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Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.

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At least 55 records · Page 3

Calcium-organic matter fouling in nanofiltration: Synchrotron-based X-ray fluorescence and absorption near-edge structure spectroscopy for speciation

Calcium (Ca)-enhanced organic matter (OM) fouling of nanofiltration (NF) membranes leads to reduced flux during desalination and requires frequent cleaning. Fouling mechanisms are not fully understood, which limits the development of targeted fouling control methods. This study employed synchrotron-based X-ray fluorescence (XRF) and X-ray absorption near-edge structure (XANES) spectroscopy to quantify the spatial distribution and mass of Ca deposition as well as changes in the Ca coordination environment characteristic of specific fouling mechanisms, respectively. Bench-scale filtration experiments were performed using feed solutions containing Ca and ten different types of organic matter (OM), as well as the common scalants, calcium carbonate (CaCO 3 ) and calcium sulfate (CaSO 4 ). Osmotic backwash (OB) was performed at regular intervals for fouling control. Ca-OM aggregation resulted in greater flux decline and lower flux recovery during OB than Ca conditioning of membranes followed by filtration of feed solution with OM. Linear combination fitting (LCF) of XANES absorption spectra from fouled membranes indicated that Ca-OM aggregation preferentially occurred for OM types that exhibited both high carboxylic group and negative charge density. Consequently, these OM types exhibited greater deposition of Ca and TOC on the membrane surface when compared to other OM types. For the coexistence of scalants and OM, Ca speciation within the fouling layer was characteristic of both Ca bound to the membrane (i.e. potential bridging, charge screening) as well as Ca-OM aggregation and deposition mechanisms, while a range of crystal polymorphs were observed to occur simultaneously. XRF and XANES represent powerful tools for the elucidation of NF fouling mechanisms by quantification of Ca deposition as well as Ca speciation. Fouling control methods should target OM types with high carboxyl group density and negative charge to neutralize or eliminate interactions with Ca.

42 ENGINEERING↗

Rapid charging made practical in graphite-based lithium batteries: surface-acoustic wave turbulent electrolyte mixing to overcome diffusion limited charging rates [Final Report]

One of the key limits in rapidly recharging a lithium-ion battery is the depletion of lithium ions within the electrolyte adjacent the anode during charging and long diffusion time to overcome this depletion. It also causes dendrite formation, inefficient use of the lithium, and battery degradation over many charge-discharge cycles. Because the liquid electrolyte remains quiescent and unmixed, this depletion layer’s depth rapidly grows to match the anode-cathode separation distance at even modest charge rates. The solution proposed by PI Prof. James Friend and Co-PI Prof. Ping Liu, both from the University of California, San Diego, is to mix the electrolyte and minimize the Li+ ion concentration gradient during charging. Even in the presence of the separator, the charging rate could then be significantly increased. They propose to accomplish this using surface acoustic wave (SAW)-driven acoustic streaming, a technique employing 10-mW fingernail-sized solid-state devices from the telecommunications industry to drive turbulent mixing to submicron length scales in a manner completely compatible with the typical 20700 and 18650 cells used in electric vehicles. 0.1. Turbulent acoustic streaming mixes the electrolyte during charging—even with separator Our proposed 100-MHz SAW device used to recirculate the electrolyte is compatible with lithium- ion battery electrochemistry, as it is made in our lab of single-crystal lithium niobate. Their solution is straightforward to drive from a DC power source alongside the signal provided during battery charging. The device is only needed during charging and does not consume power dur- ing battery discharge. Uniquely, SAW generates extreme accelerations of over 1 billion meters per second squared in the fluid, driving turbulent mixing from centimeter to submicron length scales, even through the porous separator materials that tend to be used in batteries, all while avoiding interfering with the anode’s solid electrolyte interphase layer that forms during use. By employing novel fluid mechanics, the investigators are proposing a new direction for battery research away from direct use of materials science and electrochemistry. The chemistry agnostic solution may be employed in any battery chemistry that makes use of liquid electrolytes, providing a broader transformative benefit to the battery research community. They are to produce a series of prismatic and 20700-cell sized 2 Ah batteries capable of being charged and discharged at least 500 times without more than 20% loss in battery capacity, and to provide analysis tools useful to the battery research and development community for adopting this approach for other battery chemistries and configurations.

25 ENERGY STORAGE↗

Modeling and Characterization of Surface Discharges in Insulating Material for Spacers: Electrode Shape, Discharge Mode, and Revision of the Creepage Concept

In the design of MV AC and DC spacers, the predominant factors are surface and interface conditions. Design is generally carried out on specifications and standards which are based on long-term experience and lab testing. However, the diffusion of power electronics with a trend to increase electric field, switching frequency, and rise time to achieve higher power density calls for an innovative, global approach to optimized insulation system design. A new methodology, based on field simulation, discharge modeling, and partial discharge inception measurements, called the three-leg approach, can form the basis to optimize insulation design for any type of supply voltage waveform. This paper focuses on the influence of the type of electrode on the inception and phenomenology of surface discharges and, as a consequence, on the interpretation of the results used for application of the three-leg approach. It is demonstrated that a typical electrode system used for insulating material testing can generate both gas and surface discharges at the triple point, when the electrodes have a smooth profile that is used to avoid corona or flashover. Hence, testing partial discharge may not provide a straightforward indication of the surface discharge inception and, thus, be partially misleading for insulation design. Another takeover is that such analysis must benefit from PD testing tools endowed with analytics able to provide automatic identification of the type of defect generating PD, i.e., internal, surface, and corona, since design and remedy actions can be taken, and adequate insulating materials developed, only knowing the type of source generating PD. Hence, testing partial discharge may not provide a straightforward indication of surface discharge inception and, thus, be partially misleading for insulation design. In addition to the importance of the three-leg approach to favor reliable and optimized design of insulation systems, there is a clear need to have a PD testing tool endowed with analytics. It should preferably be able to provide automatic identification of the type of defect generating PD, i.e., internal, surface, and corona.

36 MATERIALS SCIENCE↗

Low‐Loss Tunable Infrared Plasmons in the High‐Mobility Perovskite (Ba,La)SnO 3

Abstract BaSnO 3 exhibits the highest carrier mobility among perovskite oxides, making it ideal for oxide electronics. Collective charge carrier oscillations known as plasmons are expected to arise in this material, thus providing a tool to control the nanoscale optical field for optoelectronics applications. Here, the existence of relatively long‐lived plasmons supported by high‐mobility charge carriers in La‐doped BaSnO 3 (BLSO) is demonstrated. By exploiting the high spatial and energy resolution of electron energy‐loss spectroscopy with a focused beam in a scanning transmission electron microscope, the dispersion, confinement ratio, and damping of infrared localized surface plasmons (LSPs) in BLSO nanoparticles are systematically investigated. It is found that LSPs in BLSO exhibit a high degree of spatial confinement compared to those sustained by noble metals and have relatively low losses and high quality factors with respect to other doped oxides. Further analysis clarifies the relation between plasmon damping and carrier mobility in BLSO. The results support the use of nanostructured degenerate semiconductors for plasmonic applications in the infrared region and establish a solid alternative to more traditional plasmonic materials.

36 MATERIALS SCIENCE↗

Automated Adsorption Workflow for Semiconductor Surfaces and the Application to Zinc Telluride

Surface adsorption is a crucial step in numerous processes, including heterogeneous catalysis, where the adsorption of key species is often used as a descriptor of efficiency. We present here an automated adsorption workflow for semiconductors which employs density functional theory calculations to generate adsorption data in a high-throughput manner. Starting from a bulk structure, the workflow performs an exhaustive surface search, followed by an adsorption structure construction step, which generates a minimal energy landscape to determine the optimal adsorbate-surface distance. An extensive set of energy-based, charge-based, geometric, and electronic descriptors tailored toward catalysis research are computed and saved to a personal user database. Finally, the application of the workflow to zinc telluride, a promising CO 2 reduction photocatalyst, is presented as a case study to illustrate the capabilities of this method and its potential as a material discovery tool.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Ionization behavior of nanoporous polyamide membranes

Escalating global water scarcity necessitates high-performance desalination membranes, for which fundamental understanding of structure–property–performance relationships is required. In this study, we comprehensively assess the ionization behavior of nanoporous polyamide selective layers in state-of-the-art nanofiltration (NF) membranes. In these films, residual carboxylic acids and amines influence permeability and selectivity by imparting hydrophilicity and ionizable moieties that can exclude coions. We utilize layered interfacial polymerization to prepare physically and chemically similar selective layers of controlled thickness. Additionally, we then demonstrate location-dependent ionization of carboxyl groups in NF polyamide films. Specifically, only surface carboxyl groups ionize under neutral pH, whereas interior carboxyl ionization requires pH >9. Conversely, amine ionization behaves invariably across the film. First-principles simulations reveal that the low permittivity of nanoconfined water drives the anomalous carboxyl ionization behavior. Furthermore, we report that interior carboxyl ionization could improve the water–salt permselectivity of NF membranes over fourfold, suggesting that interior charge density could be an important tool to enhance the selectivity of polyamide membranes. Our findings highlight the influence of nanoconfinement on membrane transport properties and provide enhanced fundamental understanding of ionization that could enable novel membrane design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Machine Learning for Predictive Performance Analysis in Charged Particle Beam Tools

Imaging methods driven by probes, electrons, and ions have played a dominant role in modern science and engineering. Opportunities for machine vision and AI that focus on consumer problems like driving and feature recognition, are now presenting themselves for automating aspects of the scientific processes. This proposal aims to enable and drive discovery in ultra-low energy implantation by taking advantage of faster processing, flexible control and detection methods, and architecture-agnostic workflows that will result in higher efficiency and shorter scientific development cycles. Custom microscope control, collection and analysis hardware will provide a framework for conducting novel in situ experiments revealing unprecedented insight into surface dynamics at the nanoscale. Ion implantation is a key capability for the semiconductor industry. As devices shrink, novel materials enter the manufacturing line, and quantum technologies transition to being more mainstream. Traditional implantation methods fall short in terms of energy, ion species, and positional precision. Here we demonstrate 1 keV focused ion beam Au implantation into Si and validate the results via atom probe tomography. We show the Au implant depth at 1 keV is 0.8 nm and that identical results for low energy ion implants can be achieved by either lowering the column voltage, or decelerating ions using bias – while maintaining a sub-micron beam focus. We compare our experimental results to static calculations using SRIM and dynamic calculations using binary collision approximation codes TRIDYN and IMSIL. A large discrepancy between the static and dynamic simulation is found that is due to lattice enrichment with high stopping power Au and surface sputtering. Additionally, we demonstrate how model details are particularly important to the simulation of these low-energy heavy-ion implantations. Finally, we discuss how our results pave a way to much lower implantation energies, while maintaining high spatial resolution.

47 OTHER INSTRUMENTATION↗

Understanding the chemical contribution to the enhancement mechanism in SERS: Connection with Hammett parameters

The enhancement mechanism due to the molecule-surface chemical interaction in surface-enhanced Raman scattering (SERS) has been characterized using a theoretical approach based on time dependent density functional theory. This includes a systematic study of the chemical mechanism (CM) to the SERS enhancement for halogen substituted benzenethiols interacting with a silver cluster. Changing the halogen on benzenethiol enables us to systematically modulate interactions between the benzenethiol ring and the metal cluster. We observe a decrease in the CM enhancement factor with an increase in atomic number of the halogen for para- substitutions. For meta- substitutions, there is no such trend. However, the results scale linearly with the Hammett parameters for both meta and para halogens, which provides an important predictive tool for interpreting chemical enhancements. We also study the effect of solvation on the CM, showing that there is a systematic increase in enhancement with increasing solvent dielectric constant. As a result, the correlation of CM with other properties, such as the amount of charge transfer between adsorbate and metal, or the excitation energies of charge transfer states, is much less predictive than the Hammett parameter correlation.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Zentropy Theory for Transformative Functionalities of Magnetic and Superconducting Materials

The proposed research developed the zentropy theory through applications to complex magnetic materials and superconductors under the hypothesis that the emergent properties of complex magnetic materials and superconductors can be predicted by statistical mechanics of ergodic microstates with their partition functions computed from DFT-predicted free energies. The key objective is to develop approaches to systematically determine the types and number of microstates and the supercell size in DFT-based calculations through convergency of macroscopic functionalities, with the incorporation of our mixed-space approach accounting for the interactions between periodic supercells. In addition to use scientific intuitions to guide the design of important microstates, the key innovation of the proposed research is to integrate the domain knowledge and the material-property-descriptor database (MPDD) with 4 million microstates, which is supported by our deep neural network machine learning models (SIPFENN: structure-informed prediction of formation energy using neural networks) and integrated with our high throughput DFT Tool Kit (DFTTK). For complex magnetic materials, one of the objectives is to develop approaches to calculate short-range ordering from the statistical distribution of each microstate. For superconductors, the divergency of quasiparticle effective mass at a quantum critical point will be investigated, and the superconducting and non-superconducting microstates will be delineated through analysis of electronic band structure, density of states, charge density, and Fermi surface.

36 MATERIALS SCIENCE↗

Capacitance of Carbon Nanotube/Graphene Composite Electrodes with [BMIM + ][BF$_4^–$]/Acetonitrile: Fixed Voltage Molecular Dynamics Simulations

The capacitance of nanoporous carbon electrode materials is dictated by the physical interactions with electrolyte ions and molecules at the accessible interior electrode surface. While significant progress has been made in designing and synthesizing carbon materials with well-defined and relatively homogeneous nanoporosity, the majority of materials remain heterogeneous, and the resulting properties reflect an average over this distribution. In this regard, computer simulations can be a valuable tool to predict or validate structure/property relationships by systematically investigating well-defined, model electrode morphologies. In this work, we utilize fixed-voltage molecular dynamics simulations to predict structure/capacitance relationships for five different model morphologies of carbon nanotube/graphene (CNT/G) composite electrodes with 1-butyl-3-methylimidazolium tetrafluoroborate/acetonitrile electrolyte. The CNT/G electrode models are inspired by experimental “layer-by-layer” syntheses and strike a balance between realism and computational tractability. Comparison between different model electrode architectures elucidates important structure/property relationships. We find that CNT/graphene contact points serve as “hot spots” with significantly enhanced charge separation relative to the rest of the electrode. Furthermore, we demonstrate a specific nanoconfinement motif that provides substantial 3–4$\times$ enhancement of local capacitance, resulting in a ~40% increase of the total electrode differential capacitance. Because the accessible surface area of the model CNT/G electrodes is precisely determined, a comparison of per-area capacitance across systems is unambiguous. Our results thus complement a prior computational demonstration of capacitance enhancement in nanoconfinement while elucidating additional interaction motifs at CNT/G electrochemical interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Cryogenic Platforms at Fermilab: Recent Results and Outlook

The Cosmic Quantum group at Fermilab operates three cryogenic facilities dedicated to the development and calibration of superconducting low-threshold detectors and qubits. One of which (LOUD) is located at the surface, while the other two (NEXUS and QUIET) are located 100 m underground enabling low-background device characterization and rare event searches. Recently, we have demonstrated world-leading resolution in the quasiparticle channel for kinetic inductance phonon-mediated detectors as well as the lowest rate of spatially- and temporally- correlated errors ( charge jumps ) in superconducting qubit chips. We have additionally made significant progress in expanding the suite of tools for simulating signal production and readout of these devices. In this talk, I will review these recent results, discuss some nascent projects focused on enhancing sensitivity of these detectors to sub-GeV dark matter, and highlight activities in these facilities over the next year.

Temples, Dylan J.↗

Exploring the Photophysics of N-Type Polymer N2200

The polymer interphase is a complex environment comprised of polymer chains, solvent molecules, and electrolyte ions. However, the microenvironments that these ingredients produce is both poorly-understood and difficult to investigate given the system's inherent structural heterogeneity. Nonetheless, a fundamental understanding of the structure, electrochemical behavior, and excited-state dynamics is a key prerequisite to optimizing devices based on such a system - for instance, photoelectrochemical cells for the direct, light-driven production of solar hydrogen, which may minimize efficiency losses compared to sequential light harvesting and electrochemical hydrogen production in separate but linked devices. This work combines transient absorption (TA) spectroscopy, which is a powerful tool for the observation of a variety of excited states on a femto- to microsecond timescale, with time-resolved microwave conductivity (TRMC) spectroscopy, which selectively probes the dynamics of free charge carriers (FC), of a blend of a donor polymer (PTB7-Th) and acceptor polymer (N2200) in a bulk heterojunction. Initial results indicate an extension of FC lifetime and homogenization of the microenvironment on a whole-film level, not just at the surface of the polymer; however, many questions are still under active investigation, including the changes in energy of the involved polaron states, effective conjugation length, FC mobility and migration distance, etc. Additional experiments regarding the photoinitiated behavior of the blend in different environments and on different timescales are ongoing.

charge recombination↗

Terahertz-polarizing effect based on geometric anisotropy of Ti 3 C 2 T x MXene nanosheets

Two-dimensional (2D) nanomaterials have garnered considerable attention due to their unique properties, such as thinness and excellent electronic properties. The inherent anisotropy of 2D nanomaterials, which is characterized by their high aspect ratio, can maximize the directional functionality to enhance the conductivity and utilization of edges. Here, we demonstrate how to utilize the edges of titanium carbide (Ti 3 C 2 T x ) MXene nanosheet to control the linear polarization in the terahertz (THz) frequency range. By a simple and unique vertical alignment exploiting the high surface charge and excellent colloidal dispersibility of MXene nanosheets, MXene nanosheets are vertically oriented along an applied AC electric field. The well-aligned edges justify the THz polarizing effect, revealing outstanding performances such as the broadband coverage in 0.2–1.5 THz and an exceptional extinction ratio reaching 20 dB. Furthermore, we vary the local orientation of the vertical MXene nanosheets by tailoring the applied electric field, enabling spatially controllable polarization capabilities. Our results can provide a generic tool for the utilization of 2D nanomaterials in diverse potential applications in optics and electronics.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Visualizing interfacial collective reaction behaviour of Li–S batteries

Benefiting from high energy density (2,600 Wh kg -1 )) and low cost, lithium-sulfur (Li-S) batteries are considered promising candidates for advanced energy-storage systems. Despite tremendous efforts in suppressing the long-standing shuttle effect of lithium polysulfides, understanding of the interfacial reactions of lithium polysulfides at the nanoscale remains elusive. This is mainly because of the limitations of in situ characterization tools in tracing the liquid-solid conversion of unstable lithium polysulfides at high temporal-spatial resolution. There is an urgent need to understand the coupled phenomena inside Li-S batteries, specifically, the dynamic distribution, aggregation, deposition and dissolution of lithium polysulfides. Here, by using in situ liquid-cell electrochemical transmission electron microscopy, we directly visualized the transformation of lithium polysulfides over electrode surfaces at the atomic scale. Notably, an unexpected gathering-induced collective charge transfer of lithium polysulfides was captured on the nanocluster active-centre-immobilized surface. It further induced an instantaneous deposition of nonequilibrium Li2S nanocrystals from the dense liquid phase of lithium polysulfides. Without mediation of active centres, the reactions followed a classical single-molecule pathway, lithium polysulfides transforming into Li 2 S 2 and Li 2 S step by step. Molecular dynamics simulations indicated that the long-range electrostatic interaction between active centres and lithium polysulfides promoted the formation of a dense phase consisting of Li + and S n 2- (2 < n ≤ 6), and the collective charge transfer in the dense phase was further verified by ab initio molecular dynamics simulations. Finally, the collective interfacial reaction pathway unveils a new transformation mechanism and deepens the fundamental understanding of Li-S batteries.

25 ENERGY STORAGE↗

Dynamic Carrier Modulation via Nonlinear Acoustoelectric Transport in van der Waals Heterostructures

Dynamically manipulating carriers in van der Waals heterostructures could enable solid-state quantum simulators with tunable lattice parameters. A key requirement is the formation of deep potential wells to reliably trap excitations. Here, we report the observation of nonlinear acoustoelectric transport and dynamic carrier modulation in boron nitride-encapsulated graphene devices coupled to intense surface acoustic waves (SAWs) on LiNbO 3 substrates. SAWs generate strong acoustoelectric current densities ( J AE ), transitioning from linear to nonlinear regimes with increasing SAW intensity. In the nonlinear regime, periodic carrier (electrons, holes, or their mixtures) stripes emerge. Using counter-propagating SAWs, we create standing SAWs (SSAWs) to dynamically manipulate charge distributions without static gates. The saturation of J AE , attenuation transitions, and tunable resistance peaks confirms strong carrier localization. Finally, these results establish SAWs as a powerful tool for controlling carrier dynamics in two-dimensional (2D) materials, paving the way for the development of time-dependent quantum systems and acoustic lattices for quantum simulation.

2D materials↗

Real-time mass spectrometric characterization of the solid–electrolyte interphase of a lithium-ion battery

Solid-electrolyte interphase (SEI) is a key component that dictates the performance of most electrochemical devices, but the understanding of its chemistry and structure has been limited by the lack of in-situ tools. In this work, we report SEI live-formation in Li-ion battery under operando condition with liquid secondary ion mass spectrometry (SIMS), which, in combination with molecular dynamics (MD) simulation, presents the first dynamic picture with molecular-accuracy about this key component. Before any interphasial chemistry occurs during the initial charging, an electric double layer forms at the electrode-electrolyte interface via the self-assembly of solvent molecules directed by both Li+ and potential of the electrified surface. Such double layer structure predicts the eventual interphasial chemistries formed from the electrolytes, where the negatively-charged electrode surface repels salt anions from the inner-Helmholtz layer and results in an inner SEI that is thin, dense and inorganic in nature but LiF-depleted. It was this dense layer that exercises the major functions of an interphase, i.e., conducting Li+ but insulating electrons. An outer layer that is electrolyte-permeable and organic-rich appears after formation of the inner SEI. In highly-concentrated electrolyte, the presence of LiF in the inner-SEI is raised due to the high population of salt anions in the double layer. These real-time observations at nano-scale reveal in general sense how an interphase inherits chemistry from inner-Helmholtz layer structure, and establish guidelines in engineering desirable interphases for the future battery chemistries.

Zhou, Yufan↗

Molecular dopants: Tools to control the electronic structure of metal halide perovskite interfaces

In the standard configurations of metal halide perovskite solar cell, the active layer, or absorber, follows a p-i-n or n-i-p electronic structure that is designed to enhance the separation and extraction of photo-induced charge carriers. The control of the Fermi level position across the film, between electron and hole transport layers, is therefore of paramount importance. Direct localized doping in metal halide perovskites being still elusive, the design of n-i-p and p-i-n structures has so far relied predominantly on surface and interface doping of the perovskite as well as on the control of the work function of the substrate and transport layers on which, or between which, the absorber is being placed. We provide here a short review of that work, emphasizing the fundamental studies of electronic structure performed on systems modified with organic molecular dopants. The review starts with a justification for the effectiveness of interface doping, based on the ability to move the Fermi level across the gap of the perovskite. We then review work done on the deposition of molecular oxidants and reductants on perovskite surfaces, including the mitigation of the surface states, and the impact of these dopants on energy level alignment with substrate and charge transport layers. The second part of the review focuses on the use of molecular dopants to either modify the work function of electron or hole transport layers to establish the boundary conditions for a p-i-n or n-i-p structure, or to enhance the conductivity of these layers in order to facilitate charge carrier extraction. Final considerations are also given on recent work on bulk doping of the perovskite layer with molecular dopants.

14 SOLAR ENERGY↗

Communication—Controlling Etching of Germanium through Surface Charge Manipulation

Potassium hydroxide (KOH) aqueous solutions can effectively etch germanium. Etch rates were determined in an electrolytic etch cell. Electrically isolated Ge wafers were subject to an etch rate of 1.45 ± 0.07 nm min −1 , increasing to 12.6 ± 0.2 nm min −1 when grounded, 97 ± 2 nm min −1 when biased at −0.9 V, and 138 ± 2 nm min −1 with periodic biasing. Results suggest that the previously reported limited etching in KOH is associated with the recombination of holes with electrons injected from the surface reaction. The results of this study demonstrate that changing the hole concentration through biasing is an effective tool to control electrolytic etch rates, enabling future selective etching processes for germanium.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗