Weld-free mounting of lamellae for electrical biasing operando TEM.

Recent advances in microelectromechanical systems (MEMS)-based substrates and sample holders for in situ transmission electron microscopy (TEM) are currently enabling exciting new opportunities for the nanoscale investigation of materials and devices. The ability to perform electrical testing while simultaneously capturing the wide spectrum of signals detectable in a TEM, including structural, chemical, and even electronic contrast, represents a significant milestone in the realm of nanoelectronics. In situ studies hold particular promise for the development of Metal-Insulator-Metal (MIM) devices for use in next-generation computing. However, achieving successful device operation in the TEM typically necessitates meticulous sample preparation involving focused ion beam (FIB) systems. Conducting contamination introduced during the FIB thinning process and subsequent attachment of the sample onto a MEMS-based chip remains a formidable challenge. This article delineates an improved FIB-based sample preparation methodology that results in good electrical connectivity and operational functionality across various MIM devices. To exemplify the efficacy of the sample preparation technique, we demonstrate preparation of a clean cross section extracted from a Au/Pt/BaSrTiO3/SrMoO3 tunable capacitor (varactor). The FIB-prepared TEM lamella mounted on a MEMS-based chip showed current levels in the tens of picoamperes range at 0.1 V. Furthermore, the electric response and current density of the TEM lamella device closely align with macro-scale devices. These samples exhibit comparable current densities to their macro-sized counterparts thus validating the sample preparation process and confirming device connectivity. The simultaneous operation and TEM characterization of electronic devices enabled by this process enables direct correlation between device structure and function, which could prove pivotal in the development of new MIM systems.

Impact of Strain Engineering on Antiferroelectricity in NaNbO3 Thin Films.

Thin films of NaNbO3 were grown on various substrates to investigate the effect of epitaxial strain on their structural and electrical properties. Reciprocal space maps confirmed the presence of epitaxial strain from +0.8% to -1.2%. A bulk-like antipolar ground state was detected via structural characterization for NaNbO3 thin films grown with strains ranging from a compressive strain of 0.8% to small tensile strains, up to -0.2%. For larger tensile strains on the other hand, no indication of antipolar displacements can be detected, even beyond the relaxation of the film at larger thicknesses. Electrical characterization revealed a ferroelectric hysteresis loop for thin films under a strain of +0.8% to -0.2%, while the films under larger tensile strain showed no out-of-plane polarization component. However, the films with a compressive strain of 0.8% present a saturation polarization of up to 55 µC·cm-2, more than twice as large for films grown under conditions with small strain, which is also larger than the highest values reported for bulk materials. Our results indicate the high potential for strain engineering in antiferroelectric materials, as the antipolar ground state could be retained with compressive strain. The observed enhancement of the saturation polarization by strain allows for substantial increase of energy density of the capacitors with antiferroelectric materials.

Tailoring Optical Properties in Transparent Highly Conducting Perovskites by Cationic Substitution.

SrMoO3 , SrNbO3 , and SrVO3 are remarkable highly conducting d1 (V, Nb) or d2 (Mo) perovskite metals with an intrinsically high transparency in the visible. A key scientific question is how the optical properties of these materials can be manipulated to make them suitable for applications as transparent electrodes and in plasmonics. Here, it is shown how 3d/4d cationic substitution in perovskites tailors the relevant materials parameters, i.e., optical transition energy and plasma frequency. With the example of the solid-state solution SrV1- x Mox O3 , it is shown that the absorption and reflection edges can be shifted to the edges of the visible light spectrum, resulting in a material that has the potential to outperform indium tin oxide (ITO) due to its extremely low sheet resistance. An optimum for x = 0.5, where a resistivity of 32 µΩ cm (≈12 Ω sq-1 ) is paired with a transmittance above 84% in the whole visible spectrum is found. Quantitative comparison between experiments and electronic structure calculations show that the shift of the plasma frequency is governed by the interplay of d-band filling and electronic correlations. This study advances the knowledge about the peculiar class of highly conducting perovskites toward sustainable transparent conductors and emergent plasmonics.

Epitaxy Induced Highly Ordered Sm2Co17-SmCo5 Nanoscale Thin-Film Magnets.

Utilizing the molecular beam epitaxy technique, a nanoscale thin-film magnet of c-axis-oriented Sm2Co17 and SmCo5 phases is stabilized. While typically in the prototype Sm(Co, Fe, Cu, Zr)7.5-8 pinning-type magnets, an ordered nanocomposite is formed by complex thermal treatments, here, a one-step approach to induce controlled phase separation in a binary Sm-Co system is shown. A detailed analysis of the extended X-ray absorption fine structure confirmed the coexistence of Sm2Co17 and SmCo5 phases with 65% Sm2Co17 and 35% SmCo5. The SmCo5 phase is stabilized directly on an Al2O3 substrate up to a thickness of 4 nm followed by a matrix of Sm2Co17 intermixed with SmCo5. This structural transition takes place through coherent atomic layers, as revealed by scanning transmission electron microscopy. Highly crystalline growth of well-aligned Sm2Co17 and SmCo5 phases with coherent interfaces result in strong exchange interaction, leading to enhanced magnetization and magnetic coupling. The arrangement of Sm2Co17 and SmCo5 phases at the nanoscale is reflected in the observed magnetocrystalline anisotropy and coercivity. As next-generation permanent magnets require designing of materials at an atomic level, this work enhances our understanding of self-assembling and functioning of nanophased magnets and contributes to establishing new concepts to engineer the microstructure for beyond state-of-the-art magnets.

All-Oxide Varactor Electromechanical Properties Extracted by Highly Accurate Modeling Over a Broad Frequency and Electric Bias Range.

Since the dielectric permittivity of ferroelectric materials depends on the electric field, they allow designing switchable and continuously tunable devices for adaptive microwave front ends. Part of the ongoing research is the field of all-oxide devices, where epitaxial oxide conductors are used instead of polycrystalline metal electrodes, leading to epitaxial ferroelectric layers and resulting in high device performance. In particular, they allow engineering the acoustic properties separated from the electric ones due to the structural similarity between the dielectric and conducting oxide films. Two major results are reported in this work. First, a highly accurate model for the microwave impedance of ferroelectric varactors is derived that tracks the superposition of induced piezoelectricity and field extrusion into the substrate caused by thin electrodes. In difference to previous works, this model covers both a wide frequency and biasing range up to 12 GHz and 100 V/ [Formula: see text]. Second, the high model accuracy enables the determination of all relevant electric and mechanic properties based on a mere microwave characterization. This approach will be especially valuable when independent measurements of mechanical properties of the thin-film materials are impeded by a high integration of the devices. Though derived for all-oxide varactors, the presented model can as well be adapted for thin-film bulk acoustic wave resonators (FBARs) and varactors with conventional metal electrodes when eventual dead layers at the interface are modeled correctly.

Synthesis and characterisation of fluorinated epitaxial films of BaFeO2F: tailoring magnetic anisotropy via a lowering of tetragonal distortion.

In this article, we report on the synthesis and characterisation of fluorinated epitaxial films of BaFeO2F via low-temperature fluorination of thin films of BaFeO2.5+d grown by pulsed laser deposition. Diffraction measurements show that fluoride incorporation only results in a contraction of the film perpendicular to the film surface, where clamping by the substrate is prohibitive for strong in-plane changes. The fluorinated films were found to be homogenous regarding the fluorine content over the whole film thickness, and can be considered as single crystal equivalents to the bulk phase BaFeO2F. Surprisingly, fluorination resulted in the change of the tetragonal distortion to a nearly cubic symmetry, which results in a lowering of anisotropic orientation of the magnetic moments of the antiferromagnetically ordered compound, confirmed by Mössbauer spectroscopy and magnetic studies.

In-operando photoelectron spectroscopy for batteries: Set-up using pristine thin film cathode and first results on NaxCoO2.

A model all-solid-state battery cell with a thin film NaxCoO2 cathode was assembled under ultra-high vacuum conditions and cycled inside the vacuum chamber, using a dedicated sample holder. We present in-operando x-ray photoelectron spectroscopy measurements of a NaxCoO2 cathode at different charging states. During battery operation, the change in sodium content, the change in cobalt oxidation state, and the evolution of the O1s and VB emissions could be monitored. Comparison with a conventional post-mortem analysis technique showed that the new measurement technique produces comparable results regarding the oxidation state of the transition metal, but sodium and oxygen results show differences due to cathode/electrolyte interfacial reactions for conventional analysis. By using surface layer-free samples in the presented techniques, we could circumvent such reactions and obtain reliable spectra for the pure bulk-like active cathode material.