Chemo-mechanical failure mechanisms of the silicon anode in solid-state batteries.

Silicon is a promising anode material due to its high theoretical specific capacity, low lithiation potential and low lithium dendrite risk. Yet, the electrochemical performance of silicon anodes in solid-state batteries is still poor (for example, low actual specific capacity and fast capacity decay), hindering practical applications. Here the chemo-mechanical failure mechanisms of composite Si/Li6PS5Cl and solid-electrolyte-free silicon anodes are revealed by combining structural and chemical characterizations with theoretical simulations. The growth of the solid electrolyte interphase at the Si|Li6PS5Cl interface causes severe resistance increase in composite anodes, explaining their fast capacity decay. Solid-electrolyte-free silicon anodes show sufficient ionic and electronic conductivities, enabling a high specific capacity. However, microscale void formation during delithiation causes larger mechanical stress at the two-dimensional interfaces of these anodes than in composite anodes. Understanding these chemo-mechanical failure mechanisms of different anode architectures and the role of interphase formation helps to provide guidelines for the design of improved electrode materials.

Synthesis of 2D Gallium Sulfide with Ultraviolet Emission by MOCVD.

Two-dimensional (2D) materials exhibit the potential to transform semiconductor technology. Their rich compositional and stacking varieties allow tailoring materials' properties toward device applications. Monolayer to multilayer gallium sulfide (GaS) with its ultraviolet band gap, which can be tuned by varying the layer number, holds promise for solar-blind photodiodes and light-emitting diodes as applications. However, achieving commercial viability requires wafer-scale integration, contrasting with established, limited methods such as mechanical exfoliation. Here the one-step synthesis of 2D GaS is introduced via metal-organic chemical vapor deposition on sapphire substrates. The pulsed-mode deposition of industry-standard precursors promotes 2D growth by inhibiting the vapor phase and on-surface pre-reactions. The interface chemistry with the growth of a Ga adlayer that results in an epitaxial relationship is revealed. Probing structure and composition validate thin-film quality and 2D nature with the possibility to control the thickness by the number of GaS pulses. The results highlight the adaptability of established growth facilities for producing atomically thin to multilayered 2D semiconductor materials, paving the way for practical applications.

Insights into molecular cluster materials with adamantane-like core structures by considering dimer interactions.

A class of adamantane-like molecular materials attracts attention because they exhibit an extreme non-linear optical response and emit a broad white-light spectrum after illumination with a continuous-wave infrared laser source. According to recent studies, not only the nature of the cluster molecules, but also the macroscopic structure of the materials determines their non-linear optical properties. Here we present a systematic study of cluster dimers of the compounds AdR4 and [(RT)4 S6 ] (T = Si, Ge, Sn) with R = methyl, phenyl or 1-naphthyl to gain fundamental knowledge about the interactions in the materials. For all compounds, a similar type of dimer structures with a staggered arrangement of substituents was determined as the energetically most favorable configuration. The binding energy between the dimers, determined by including London dispersion interactions, increases with the size of the core and the substituents. The cluster interactions can be classified as substituent-substituent-dominated (small cores, large substituents) or core-core-dominated (large cores, small substituents). Among various possible dimer conformers, those with small core-core distances are energetically preferred. Trimer and tetramer clusters display similar trends regarding the minimal core-core distances and binding energies. The much lower energy barrier determined for the rotation of substituents as compared to the rotation of the cluster dimers past each other indicates that the rotation of substituents more easily leads to different conformers in the material. Thus, understanding the interaction of the cluster dimers allows an initial assessment of the interactions in the materials.

Probing the Ni(OH)2 Precursor for LiNiO2 at the Atomic Scale: Insights into the Origin of Structural Defect in a Layered Cathode Active Material.

In lithium ion batteries (LIBs), the layered cathode materials of composition LiNi1- x - y Cox Mny O2  are critical for achieving high energy densities. A high nickel content (>80%) provides an attractive balance between high energy density, long lifetime, and low cost. Consequently, Ni-rich layered oxides cathode active materials (CAMs) are in high demand, and the importance of LiNiO2 (LNO) as limiting case, is hence paramount. However, achieving perfect stoichiometry is a challenge resulting in various structural issues, which successively impact physicochemical properties and result in the capacity fade of LIBs. To better understand defect formation in LNO, the role of the Ni(OH)2  precursor morphology in the synthesis of LNO requires in-depth investigation. By employing aberration-corrected scanning transmission electron microscopy, electron energy loss spectroscopy, and precession electron diffraction, a direct observation of defects in the Ni(OH)2  precursor preparedis reported and the ex situ structural evolution from the precursor to the end product is monitored. During synthesis, the layered Ni(OH)2  structure transforms to partially lithiated (non-layered) NiO and finally to layered LNO. The results suggest that the defects observed in commercially relevant CAMs originate to a large extent from the precursors, hence care must be taken in tuning the co-precipitation parameters to synthesize defect-free Ni-rich layered oxides CAMs.

Terahertz radiation from propagating acoustic phonons based on deformation potential coupling.

We report on new THz electromagnetic emission mechanism from deformational coupling of acoustic (AC) phonons with electrons in the propagation medium of non-polar Si. The epicenters of the AC phonon pulses are the surface and interface of a GaP transducer layer whose thickness (d) is varied in nanoscale from 16 to 45 nm. The propagating AC pulses locally modulate the bandgap, which in turn generates a train of electric field pulses, inducing an abrupt drift motion at the depletion edge of Si. The fairly time-delayed THz bursts, centered at different times (t1T H z, t2T H z, and t3T H z), are concurrently emitted only when a series of AC pulses reach the point of the depletion edge of Si, even without any piezoelectricity. The analysis on the observed peak emission amplitudes is consistent with calculations based on the combined effects of mobile charge carrier density and AC-phonon-induced local deformation, which recapitulates the role of deformational potential coupling in THz wave emission in a formulatively distinct manner from piezoelectric counterpart.

Quantitative Characterization of Nanometer-Scale Electric Fields via Momentum-Resolved STEM.

Most of today's electronic devices, like solar cells and batteries, are based on nanometer-scale built-in electric fields. Accordingly, characterization of fields at such small scales has become an important task in the optimization of these devices. In this study, with GaAs-based p-n junctions as the example, key characteristics such as doping concentrations, polarity, and the depletion width are derived quantitatively using four-dimensional scanning transmission electron microscopy (4DSTEM). The built-in electric fields are determined by the shift they introduce to the center-of-mass of electron diffraction patterns at subnanometer spatial resolution. The method is applied successfully to characterize two p-n junctions with different doping concentrations. This highlights the potential of this method to directly visualize intentional or unintentional nanoscale electric fields in real-life devices, e.g., batteries, transistors, and solar cells.

Optimized atomic layer deposition of homogeneous, conductive Al2O3 coatings for high-nickel NCM containing ready-to-use electrodes.

Atomic layer deposition (ALD) derived ultrathin conformal Al2O3 coating has been identified as an effective strategy for enhancing the electrochemical performance of Ni-rich LiNixCoyMnzO2 (NCM; 0 ≤x, y, z < 1) based cathode active materials (CAM) in Li-ion batteries. However, there is still a need to better understand the beneficial effect of ALD derived surface coatings on the performance of NCM based composite cathodes. In this work, we applied and optimized a low-temperature ALD derived Al2O3 coating on a series of Ni-rich NCM-based (NCM622, NCM71.51.5 and NCM811) ready-to-use composite cathodes and investigated the effect of coating on the surface conductivity of the electrode as well as its electrochemical performance. A highly uniform and conformal coating was successfully achieved on all three different cathode compositions under the same ALD deposition conditions. All the coated cathodes were found to exhibit an improved electrochemical performance during long-term cycling under moderate cycling conditions. The improvement in the electrochemical performance after Al2O3 coating is attributed to the suppression of parasitic side reactions between the electrode and the electrolyte during cycling. Furthermore, conductive atomic force microscopy (C-AFM) was performed on the electrode surface as a non-destructive technique to determine the difference in surface morphology and conductivity between uncoated and coated electrodes before and after cycling. C-AFM measurements on pristine cathodes before cycling allow clear separation between the conductive carbon additives and the embedded NCM secondary particles, which show an electrically insulating behavior. More importantly, the measurements reveal that the ALD-derived Al2O3 coating with an optimized thickness is thin enough to retain the original conduction properties of the coated electrodes, while thicker coating layers are insulating resulting in a worse cycling performance. After cycling, the surface conductivity of the coated electrodes is maintained, while in the case of uncoated electrodes the surface conductivity is completely suppressed confirming the formation of an insulating cathode electrolyte interface due to the parasitic side reactions. The results not only show the possibilities of C-AFM as a non-destructive evaluation of the surface properties, but also reveal that an optimized coating, which preserves the conductive properties of the electrode surface, is a crucial factor for stabilising the long-term battery performance.

Anomalous Angle-Dependent Magnetotransport Properties of Single InAs Nanowires.

We study the magnetotransport properties of single InAs nanowires grown by selective-area metal-organic vapor-phase epitaxy. The semiconducting InAs nanowires exhibit a large positive ordinary magnetoresistance effect. However, a deviation from the corresponding quadratic behavior is observed for an orientation of the applied magnetic field perpendicular to the nanowire axis. This additional contribution to the magnetoresistance can be explained by diffuse boundary scattering of free carriers in the InAs nanowire and results in a reduction of the charge carrier mobility. As a consequence, angle-dependent magnetotransport measurements reveal a highly anomalous behavior. Numerical simulations have been conducted to further investigate the effect of classical boundary scattering in the nanowires. On the basis of the numerical simulations, an empirical description is derived, which yields excellent agreement with the experimental data and allows one to quantify the contribution of boundary scattering to the magnetoresistance effect.

Formation and Structural Diversity of Organo-Functionalized Tin-Silver Selenide Clusters.

When reacting the organic functionalized tin selenide clusters [(SnR1 )3 Se4 Cl] (A, R1 =CMe2 CH2 C(O)Me) or [(SnR1 )4 Se6 ] (B) with (SiMe3 )2 Se and [Ag(PPh3 )3 Cl] at -78 °C in CH2 Cl2 , a microcrystalline intermediate (compound 1) precipitates, which was investigated by magic angle spinning (MAS) NMR spectroscopy, powder X-ray diffraction (PXRD), energy dispersive X-ray (EDX) spectroscopy, and quantum chemistry calculations, to derive information about its composition and structure. Compound 1 re-dissolves under reorganization into the organo-functionalized Ag/Sn/Se cluster compound [Ag6 (µ6 -Se)(Ag8 Se12 ){(R1 Sn)2 Se2 }6 ] (2), or the mixed-valence cluster [(AgPPh3 )2 (SnII Cl)2 Se2 {(R1 SnIV )2 Se2 }2 ] (3), depending on the presence or the exclusion of daylight, respectively. The addition of N2 H4 ⋅H2 O to a solution of 1 yields selectively [Ag7 (µ7 -Se)(Ag7 Se12 ){(R2 Sn)2 Se2 }6 ] (4, R2 =CMe2 CH2 C(N2 H2 )Me), the Ag/Sn/Se core of which is isomeric to that of 2. 2-4 were characterized by X-ray diffraction. NMR spectroscopic studies on solutions of 1 indicate the co-existence of different species.

Surface relaxation of strained Ga(P,As)/GaP heterostructures investigated by HAADF STEM.

The surfaces of thin transmission electron microscopy (TEM) specimens of strained heterostructures can relax. The resulting bending of the lattice planes significantly influences high-angle annular dark field (HAADF) measurements. We investigate the impact by evaluating the intensities measured at the atomic columns as well as their positions in high-resolution HAADF images. In addition, the consequences in the diffraction plane will be addressed by simulated position averaged convergent beam electron diffraction (PACBED) patterns. The experimental column intensities and positions acquired from a strained Ga(P,As) quantum well (QW) embedded in a in a GaP matrix agree very well with frozen phonon contrast simulations, if the surface relaxation is taken into account by finite element relaxation. Neglecting the surface relaxation the As content of the QW can be significantly underestimated. Taking the effects into account correctly, we find that the lower interface of the investigated Ga(P,As) QW is atomically abrupt whereas the upper one is smeared out.

In Situ Thermal Annealing Transmission Electron Microscopy (TEM) Investigation of III/V Semiconductor Heterostructures Using a Setup for Safe Usage of Toxic and Pyrophoric Gases.

In this study we compare two thermal annealing series of III/V semiconductor heterostructures on Si, where during the first series nitrogen is present in the in situ holder. The second, comparative, measurement is done in a tertiarybutylphosphine (TBP) environment. The sample annealed in a TBP environment shows favorable thermal stability up to 500°C compared to the unstabilized sample, which begins to degrade at less than 300°C. Evaporation of P from the material is tracked qualitatively by measuring the thickness of the sample during thermal annealing with and without stabilization. Finally, we investigate the in situ thermal annealing processes at atomic resolution. Here it is possible to study phase separation as well as the diffusion of As from a Ga(NAsP) quantum well in the surrounding GaP material during thermal annealing. To make these investigations possible we developed an extension for our in situ transmission electron microscopy setup for the safe usage of toxic and pyrophoric III/V semiconductor precursors. A commercially available gas cell and gas supply system were expanded with a gas mixing system, an appropriate toxic gas monitoring system and a gas scrubbing system. These components allow in situ studies of semiconductor growth and annealing under the purity conditions required for these materials.

Surface Chemistry of tert-Butylphosphine (TBP) on Si(001) in the Nucleation Phase of Thin-Film Growth.

We combine density functional theory calculations and scanning tunneling microscopy investigations to identify the relevant chemical species and reactions in the nucleation phase of chemical vapor deposition. tert-Butylphosphine (TBP) was deposited on a silicon substrate under conditions typical for surface functionalization and growth of semiconductor materials. On the activated hydrogen-covered surface H/Si(001) it forms a strong covalent P-Si bond without loss of the tert-butyl group. Calculations show that site preference for multiple adsorption of TBP is influenced by steric repulsion of the adsorbate's bulky substituent. STM imaging furthermore revealed an anisotropic distribution of TBP with a preference for adsorption perpendicular to the surface dimer rows. The adsorption patterns found can be understood by a mechanism invoking stabilization of surface hydrogen vacancies through electron donation by an adsorbate. The now improved understanding of nucleation in thin-film growth may help to optimize molecular precursors and experimental conditions and will ultimately lead to higher quality materials.

Preparation and Loading Process of Single Crystalline Samples into a Gas Environmental Cell Holder for In Situ Atomic Resolution Scanning Transmission Electron Microscopic Observation.

A reproducible way to transfer a single crystalline sample into a gas environmental cell holder for in situ transmission electron microscopic (TEM) analysis is shown in this study. As in situ holders have only single-tilt capability, it is necessary to prepare the sample precisely along a specific zone axis. This can be achieved by a very accurate focused ion beam lift-out preparation. We show a step-by-step procedure to prepare the sample and transfer it into the gas environmental cell. The sample material is a GaP/Ga(NAsP)/GaP multi-quantum well structure on Si. Scanning TEM observations prove that it is possible to achieve atomic resolution at very high temperatures in a nitrogen environment of 100,000 Pa.

FIB Plan View Preparation and Electron Tomography of Ga-Containing Droplets Induced by Melt-Back Etching in Si.

Melt-back etching is an effect that can occur for gallium (Ga) containing III/V semiconductors grown on Si. Since this effect influences interfaces between the two compounds and therefore the physical characteristics of the material composition, it is desirable to understand its driving forces. Therefore, we investigated Ga grown on Si (001) via metal organic chemical vapor deposition using trimethyl Ga as a precursor. As a result of the melt-back etching, Ga-containing droplets formed on the Si surface which reach into the Si wafer. The shape of these structures was analyzed by plan view investigation and cross sectional tomography in a (scanning) transmission electron microscope. For plan view preparation a focused ion beam was used to avoid damage to the Ga-containing structures, which are sensitive to the chemicals normally used during conventional plan view preparation. Combining the results of both investigation methods confirms that the Ga-containing structure within the Si exhibits a pyramid shape with facets along the Si {111} lattice planes.

Simultaneous quantification of indium and nitrogen concentration in InGaNAs using HAADF-STEM.

To unambiguously evaluate the indium and nitrogen concentrations in In(x)Ga(1-x)N(y)As(1-y), two independent sources of information must be obtained experimentally. Based on high-resolution scanning transmission electron microscopy (STEM) images taken with a high-angle annular dark-field (HAADF) detector the strain state of the InGaNAs quantum well is determined as well as its characteristic HAADF-scattering intensity. The strain state is evaluated by applying elasticity theory and the HAADF intensity is used for a comparison with multislice simulations. The combination of both allows for determination of the chemical composition where the results are in accordance with X-ray diffraction measurements, three-dimensional atom probe tomography, and further transmission electron microscopy analysis. The HAADF-STEM evaluation was used to investigate the influence of As-stabilized annealing on the InGaNAs/GaAs sample. Photoluminescence measurements show an annealing-induced blue shift of the emission wavelength. The chemical analysis precludes an elemental diffusion as origin of the energy shift--instead the results are in agreement with a model based on an annealing-induced redistribution of the atomic next-neighbor configuration.

"Depo-all-around": A novel FIB-based TEM specimen preparation technique for solid state battery composites and other loosely bound samples.

Interfacial phenomena between active cathode materials and solid electrolytes play an important role in the function of solid-state batteries. (S)TEM imaging can give valuable insight into the atomic structure and composition at the various interfaces, yet the preparation of TEM specimen by FIB (focused ion beam) is challenging for loosely bound samples like composites, as they easily break apart during conventional preparation routines. We propose a novel preparation method that uses a frame made of deposition layers from the FIB's gas injection system to prevent the sample from breaking apart. This technique can of course be also applied to other loosely bound samples, not only those in the field of batteries.

Imaging built-in electric fields and light matter by Fourier-precession TEM.

We report the precise measurement of electric fields in nanostructures, and high-contrast imaging of soft matter at ultralow electron doses by transmission electron microscopy (TEM). In particular, a versatile method based on the theorem of reciprocity is introduced to enable differential phase contrast imaging and ptychography in conventional, plane-wave illumination TEM. This is realised by a series of TEM images acquired under different tilts, thereby introducing the sampling rate in reciprocal space as a tuneable parameter, in contrast to momentum-resolved scanning techniques. First, the electric field of a p-n junction in GaAs is imaged. Second, low-dose, in-focus ptychographic and DPC characterisation of Kagome pores in weakly scattering covalent organic frameworks is demonstrated by using a precessing electron beam in combination with a direct electron detector. The approach offers utmost flexibility to record relevant spatial frequencies selectively, while acquisition times and dose requirements are significantly reduced compared to the 4D-STEM counterpart.

Metal Organic Vapor Phase Epitaxy in a Transmission Electron Microscope.

In situ transmission electron microscopy (TEM) observations of the metal-organic vapor phase epitaxy (MOVPE) growth promise to enhance the understanding of this complex process. However, a new experimental approach is required, capable of live imaging at the atomic scale and simultaneously reflecting this method's elevated pressures. To this end, a closed gas cell in situ TEM setup is used as a micrometer-scaled MOVPE reactor to grow GaP using tertiary butyl phosphine (TBP) and trimethyl gallium (TMGa). To prove the MOVPE reactor ability of the in situ TEM holder, the thermal decomposition of TBP and TMGa is shown to proceed similarly to conventional reactor setups. Decomposition temperatures align with susceptor temperatures in MOVPE machines. Formed products and their temperature decomposition curves are comparable to previous investigations performed in conventional reactors, even though the setups significantly differ. The obtained results are exploited to grow GaP nanostructures via the MOVPE growth process inside the TEM. To prepare a substrate surface for GaP growth, which is highly challenging, Au-catalyzed vapor-liquid-solid-grown GaP nanowires are grown in the reactor cell. Subsequently, the nanowire's sidewalls serve as MOVPE substrates. These results lay the foundation for crystal growth observation under MOVPE conditions in a TEM.