Creation of flexible spin-caloritronic material with giant transverse thermoelectric conversion by nanostructure engineering.

Functional materials such as magnetic, thermoelectric, and battery materials have been revolutionized through nanostructure engineering. However, spin caloritronics, an advancing field based on spintronics and thermoelectrics with fundamental physics studies, has focused only on uniform materials without complex microstructures. Here, we show how nanostructure engineering enables transforming simple magnetic alloys into spin-caloritronic materials displaying significantly large transverse thermoelectric conversion properties. The anomalous Nernst effect, a promising transverse thermoelectric phenomenon for energy harvesting and heat sensing, has been challenging to utilize due to the scarcity of materials with large anomalous Nernst coefficients. We demonstrate a remarkable ~ 70% improvement in the anomalous Nernst coefficients (reaching ~ 3.7 µVK-1) and a significant ~ 200% enhancement in the power factor (reaching ~ 7.7 µWm-1K-2) in flexible Fe-based amorphous materials by nanostructure engineering without changing their composition. This surpasses all reported amorphous alloys and is comparable to single crystals showing large anomalous Nernst effect. The enhancement is attributed to Cu nano-clustering, facilitating efficient transverse thermoelectric conversion. This discovery advances the materials science of spin caloritronics, opening new avenues for designing high-performance transverse thermoelectric devices for practical applications.

Atomic-Scale Multimodal Characterization of Self-Assembled InAs/InGaAlAs Quantum Dots.

Self-assembled quantum dots (QDs) are potential candidates for photoelectric and photovoltaic devices, because of their discrete energy levels. The characterization of QDs at the atomic level using a multimodal approach is crucial to improving device performance because QDs are nanostructures with highly correlated structural parameters. In this study, scanning transmission electron microscopy, geometric phase analysis, and atom probe tomography were employed to characterize structural parameters such as the shape, strain, and composition of self-assembled InAs-QDs with InGaAlAs spacer layers. The measurements revealed characteristic AlAs-rich regions above the QDs and InAs-rich regions surrounding the QD columns, which can be explained by the relationship between the effect of strain and surface curvature around the QD. The methodology described in this study accelerates the development of future QD devices because its multiple perspectives reveal phenomena such as atomic-scale segregations and allow for more detailed discussions of the mechanisms of these phenomena.

An Automated Site-Specific Tip Preparation Method for Atom Probe Tomography Using Script-Controlled Focused Ion Beam/Scanning Electron Microscopy.

The automation of the atom probe tomography (APT) tip preparation using a focused ion beam (FIB) with a scanning electron microscopy (SEM) dual-beam system will certainly contribute to systematic APT research with higher throughput and reliability. While our previous work established a method to prepare tips with a specified tip curvature and taper angle automatically, by using script-controlled FIB/SEM, the technique has been expanded to automated "site-specific" tip preparation in the current work. The improved procedure can automatically detect not only the tip shape but also the interface position in the tip; thus, the new function allows for control of the tip apex position. In other words, automated "site-specific" tip preparations are possible. The details of the automation procedure and some experimental demonstrations, that is, a Pt cap on Si, InGaN-based MQWs, and a p-n junction of GaAs, are presented.

Robust Preparation of Sub-20-nm-Thin Lamellae for Aberration-Corrected Electron Microscopy.

Aberration-corrected scanning transmission electron microscopy (STEM) has been advancing resolution, sensitivity, and microanalysis due to the intense demands of atomic-level microstructural investigations. Recent STEM technologies require preparing a thin lamella whose thickness is ideally below 20 nm. Although focused-ion-beam/scanning-electron-microscopy (FIB/SEM) is an established method to prepare a high-quality lamella, nanometer-level controllability of lamella thickness remains a fundamental problem. Here, the robust preparation of a sub-20-nm-thin lamella is demonstrated by FIB/SEM with real-time feedback from thickness quantification. The lamella thickness is quantified by back-scattered-electron SEM imaging in a thickness range between 0 and 100 nm without any reference to numerical simulation. Using real-time feedback from the thickness quantification, the FIB/SEM terminates thinning a lamella at a targeted thickness. The real-time feedback system eventually provides 1-nm-level controllability of the lamella thickness. As a proof-of-concept, a near-10-nm-thin lamella is prepared from a SrTiO3 crystal by our methodology. Moreover, the lamella thickness is controllable at a target heterointerface. Thus, a sub-20-nm-thin lamella is prepared from a LaAlO3 /SrTiO3 heterointerface. The methodology offers a robust and operator-independent platform to prepare a sub-20-nm-thin lamella from various materials. This platform will broadly impact aberration-corrected STEM studies in materials science and the semiconductor industry.

Combined effect of interstitial-substitutional elements on dislocation dynamics in nitrogen-added austenitic stainless steels.

Combined addition of interstitial-substitutional elements has been acknowledged to contribute to the increase in the strengths of steels. For further improvements in mechanical properties, their atomic-scale interaction mechanisms with dislocations are required to be examined. In this study, both high-resolution transmission electron microscopy and atom-probe tomography were used to correlate interstitial-substitutional elements with dislocation characteristics in austenitic stainless steels. Three types of dislocation core structures are identified and associated with their strain fields as well as N and Cr atoms in the N-added steels. It is revealed that N atoms interact elastically with the dislocations, followed by the segregation of Cr atoms via the chemical interaction between N and Cr atoms. This insight significantly improves the understanding of the multiple alloying mechanism in metallic materials such as interstitial alloys and high-entropy alloys.

Neutron imaging for magnetization inside an operating inductor.

Magnetic components are key parts of energy conversion systems, such as electric generators, motors, power electric devices, and magnetic refrigerators. Toroidal inductors with magnetic ring cores can be found inside such electric devices that are used daily. For such inductors, magnetization vector M is believed to circulate with/without distribution inside magnetic cores as electric power was used in the late nineteenth century. Nevertheless, notably, the distribution of M has never been directly verified. Herein, we measured a map of polarized neutron transmission spectra for a ferrite ring core assembled on a familiar inductor device. The results showed that M circulates inside the ring core with a ferrimagnetic spin order when power is supplied to the coil. In other words, this method enables the multiscale operando imaging of magnetic states, allowing us to evaluate the novel architectures of high-performance energy conversion systems using magnetic components with complex magnetic states.

Charge-to-spin conversion in fully epitaxial Ru/Cu hybrid nanolayers with interface control.

The demonstration of the charge-to-spin conversion, especially with enhanced spin Hall conductivity, is crucial for the development of energy-efficient spintronic devices such as spin-orbit torque (SOT) based magnetoresistive random access memories. In this work, fully epitaxial Ru/Cu heterostructures were fabricated with interface engineering and nanolayer insertions consisting of Cu (1 nm)/Ru (1 nm) structures with different numbers of periods. The atomically controlled interface was confirmed by the high-resolution high-angle annular dark-field scanning transmission electron microscopy, and the epitaxial relationship persists even in the hybrid nanolayer insertion structures. The spin current generation was detected by the measurement of unidirectional spin Hall magnetoresistance, and the effective damping-like spin Hall efficiency (ξDL) was further quantitatively evaluated by the spin-torque ferromagnetic resonance with thickness dependence of the ferromagnetic layer. It is found that the sharp interface Ru/Cu film has a sizeableξDLof -2.2% and the insertion of Cu/Ru nanolayers at the interface can increase theξDLvalue to -3.7%. The former could be attributed to the interface spin-orbit filtering effect and the latter may be further understood by the intrinsic contribution from the local electronic structure tuning due to the lattice distortion near the interface. A large effective spin Hall conductivity is achieved to be (3∼5) × 105ℏ2eΩ-1m-1in the epitaxial Ru/Cu hybrid nanolayers, which is in the same range as that of platinum. This work indicates that the interfacial control with hybrid nanolayer structures can extend the SOT-based materials to highly conductive metals, even with weak spin-orbit interactions, toward high stability, low cost, and low energy consumption for spintronic applications.

Development of automated tip preparation for atom probe tomography by using script-controlled FIB-SEM.

Atom probe tomography (APT) has become a popular technique for microstructural analysis of a wide range of alloys and devices over the past two decades owing to the employment of laser-assisted field evaporation and the development of site-specific tip preparation using a focused ion beam (FIB) with a scanning electron microscopy (SEM) system. In laser-assisted field evaporation, laser irradiation conditions largely influence mass resolution; therefore, recent commercial APT instruments allow strict control of the analysis conditions. However, the mass resolution is affected not only by the laser condition but also by the thermal conductivity of the material and the tip shape. In addition, it is also important to keep the tip shape constant in order to obtain tomography data with good reproducibility since the analytical volume highly depends on the tip shape. In this study, we have developed a method to fabricate the tip with the desired shape automatically by using a script-controlled FIB-SEM system, which has traditionally depended on the skill of the FIB-SEM operator. The tip shape was then intentionally changed by using this method, and its effect on the APT data is also discussed.

Extraction of phase information approximating the demagnetization field within a thin-foiled magnet using electron holography observation.

This paper proposes a method that provides a phase image related to the demagnetization field (Hd) within a thin-foil permanent magnet using electron holography. The observation of Hd remains a significant challenge because electron holography in principle allows only imaging of the magnetic flux density (B), which is a mixture of the contributions from magnetization (M), stray magnetic field (Hs) outside of the specimen and Hd inside of the specimen. The phase map approximating Hd, which was determined by processing of the electron holography observation from a Nd2Fe14B single-crystalline specimen, showed a good agreement with the prediction by micromagnetic theory. With respect to permanent magnets, this method can be applied to examinations about the coercivity mechanism, which is sensitive to the demagnetization field. Graphical Abstract.

Sm-Co-based amorphous alloy films for zero-field operation of transverse thermoelectric generation.

Transverse thermoelectric generation using magnetic materials is essential to develop active thermal engineering technologies, for which the improvements of not only the thermoelectric output but also applicability and versatility are required. In this study, using combinatorial material science and lock-in thermography technique, we have systematically investigated the transverse thermoelectric performance of Sm-Co-based alloy films. The high-throughput material investigation revealed the best Sm-Co-based alloys with the large anomalous Nernst effect (ANE) as well as the anomalous Ettingshausen effect (AEE). In addition to ANE/AEE, we discovered unique and superior material properties in these alloys: the amorphous structure, low thermal conductivity, and large in-plane coercivity and remanent magnetization. These properties make it advantageous over conventional materials to realize heat flux sensing applications based on ANE, as our Sm-Co-based films can generate thermoelectric output without an external magnetic field. Importantly, the amorphous nature enables the fabrication of these films on various substrates including flexible sheets, making the large-scale and low-cost manufacturing easier. Our demonstration will provide a pathway to develop flexible transverse thermoelectric devices for smart thermal management.

Atomic Diffusion of Indium through Threading Dislocations in InGaN Quantum Wells.

The compositional and structural investigations of threading dislocations (TDs) in InGaN/GaN multiple quantum wells were carried out using correlative transmission electron microscopy (TEM) and atom probe tomography (APT). The correlative TEM/APT analysis on the same TD reveals that the indium atoms are diffused along the TD and its concentration decreases with distance from the InGaN layer. On the basis of the results, we directly observed that the indium atoms originating from the InGaN layer diffuse toward the epitaxial GaN surface through the TD, and it is considered to have occurred via the pipe diffusion mechanism induced by strain energy relaxation.

Stable field-emission from a CeB6 nanoneedle point electron source.

A single CeB6 nanoneedle structure has been fabricated using a focused ion beam (FIB) and its field emission characteristics have been evaluated. A converged electron beam has been obtained, attributed to its sharpened tip with a radius of curvature of about 10 nm. Combined with its low work function, the required electric field is as low as 1.6 V nm-1 to generate a field emission current of 50 nA. The most outstanding feature of the CeB6 nanoneedle emitter is its excellent current stability that enabled continuous emission for 16 hours with a fluctuation of 1.6% and without deterioration even in a vacuum of 10-7 Pa. The stable field-emission is attributed to the nanometric tip radius that led to reduction in gas adsorption and desorption. In addition, the downward dipolar structure on the emission surface is also beneficial for making the surface inert. These performance factors make CeB6 a practical field-emission point electron source for microscopy applications.

Most frequently asked questions about the coercivity of Nd-Fe-B permanent magnets.

Physically, the coercivity of permanent magnets should scale with the anisotropy field of ferromagnetic compounds, H A; however, the typical coercivity values of commercial polycrystalline sintered magnets are only ~0.2 H A, which is known as Brown's paradox. Recent advances in multi-scale microstructure characterizations using focused ion beam scanning electron microscope (FIB/SEM), aberration corrected scanning transmission electron microscopy (Cs-corrected STEM), and atom probe tomography (APT) revealed detailed microstructural features of commercial and experimental Nd-Fe-B magnets. These investigations suggest the magnetism of a thin layer formed along grain boundaries (intergranular phase) is a critical factor that influences the coercivity of polycrystalline magnets. To determine the magnetism of the thin intergranular phase, soft X-ray magnetic circular dichroism and electron holography play critical roles. Large-scale micromagnetic simulations using the models that are close to real microstructure incorporating the recent microstructure characterization results gave insights on how the coercivity and its thermal stability is influenced by the microstructures. Based on these new findings, coercivity of Nd-Fe-B magnets is being improved to its limit. This review replies to the most frequently asked questions about the coercivity of Nd-Fe-B permanent magnets based on our recent studies.

A stable LaB6 nanoneedle field-emission point electron source.

A material with a low work function exhibiting field-emission of electrons has long been sought as an ideal point electron source to generate a coherent electron beam with high brightness, long service life, low energy spread, and especially stable emission current. The quality and performance of the electron source are now becoming limiting factors for further improving the spatial resolution and analytical capabilities of the electron microscope. While tungsten (W) is still the only material of choice as a practically usable field emission filament since it was identified more than six decades ago, its electron optical performance remains unsatisfactory, especially the poor emission stability (>5% per hour), rapid current decay (20% in 10 hours), and relatively large energy spread (0.4 eV), even in an extremely high vacuum (10-9 Pa). Herein, we report a LaB6 nanoneedle structure having a sharpened tip apex with a radius of curvature of about 10 nm that is fabricated and finished using a focused ion beam (FIB) and show that it can produce a field emission electron beam meeting the application criteria with a high reduced brightness (1010 A m-2 sr-1 V-1), small energy spread (0.2 eV), and especially high emission stability (<1% fluctuation in 16 hours without decay). It can now be used practically as a next-generation field-emission point electron source.

X-ray diffraction and in situ pressurization of dentine apatite reveals nanocrystal modulus stiffening upon carbonate removal.

Bone-like materials comprise carbonated-hydroxyapatite nanocrystals (c-Ap) embedding a fibrillar collagen matrix. The mineral particles stiffen the nanocomposite by tight attachment to the protein fibrils creating a high strength and toughness material. The nanometer dimensions of c-Ap crystals make it very challenging to measure their mechanical properties. Mineral in bony tissues such as dentine contains 2~6 wt.% carbonate with possibly different elastic properties as compared with crystalline hydroxyapatite. Here we determine strain in biogenic apatite nanocrystals by directly measuring atomic deformation in pig dentine before and after removing carbonate. Transmission electron microscopy revealed the platy 3D morphology while atom probe tomography revealed carbon inside the calcium rich domains. High-energy X-ray diffraction in combination with in situ hydrostatic pressurization quantified reversible c-Ap deformations. Crystal strains differed between annealed and ashed (decarbonated) samples, following 1 or 10 h heating at 250 °C or 550 °C respectively. Measured bulk moduli (K) and a-/c-lattice deformation ratios (η) were used to generate synthetic Ksyn and ηsyn identifying the most likely elastic constants C33 and C13 for c-Ap. These were then used to calculate the nanoparticle elastic moduli. For ashed samples, we find an average E11=107 GPa and E33 =128 GPa corresponding to ~5% and ~17% stiffening of the a-/c-axes of the nanocrystals as compared with the biogenic nanocrystals in annealed samples. Ashed samples exhibit ~10% lower Poisson's ratios as compared with the 0.25~0.36 range of carbonated apatite. Carbonate in c-Ap may therefore serve for tuning local deformability within bony tissues. STATEMENT OF SIGNIFICANCE: Carbonated apatite nanoparticles, typical for bony tissues, stiffen the network of collagen fibrils. However, it is not known if the biogenic apatite mechanical (elastic) properties differ from those of geologic mineral counterparts. Indeed the tiny dimensions and variable carbonate composition may have strong effects on deformation resistance. The present study provides experimental measurements of the elastic constants which we use to estimate Young's moduli and Poisson's ratio values. Comparison between ashed and annealed dentine samples quantifies the properties of both carbonated and decarbonated apatite nanocrystals. The results reveal fundamental attributes of bony mineral and showcase the additive advantages of combining X-ray diffraction with in situ hydrostatic compression, backed by atom probe and transmission electron microscopy tomography.

A controllable and efficient method for the fabrication of a single HfC nanowire field-emission point electron source aided by low keV FIB milling.

A single hafnium carbide (HfC) nanowire field-induced electron emitter with a sharp tip apex is fabricated by Pt deposition and focused ion beam (FIB) milling. The structure of the electron emitter is characterized by scanning transmission electron microscopy (STEM) and atom probe tomography (APT). The HfC nanowire is single-crystalline with a thin oxide layer on its tip surface. The field emission properties are determined by using both in situ transmission electron microscopy (TEM) and a field-emission probe in a high-vacuum chamber. A high current of 173 nA was obtained at a low extraction voltage of 631 V with an emission gap of 5 mm. The emission current is stable at 60 nA for 100 min with a fluctuation of 0.7%. The deduced work function was 3.1 eV. It is suggested that the implanted Ga ions and the oxide layer induce more downward dipoles that are beneficial for lowering the work function and creating a stable surface. When the low keV FIB processing is applied, it takes within 30 minutes to finish a HfC nanowire emitter, establishing an efficient procedure for the preparation of nanowire emitters. These results provide a controllable and fast production method for the fabrication of single nanowire field-emission point electron sources.

The spin Hall effect of Bi-Sb alloys driven by thermally excited Dirac-like electrons.

We have studied the charge to spin conversion in Bi1-x Sb x /CoFeB heterostructures. The spin Hall conductivity (SHC) of the sputter-deposited heterostructures exhibits a high plateau at Bi-rich compositions, corresponding to the topological insulator phase, followed by a decrease of SHC for Sb-richer alloys, in agreement with the calculated intrinsic spin Hall effect of Bi1-x Sb x . The SHC increases with increasing Bi1-x Sb x thickness before it saturates, indicating that it is the bulk of the alloy that predominantly contributes to the generation of spin current; the topological surface states, if present, play little role. Unexpectedly, the SHC is found to increase with increasing temperature, following the trend of carrier density. These results suggest that the large SHC at room temperature, with a spin Hall efficiency exceeding 1 and an extremely large spin current mobility, is due to increased number of thermally excited Dirac-like electrons in the L valley of the narrow gap Bi1-x Sb x alloy.

Predictive Materials Design of Magnetic Random-Access Memory Based on Nanoscale Atomic Structure and Element Distribution.

Magnetic tunnel junctions (MTJs) capable of electrical read and write operations have emerged as a canonical building block for nonvolatile memory and logic. However, the cause of the widespread device properties found experimentally in various MTJ stacks, including tunneling magnetoresistance (TMR), perpendicular magnetic anisotropy (PMA), and voltage-controlled magnetic anisotropy (VCMA), remains elusive. Here, using high-resolution transmission electron microscopy and energy-dispersive X-ray spectroscopy, we found that the MTJ crystallization quality, boron diffusion out of the CoFeB fixed layer, and minimal oxidation of the fixed layer correlate with the TMR. As with the CoFeB free layer, seed layer diffusion into the free layer/MgO interface is negatively correlated with the interfacial PMA, whereas the metal-oxides concentrations in the free layer correlate with the VCMA. Combined with formation enthalpy and thermal diffusion analysis that can explain the evolution of element distribution from MTJ stack designs and annealing temperatures, we further established a predictive materials design framework to guide the complex design space explorations for high-performance MTJs. On the basis of this framework, we demonstrate experimentally high PMA and VCMA values of 1.74 mJ/m2 and 115 fJ/V·m-1 with annealing stability above 400 °C.

Voltage-Controlled Magnetic Anisotropy in Fe1-xCox/Pd/MgO system.

Voltage-controlled magnetic anisotropy (VCMA) in an epitaxially grown Fe/Fe1-xCox/Pd/MgO system was investigated using spin-wave spectroscopy. The spin-wave resonant frequency linearly depended on the bias-voltage. The resonant-frequency shift increased with the Co fraction in Fe1-xCox/Pd. We achieved a VCMA of approximately 250 fJ/Vm at the Co/Pd/MgO region.