Toward Operando Structural, Chemical, and Electrochemical Analyses of Solid-State Batteries Using Correlative Secondary Ion Mass Spectrometry Imaging.

The global transition from fossil fuels to green energy underpins the need for efficient and reliable energy storage systems. Advanced analysis and characterization of battery materials is not only important to understand fundamental battery properties but also crucial for their continued development. A deep understanding of these systems is often difficult to obtain through only pre- and/or post-mortem analyses, with the full complexity of a battery being hidden in its operational state. Thus, we have developed an operando methodology to analyze solid-state batteries (SSBs) structurally as well as chemically before, during, and after cycling. The approach is based on a specially designed sample holder, which enables a variety of electrochemical experiments. Since the entire workflow is performed within a single focused ion beam scanning electron microscope equipped with an in-house developed magnetic sector secondary ion mass spectrometer, we are able to pause the cycling at any time, perform analysis, and then continue cycling. Microstructural analysis is performed via secondary electron imaging, and the chemical mapping is performed using the secondary ion mass spectrometer. In this proof-of-concept study, we were able to identify dendrites in a short-circuited symmetric cell and to chemically map dendritic structures. While this methodology focuses on SSBs, the approach can directly be adapted to different battery systems and beyond. Our technique clearly has an advantage over many alternatives for battery analysis as no transfer of samples between instruments is needed and a correlation between the microstructure, chemical composition, and electrochemical performance is obtained directly.

Effect of Surface Roughness and Droplet Size on Solder Wetting Angles.

Reactive wetting is a process ubiquitous in modern electronic soldering processes. Nonetheless, the dependencies of reactive wetting angles on surface roughness and droplet size are not well understood but become increasingly important for reliable miniaturization of devices. In this study, advancing contact angles of the Sn(l)/Cu(s) reactive solder system are investigated and the aforementioned dependencies are evaluated. Several surface roughnesses and a large array of droplet sizes are measured. Clear size dependencies are observed for both smooth and rough substrates, yet interestingly, the trends are inverted. This inversion of the size dependence of the wetting angle is discussed on the basis of the triple line pinning phenomenon, Wenzel's wetting model, and the consumption of Sn by a solder reaction. Quantitative models are proposed, with which size dependencies on rough and smooth surfaces can be better understood. Triple line pinning barrier energies are calculated. Larger pinning barriers are determined for rougher substrates.

Nanoscale analysis of frozen honey by atom probe tomography.

Three-dimensional reconstruction of the analysed volume is one of the main goals of atom probe tomography (APT) and can deliver nearly atomic resolution (~ 0.2 nm spatial resolution) and chemical information with a mass sensitivity down to the ppm range. Extending this technique to frozen biological systems would have an enormous impact on the structural analysis of biomolecules. In previous works, we have shown that it is possible to measure frozen liquids with APT. In this paper, we demonstrate the ability of APT to trace nanoscale precipitation in frozen natural honey. While the mass signals of the common sugar fragments CxHy and CxOyHz overlap with (H2O)nH from water, we achieved correct stoichiometric values via different interpretation approaches for the peaks and thus determined the water content reliably. Next, we use honey to investigate the spatial resolution capabilities as a step toward the measurement of biological molecules in solution in 3D with sub-nanometer resolution. This may take analytical techniques to a new level, since methods of chemical characterization for cryogenic samples, especially biological samples, are still limited.

Understanding the Underlying Field Evaporation Mechanism of Pure Water Tips in High Electrical Fields.

We investigated the field evaporation process of frozen water in atom probe tomography (APT) by density functional simulations. In previous experiments, a strong tailing effect was observed for peaks caused by the molecular structure (H2O)nH+, in contrast to other peaks. In purely field-induced and thermally assisted evaporation simulations, we found that chains of protonated water molecules were pulled out of the dielectric surface by up to 6 Å, which are stable over a wide range of field strengths. Therefore, the resulting water clusters experience only part of the acceleration after evaporation compared to molecules evaporating directly from the surface and, thus, exhibit an energy deficit, which explains the tailing effect. Our simulations provide new insight into the complex evaporation behavior of water in high electrical fields and reveal possibilities for adapting the existing reconstruction algorithms.

A Modular Atom Probe Concept: Design, Operational Aspects, and Performance of an Integrated APT-FIB/SEM Solution.

Atomic probe tomography (APT) is able to generate three-dimensional chemical maps in atomic resolution. The required instruments for APT have evolved over the last 20 years from an experimental to an established method of materials analysis. Here, we describe the realization of a new modular instrument concept that allows the direct attachment of APT to a dual-beam SEM microscope with the main achievement of fast and direct sample transfer and high flexibility in chamber and component configuration. New operational modes are enabled regarding sample geometry, alignment of tips, and the microelectrode. The instrument is optimized to handle cryo-samples at all stages of preparation and storage. It comes with its own software for evaluation and reconstruction. The performance in terms of mass resolution, aperture angle, and detection efficiency is demonstrated with a few application examples.

Status and Direction of Atom Probe Analysis of Frozen Liquids.

Imaging of liquids and cryogenic biological materials by electron microscopy has been recently enabled by innovative approaches for specimen preparation and the fast development of optimized instruments for cryo-enabled electron microscopy (cryo-EM). Yet, cryo-EM typically lacks advanced analytical capabilities, in particular for light elements. With the development of protocols for frozen wet specimen preparation, atom probe tomography (APT) could advantageously complement insights gained by cryo-EM. Here, we report on different approaches that have been recently proposed to enable the analysis of relatively large volumes of frozen liquids from either a flat substrate or the fractured surface of a wire. Both allowed for analyzing water ice layers which are several micrometers thick consisting of pure water, pure heavy water, and aqueous solutions. We discuss the merits of both approaches and prospects for further developments in this area. Preliminary results raise numerous questions, in part concerning the physics underpinning field evaporation. We discuss these aspects and lay out some of the challenges regarding the APT analysis of frozen liquids.

Slow-Moving Phase Boundary in Li4/3+ x Ti5/3 O4.

Lithium titanate is one of the most promising anode materials for high-power demands but such applications desire a complete understanding of the kinetics of lithium transport. The poor diffusivity of lithium in the completely lithiated and delithiated (pseudo spinel) phases challenges to explain the high-rate performance. This study aims at clearing the kinetics of lithium transport using an innovative technique that employs optical microscopy in a constrained region of sputter-deposited thin-film samples. It enables the in situ observation of the transport of lithium through the electrode. Furthermore, with a thermostatically controlled cell, the Arrhenius-like temperature dependence is revealed. The quantitative findings demonstrate that indeed the end phases have poor diffusivity which is, however, accelerated at intermediate Li concentrations in the spinel structured Li4/3+ δ Ti5/3 O4 phase. Surprisingly, the slow migration of the phase boundary hinders the formation of the Li-rich (rock-salt) phase in the initial stages. Such kinetic control by the phase boundary stands in obvious contrast to a prior (theoretical) study postulating almost "liquid" behavior of the interface. Only after the Li diffusion into the Li-poor (spinel) phase has faded, when approaching the solubility limit, the further growth of the rock-salt phase becomes diffusion controlled.

Atom Probe Study of the Miscibility Gap in CuNi Thin Films and Microstructure Development.

The unclear miscibility of CuNi alloys was investigated with atom probe tomography (APT). Multilayered thin film samples were prepared by ion beam sputtering (IBS) and focused ion beam (FIB) shaping. Long-term isothermal annealing treatments in a UHV furnace were conducted at temperatures of 573, 623, and 673 K to investigate the mixing process. The effective interdiffusion coefficient of the nanocrystalline microstructure (including defect diffusion) was determined to be Deff = 1.86 × 10−10 m2/s × exp(−164 kJ/mol/RT) by fitting periodic composition profiles through a Fourier series. In nonequilibrium states, microstructural defects like grain boundaries and precipitates were observed. While at the two higher temperatures total mixing is observed, a clear experimental evidence is found for a miscibility gap at 573 K with the boundary concentrations of 26 and 66 at%. These two compositions are used in a subregular solution model to reconstruct the phase miscibility gap. So, the critical temperature TC of the miscibility gap is found to be 608 K at a concentration of 45 at% Ni.

Atom Probe Study of 1-Octadecanethiol Self-Assembled Monolayers on Platinum (111) and (200) Surfaces.

Atom probe tomography measurements of self-assembled monolayers of 1-octadecanethiol on platinum tips were performed and their fragmentation behavior under the influence of different laser powers was investigated. The carbon backbone evaporates in the form of small hydrocarbon fragments consisting of one to four carbon atoms, while sulfur evaporates exclusively as single ions. The carbon molecules evaporate at very low fields of 5.9 V/nm, while S requires a considerably higher evaporation field of 23.4 V/nm. With increasing laser power, a weak, but noticeable trend toward larger fragment sizes is observed. No hydrocarbon fragments containing S are detected, indicating that a strong S­Pt bond has formed. The observed surface coverage of S fits well with literature values and is higher for (111)-oriented samples than for (200).

Quantitative Distinction between Noble Metals Located in Mesopores from Those on the External Surface.

We compare three methods for quantitatively distinguishing the location of noble metal (NM) particles in mesopores from those found on the external support surface. MCM-41 and SBA-15 with NM located in mesopores or on the external surface were prepared and characterized by TEM. 31 P MAS NMR spectroscopy was used to quantify arylphosphines in complexes with NM. Phosphine/NM ratios drop from 2.0 to 0.2 when increasing the probe diameter from 1.08 to 1.54 nm. The reaction between NM and triphenylphosphine (TPP) within 3.0 nm MCM-41 pores takes due to confinement effects multiple weeks. In contrast, external NM react with TPP instantly. A promising method is filling the pores by using the pore volume impregnation technique with tetraethylorthosilicate (TEOS). TPP loading revealed that 66 % of NMs are located on the external surface of MCM-41. The pore filling method can be used in association with any probe molecule, also for the quantification of acid sites.

Elastic Behavior of Nb2O5/Al2O3 Core-Shell Nanowires in Terms of Short-Range-Order Structures.

Single-crystalline niobium pentoxide nanowires (NWs) of length 10-15 µm and diameter 100-200 nm are synthesized by thermal oxidation of niobium substrates in a mild vacuum (3-10 mbar). Amorphous Al2O3 shells of varying thicknesses (10, 30, 40, and 50 nm) are deposited on top of the wires using atomic layer deposition. Bending tests of the uncoated Nb2O5 NWs and the Nb2O5/Al2O3 core-shell NWs are carried out inside a scanning electron microscope using a micromanipulator with a force measurement tip. The experimental deflection curves are modeled with Euler-Bernoulli (E-B) beam theory, and the Young's modulus is manipulated to determine the best fit. The Nb2O5 NWs with no shell are determined to have a Young's modulus of 67 ± 10 GPa, which agrees with the published data on Nb2O5 thin films. For core-shell NWs, only small deflections of the wires with 10 and 30 nm thick shells can be fitted with the E-B model when utilizing constant Young's modulus values of 67 GPa for the Nb2O5 core and about 160 GPa for the Al2O3 shell. When allowing for a change in the Young's modulus of the Al2O3 shell, the Young's modulus is determined to be at 120 ± 10 GPa for 10 nm and 145 ± 12 GPa for 30 nm at the highest applied load. For thicknesses of 40 nm and 50 nm, we observed a reduced but constant 120 ± 11 and 111 ± 10 GPa, respectively. Such behavior may result from structural disordering of the amorphous Al2O3 through reducing fractions of the densely packed polyhedra, while the fractions of the loosely packed polyhedra increase as a result of the increasing strain or the fabrication process. The increased disorder is associated with increased average interatomic spacing. Thus, the atomic bonding force and also the Young's modulus decrease.

Optimizing the plasma oxidation of aluminum gate electrodes for ultrathin gate oxides in organic transistors.

A critical requirement for the application of organic thin-film transistors (TFTs) in mobile or wearable applications is low-voltage operation, which can be achieved by employing ultrathin, high-capacitance gate dielectrics. One option is a hybrid dielectric composed of a thin film of aluminum oxide and a molecular self-assembled monolayer in which the aluminum oxide is formed by exposure of the surface of the aluminum gate electrode to a radio-frequency-generated oxygen plasma. This work investigates how the properties of such dielectrics are affected by the plasma power and the duration of the plasma exposure. For various combinations of plasma power and duration, the thickness and the capacitance of the dielectrics, the leakage-current density through the dielectrics, and the current-voltage characteristics of organic TFTs in which these dielectrics serve as the gate insulator have been evaluated. The influence of the plasma parameters on the surface properties of the dielectrics, the thin-film morphology of the vacuum-deposited organic-semiconductor films, and the resulting TFT characteristics has also been investigated.

Compensating Local Magnifications in Atom Probe Tomography for Accurate Analysis of Nano-Sized Precipitates.

Local magnification artifacts in atom probe tomography (APT) caused by multiphase materials with heterogeneous evaporation behavior are a well-known problem. In particular, the analysis of the exact size, shape, and composition of small precipitates is, therefore, not trivial. We performed numerical simulations of APT measurements to predict the reconstructed morphology of precipitates with contrasting evaporation thresholds. Based on a statistical approach that avoids coarse graining, the simulated data are evaluated to develop a model for the calculation of the original size of the precipitates. The model is tested on experimental APT data of precipitates with a higher and lower evaporation field in a ferritic alloy. Accurate sizes, proven by a complementary investigation by transmission electron microscopy, are obtained. We show further, how the size information can be used to obtain compositional information of the smallest precipitates and present a new methodology to determine a correct in-depth scaling of the APT reconstruction in case no complementary geometric information about the specimen exists or if no lattice planes are visible in the reconstruction.

Evaporation and Fragmentation of Organic Molecules in Strong Electric Fields Simulated with DFT.

Atom probe tomography allows us to measure the three-dimensional composition of materials with up to atomic resolution by evaporating the material using high electric fields. Initially developed for metals, it is increasingly used for covalently bound structures. To aid the interpretation of the obtained fragmentation pattern, we modeled the fragmentation and desorption of self-assembled monolayers of thiolate molecules on a gold surface in strong electrostatic fields using density functional theory. We used a cluster model and a periodic model of amino-undecanethiolate, NH2(CH2)11S, and fluoro-decanethiolate, CF3(CF2)7(CH2)2S. In the former molecule, the fragment CH2NH2+ was found to evaporate at fields of 5.4-7.7 V/nm. It was followed by different hydrocarbon fragments. Fluoro-decanethiolate evaporates CF3+ at fields of 5.7-6.7 V/nm in the cluster model and at 15.4-23.1 V/nm in the periodic model, followed by CF2+ and C2F42+. Detailed analysis of the electronic structure during the evaporation process revealed a stepwise accumulation of the charge in the head groups exposed to the strongest fields, followed by dissociation of covalent bonds. These observations will facilitate the analysis of atom probe experiments of covalently bound structures.

Miniaturization, Triple-Line Effects, and Reactive Wetting of Microsolder Interfaces.

While reactive microsolder joints are of ubiquitous importance in modern electronics, the effects of joint miniaturization on wetting behavior remain largely unexplored. We elucidate this fundamental question of scalability by investigating the wettability of eutectic SnPb solder on Cu and Ni-electrodeposited metallization strips of varying widths. Contact angles are presented in dependence of the metallization width which is varied from 3 mm down to ∼100 µm. The measured angles clearly increase with decreasing metallization width. Based on the measurements and by modifying Young's equation, it is shown that the behavior of the wetting angle can be quantitatively understood with an "effective" triple-line energy of ϵt = (753 ± 31) × 10-9J/m for SnPb on Cu. The interpretation of this energy term is discussed in relation to the forming intermetallic phase and the ensuing surface roughness. A remarkable similarity between the experimentally observed size dependence and the crossed-groove perturbation model of Huh and Mason demonstrates that the rough intermetallic phase induces wetting hysteresis such that it is quantitatively well described by an effective triple-line energy.

Electrochromic Behavior and Phase Transformation in Li4+xTi5O12 upon Lithium-Ion Deintercalation/Intercalation.

The impact of phase transformation from spinel-structured Li4Ti5O12 to rocksalt-type Li7Ti5O12 on the electrochromic properties of the material is studied. Thin films of Li4Ti5O12 are deposited on platinum-coated substrates using radio-frequency-ion beam sputtering. In situ and ex situ optical spectroscopy (in reflectance geometry) is performed along with electrochemical characterization. In situ measurements demonstrate the reversible electrochromic behavior of the deposited thin films and the effect of the change of lithium content on the reflectance spectrum. Ex situ measurements quantify the optical constants of thin films for different charge states by modeling the reflectance spectrum with a Clausius-Mossotti relation. The model reveals the presence of one or two dominant resonant frequencies in the case of Li4Ti5O12 or Li7Ti5O12, respectively, in the UV/visible/NIR region of light. The single strong resonance in the case of Li4Ti5O12 is assigned to transition from O 2p to Ti t2g, that is, across the band gap, whereas for the Li7Ti5O12 phase, the two resonances correspond to the electronic transitions from O 2p to empty Ti t2g and from filled Ti t2g to empty Ti eg. The concentration dependence of the derived dielectric constants points out a fast lithium ion transport through the grain boundaries, thereby segregating a conductive lithium-rich phase at the grain boundaries. This increases the electronic conductivity of the thin films in the initial stages of intercalation and explains the debated mechanism of the fast discharge/charge capability of Li4Ti5O12 electrodes.

Extracting the shape of nanometric field emitters.

The high resolution nanoanalysis by atom probe tomography is based on needle-shaped samples that represent nanometric field emitters with typical curvature radii of 50 nm. After field desorption and detection of a large set of atoms, the sample volume has to be numerically reconstructed. Conventionally, this reconstruction is performed with the assumption of a hemispherical apex. This established practice can lead to serious distortions of the tomography. In this work, we demonstrate how the real shape of the emitter can be extracted from the event density on the 2D detector setup. Except for convexity, no other restriction is imposed on the shape. The required mathematics is derived and the method is demonstrated with numerically simulated and experimental data sets of complex tip shapes. The computational effort of the method is also suitable to handle data sets of a few hundred million atoms.

High capacity rock salt type Li2MnO3-δ thin film battery electrodes.

Recent investigations of layered, rock salt and spinel-type manganese oxides in composite powder electrodes revealed the mutual stabilization of the Li-Mn-O compounds during electrochemical cycling. A novel approach of depositing such complex compounds as an active cathode material in thin-film battery electrodes is demonstrated in this work. It shows the maximum capacity of 226 mA h g-1 which is superior in comparison to that of commercial LiMn2O4 powder as well as thin films. Reactive ion beam sputtering is used to deposit films of a Li2MnO3-δ composition. The method allows for tailoring of the active layer's crystal structure by controlling the oxygen partial pressure during deposition. Electron diffractometry reveals the presence of layered monoclinic and defect rock salt structures, the former transforms during cycling and results in thin films with extraordinary electrochemical properties. X-ray photoelectron spectroscopy shows that a large amount of disorder on the cation sub-lattices has been incorporated in the structure, which is beneficial for lithium migration and cycle stability.

Beyond linearity: bent crystalline copper nanowires in the small-to-moderate regime.

Several models can describe the nonlinear response of 1D objects to bending under a concentrated load. Successive stages consisting of geometrical and, additionally, mechanical non-linearity can be identified in moderately large extensions. We provide an explicit bending moment function with terms accounting for the linearity (Euler-Bernoulli), quasi-linearity, geometrical and finally, mechanical non-linearity as global features of a moderately large elastic deformation. We apply our method, also suitable for other metals, to the experimental data of Cu nanowires (NWs) with an aspect ratio of about 16 under different concentrated loadings. The spatial distribution of strain-hardening/softening along the wire or through the cross-section is also demonstrated. As a constitutive parameter, the strain-dependent stretch modulus represents, undoubtedly, changes in the material properties as the deformation progresses. At the highest load, the Green-Lagrange strain reaches a 12.5% extension with a corresponding ultra-high strength of about 7.45 GPa at the most strained volume still in the elastic regime. The determined stretch modulus indicates a significantly lower elastic response with an approximated Young's modulus (E ≅ 65 GPa) and a third-order elastic constant, C 111 ≅ -350 GPa. Surprisingly, these constants suggest a 25-35% of that of the bulk counterparts. Ultimately, the method not only provides a quantitative description of the bent Cu NWs, but also indicates the robustness of the theory of nonlinear elasticity.