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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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1,122 records · Page 63

Microscopic Observation of Solid Electrolyte Interphase Bilayer Inversion on Silicon Oxide

Silicon has been investigated in recent years as an alloying anode material to enhance gravimetric energy density in lithium-ion batteries. Although recent developments have suggested that silicon oxides exhibit improved cycling stability over pure Si, the origin of the improved cycling performance is still poorly understood. The initial solid electrolyte interphase (SEI) formation mechanisms on Si wafers with both native oxide and chemically etched thermal oxide coatings are investigated structurally, chemically, and morphologically in the nanoscale. After one electrochemical cycle, microscopy reveals that SEI formed on native SiO x features the typical SEI bilayer structure with a carbon-rich outer SEI layer and an inorganic-rich inner SEI layer. In contrast, the SEI formed on chemically etched thermal oxide shows an inversion in the structure. This work observes distinct initial SEI formation mechanisms on the HF-etched SiO 2 surface, which may be partially responsible for improved cycle life observed in SiO x -based anode materials.

25 ENERGY STORAGE↗

Quantifying the Variation in the Number of Donors in Quantum Dots Created Using Atomic Precision Advanced Manufacturing

Atomic-precision advanced manufacturing enables unique silicon quantum electronics built on quantum dots fabricated from small numbers of phosphorus dopants. The number of dopant atoms comprising a dot plays a central role in determining the behavior of charge and spin confined to the dots and thus overall device performance. Here in this work, we use both theoretical and experimental techniques to explore the combined impact of lithographic variation and stochastic kinetics on the number of P incorporations in quantum dots made using these techniques and how this variation changes as a function of the size of the dot. Using a kinetic model of PH3 dissociation augmented with novel reaction barriers, we demonstrate that for a 2 × 3 silicon dimer window the probability that no donor incorporates goes to zero, allowing for certainty in the placement of at least one donor. However, this still comes with some uncertainty in the precise number of incorporated donors (either one or two), and this variability may still impact certain applications. We also examine the impact of the size of the initial lithographic window, finding that the incorporation fraction saturates to δ-layer-like coverage as the circumference-to-area ratio decreases. We predict that this incorporation fraction depends strongly on the dosage of the precursor and that the standard deviation of the number of incorporations scales as ~√n, as would be expected for a sequence of largely independent incorporation events. Finally, we characterize an array of 36 experimentally prepared multidonor 3 × 3 nm lithographic windows with scanning tunneling microscopy, measuring the fidelity of the lithography to the desired array and the final location of PH x fragments within these lithographic windows. We use our kinetic model to examine the expected variability due to the observed lithographic error, predicting a negligible impact on incorporation statistics. We find good agreement between our model and the inferred incorporation locations in these windows from scanning tunneling microscope measurements.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Imaging moiré flat bands in three-dimensional reconstructed WSe 2 /WS 2 superlattices

Moiré superlattices in transition metal dichalcogenide (TMD) heterostructures can host novel correlated quantum phenomena due to the interplay of narrow moiré flat bands and strong, long-range Coulomb interactions. However, microscopic knowledge of the atomically reconstructed moiré superlattice and resulting flat bands is still lacking, which is critical for fundamental understanding and control of the correlated moiré phenomena. Here we quantitatively study the moiré flat bands in three-dimensional (3D) reconstructed WSe 2 /WS 2 moiré superlattices by comparing scanning tunnelling spectroscopy (STS) of high-quality exfoliated TMD heterostructure devices with ab initio simulations of TMD moiré superlattices. A strong 3D buckling reconstruction accompanied by large in-plane strain redistribution is identified in our WSe 2 /WS 2 moiré heterostructures. STS imaging demonstrates that this results in a remarkably narrow and highly localized K-point moiré flat band at the valence band edge of the heterostructure. A series of moiré flat bands are observed at different energies that exhibit varying degrees of localization. Our observations contradict previous simplified theoretical models but agree quantitatively with ab initio simulations that fully capture the 3D structural reconstruction. Furthermore, our results reveal that the strain redistribution and 3D buckling in TMD heterostructures dominate the effective moiré potential and the corresponding moiré flat bands at the Brillouin zone K points.

36 MATERIALS SCIENCE↗

Charge Disproportionation at Twisted SrTiO 3 Bilayer Interface Driven by Local Atomic Registry

The interplay of lattice, orbital, and charge degrees of freedom in complex oxide materials has hosted a plethora of exotic quantum phases and physical properties. Recent advances in the synthesis of freestanding complex oxide membranes and twisted heterostructures assembled from membranes provide diverse opportunities for discovery using moiré design with local lattice control. To this end, we designed moiré crystals at the coincidence site lattice condition, providing commensurate structure within the moiré supercell arising from the multiatom complex oxide unit cell. We fabricated such twisted bilayers from freestanding SrTiO 3 membranes and used depth-sectioning-based electron microscopic methods to investigate ordered charge states at the moiré interface. By selectively imaging SrTiO 3 atomic planes at different depths through the bilayer, we clearly resolved the moiré periodic structure at the twisted interface and found that it exhibits lattice-dependent charge disproportionation in the local atomic registry within the moiré supercell. Density functional modeling of the twisted oxide interface predicts that these moiré phenomena are accompanied by a two-dimensional flat band that can drive exceptional electronic phases. Our work provides a robust strategy for controlling moiré periodicity in twisted oxides and paves pathways to exploit the extraordinary functionalities via moiré lattice-driven charge-orbital correlation.

charge disproportionation↗

Unraveling Solar Wind Space Weathering of Carbon-Rich Asterods: Low-Flux VS. High-Flux Ion Irradiation of Murchison

Introduction: Space weathering processesalter the microstructural, compositional, and optical properties of airless planetary surfaces.Solar wind space weatheringforms ion-damaged rims within the outermost ~100 nm of regolith grains through atomic-displacements and implantation of energetic H+and He+ions[1]. Transmission electron microscope(TEM)studies of space weathered Itokawa and lunar olivine particles reveal predominantly nanocrystalline solar wind-damaged rims with only minor regions of amorphization[2-5]. This finding differs from laboratoryion irradiation experiments in which samples become amorphous at fluences 2-3 orders of magnitude lower than the independentlyconstrained fluences for still-crystalline natural samples [6-7].Ion flux is generally considered to have a secondaryeffectcompared to fluence in these irradiation experiments. However, solar wind irradiation of natural samples occurs at a flux that is ~4-5 orders of magnitude lower than whatisused inlaboratory simulations (e.g., [6,8-9]). Constraining how the very low ion flux of solar wind influences the microstructural, chemical, and spectral alteration of silicate minerals will improve our understanding of solar wind space weathering and aid in the analysis of returned samples from the Hayabusa2 and OSIRIS-REx missions. Here we report results from low-and high-flux ion irradiation experiments on the Murchison (CM2)meteoritewithcomparable total fluences. Methods: We performed low-flux and high-flux He+(4 keV) and H+(1 keV) irradiation experiments on separate, dry-cut Murchison slabs. Low-flux He+irradiation reached a total fluence of 2.1 x 1016ions/cm2(~400 years of exposure at Bennu) using a flux of 3.6 x 1011ions/cm2/s; low-flux H+irradiation reached a total fluence of 3.9 x 1016ions/cm2(~30 years) using a flux of 6.6 x 1011ions/cm2/s. High-flux He+irradiation reached a total fluence of 2.0 x 1016ions/cm2(~400 years)using a flux of 9.1 x 1012ions/cm2/s; high-flux H+irradiation reached a total fluence of 5.8 x 1016ions/cm2(~50 years)using flux of 8.4 x 1012ions/cm2/s. By irradiating to similar total fluences in both the low-flux and high-flux experiments, we can better isolate and evaluatethe effects of ion flux. Differences between unirradiatedand irradiated surfaces are determined using threeanalytical techniques:(1) in situX-ray photoelectron spectroscopy(XPS) reveals changes in surface chemistry,(2) visible to near-infrared spectroscopy (VNIR; 0.35-2.5 μm) highlights changes in spectraltrends, such as albedo and slope, and (3) TEM and energy-dispersive X-ray spectroscopy (EDS) identifieschanges in nanoscale structure and elemental composition within olivine and matrix electron-transparent thin sections prepared using focused ion beam scanning electron microscopy (FIB-SEM). Results and Discussion: XPS analyses of the low-fluxand high-fluxHe+-and H+-irradiated samples showa minorreduction in surface carbon contentand chemicalreduction ofFe3+to Fe2+. The latter result is consistent with the higher Fe2+/Fe3+ratios observed in phyllosilicate-rich space weathered rims of Ryugu grains [10].VNIR analyses suggest that the low-flux H+-irradiated spectrum has a slightly bluer slope (over 0.65-2.5 μm) compared to the unirradiated VNIR spectrum from [9] while the low-flux He+-irradiated spectral slope is comparable to the unirradiated surface. Both the high-flux He+-and H+-irradiated VNIR spectra exhibitslightlyhigheralbedos at shorter wavelengths relativeto their unirradiated counterparts, with He+irradiation yielding a greater change. Thus far, the low-flux He+-irradiated matrix and olivine FIBsections as well as the low-flux H+-irradiated olivine FIBsection have been examined with TEM. The surfaces of all three samplesshowless vesiculation than high-flux/high-fluenceirradiated matrix and olivine samples from [9]. The depth of phyllosilicate amorphization in thelow-fluxHe+-irradiated matrix FIBsection varieslaterally, with crystalline domains occurring as shallow as ~25 nm in some regions. Thelow-flux He+-irradiated olivine FIBsection has acontinuous,~40-90 nm thick ion-affected layer with polycrystalline and amorphous microstructures. The low-flux H+-irradiated olivine sampleexhibits a distinct, ~10-40 nm ion-affected layer whose uppermost ~20 nmin thicker regions is predominantly amorphous.Continuing to compare results from this work to those from [9] will provide a comprehensive understanding of how ion flux impacts the microstructural, chemical, and optical modification of various mineral phases and, in turn,help identify space weathering features from parent body alteration in Hayabusa2 and OSIRIS-REx returned samples.

D L Laczniak↗

Multimodal characterization of Te inclusions in Cd 1−x Zn x Te and Cd 1−x Zn x Te 1−y Se y for gamma and X-ray detectors

While CdZnTe (CZT) and CdZnTeSe (CZTS) semiconductors have emerged as compounds for room-temperature gamma and X-ray detection materials, they continue to be constrained by the formation of Te-inclusion defects generated during the growth and post-growth phases of the material, which adversely affect the detector performance. We demonstrate the utility of multimodal microscopic imaging and analysis for the characterization of the optical and electronic properties of Te inclusions in CZT and CZTS crystals at both micron and nanometer length scales. Having first identified regions with micron-scale Te inclusions using confocal Raman microscopy techniques, optically coupled infrared scattering near-field optical microscopic mapping was performed to map the distribution of these inclusions with nanometer spatial resolution and correlate the presence of Te inclusions in the matrix with other properties. Kelvin probe force microscopy was then utilized to characterize the variations of the work function associated with the presence of Te inclusions. Here, we observe an increase of ~ 240 mV in the work function associated with Te inclusions compared to the bulk CZT/CZTS crystals. Additionally, we observe that individual bulk grains in CZT can exhibit slight potential variations. Our findings develop a portrait of the charge trapping mechanisms in CZT and CZTS that act to degrade detector performance, while the demonstration of these combined microscopy techniques provides a new analytical tool that can be utilized for further optimization of the detector performance for these semiconducting compounds.

36 MATERIALS SCIENCE↗