits of magnetosomes and magnetic microstructure in two coccoid morphotypes of magnetotactic bacteria collected from a brackish lagoon at Itaipu, Brazil. Itaipu-1, the larger coccoid organism, contains two separated chains of unusually large magnetosomes; the magnetosome crystals have roughly square projections, lengths up to 250 nm and are slightly elongated along [111] (width/length ratio of about 0.9). Itaipu-3 magnetosome crystals have lengths up to 120 nm, greater elongation along [111] (width/length approximately 0.6), and prominent corner facets. The results show that Itaipu-1 and Itaipu-3 magnetosome crystal habits are related, differing only in the relative sizes of their crystal facets. In both cases, the crystals are aligned with their [111] elongation axes parallel to the chain direction. In Itaipu-1, but not Itaipu-3, crystallographic positioning perpendicular to [111] of successive crystals in the magnetosome chain appears to be under biological control. Whereas the large magnetosomes in Itaipu-1 are metastable, single-magnetic domains, magnetosomes in Itaipu-3 are permanent, single-magnetic domains, as in most magnetotactic bacteria.

Sample preparation for precise and quantitative electron holographic analysis of semiconductor devices.

Wedge polishing was used to prepare one-dimensional Si n-p junction and Si p-channel metal-oxide-silicon field effect transistor (pMOSFET) samples for precise and quantitative electrostatic potential analysis using off-axis electron holography. To avoid artifacts associated with ion milling, cloth polishing with 0.02-microm colloidal silica suspension was used for final thinning. Uniform thickness and no significant charging were observed by electron holography analysis for samples prepared entirely by this method. The effect of sample thickness was investigated and the minimum thickness for reliable results was found to be approximately 160 nm. Below this thickness, measured phase changes were smaller than expected. For the pMOSFET sample, quantitative analysis of two-dimensional electrostatic potential distribution showed that the metallurgical gate length (separation between two extension junctions) was approximately 54 nm, whereas the actual gate length was measured to be approximately 70 nm by conventional transmission electron microscopy. Thus, source and drain junction encroachment under the gate was 16 nm.

Reconstruction technique for off-axis electron holography using coarse fringes.

A reconstruction technique for off-axis electron holography not requiring Fourier transformation is presented. Background intensity and amplitude modulation recorded in a hologram are normalized using an envelope function, and a cosine-function image corresponding to interference fringes is retrieved from the hologram. A reconstructed phase image is then calculated from the retrieved cosine image. After phase unwrapping, the phases due to carrier frequency and Fresnel diffraction from the biprism are removed using a reference hologram, and the corrected phase image is obtained. One advantage of this method is that the spatial resolution does not rely on the interference fringe spacing. Another advantage is that the phase image has no artifacts due to windowing of the sideband, which occurs in the usual Fourier-transformation method. Details of the calculation process and demonstrations of the method using a latex sphere particle and self-assembled Co nanoparticles are described.

Characterization of charging in semiconductor device materials by electron holography.

Quantitative analysis of electrostatic potential in semiconductor device samples using off-axis electron holography in the electron microscope is complicated by the presence of charged insulating layers. Preliminary results indicate that the behavior of p-type material near the Si-insulator interface may differ from that of n-type if the insulator is charging. Coating one side of the sample surface with carbon usually eliminates charging effects. Holographic phase measurements on thin silicon oxide film at liquid nitrogen temperature indicates that the maximum electric field near the edge of an charged region is 18 MV cm(-1), on the order of the breakdown voltage.