Thin Layer Research Articles

Harnessing a WOx-based flexible transparent memristor synapse with a hafnium oxide layer for neuromorphic computing.

Transparent memristor-based neuromorphic synapses are expected to be specialised devices for high-speed information transmission and processing. The synaptic linearity and potentiation/depression cycles are imperative issues for the application of memristors. This work explores a memristor for improving switching uniformity by introducing a thin HfOx interfacial layer as a diffusion-limiting layer sandwiched between WOx and ITO bottom electrodes. An optimized HfOx thickness not only provides the best switching properties but also shows superior synaptic properties. The optimized 15 nm thin WOx layer can retain the memristor's excellence in P/D linearity, a cycling stability of 494 epochs and image recognition up to 3 mm bending, making it suitable for flexible devices. The artificial synapse is capable of reversible short-term and long-term learning behaviors confirmed by spike-timing-dependent-plasticity (STDP) results. X-ray photoelectron spectroscopy confirms the device composition and provides the oxygen vacancy concentration at the WOx/HfOx interface to realize the switching mechanism. The thicknesses of the different layers are estimated from the high-resolution transmission electron microscopy observations. The fabricated device exhibits 92.2% transparency, as confirmed by the UV-Vis spectrum.

High Density Two-Component Glasses of Organic Semiconductors Prepared by Physical Vapor Deposition.

Physical vapor deposition (PVD) is widely utilized for the production of organic semiconductor devices due to its ability to form thin layers with exceptional properties. Although the layers in the device usually consist of two or more components, there is limited understanding about the fundamental characteristics of such multicomponent vapor-deposited glasses. Here, spectroscopic ellipsometry was employed to characterize the densities, thermal stabilities, and optical properties of covapor deposited NPD and TPD glasses across the entire range of composition. We find that codeposited NPD and TPD form high density glasses with enhanced thermal stability. The dependences of density and stability upon substrate temperature are correlated, and the birefringence of the codeposited glasses is determined by the reduced substrate temperature of mixtures. Additionally, we observe that the transformation of a highly stable and dense two-component glass into its supercooled liquid initiates from the free surface and propagates into the bulk at a constant velocity, like single component PVD glasses. All of these features are consistent with the surface equilibration mechanism.

Donnan equilibrium in charged slit-pores from a hybrid nonequilibrium molecular dynamics/Monte Carlo method with ions and solvent exchange.

Ion partitioning between different compartments (e.g., a porous material and a bulk solution reservoir), known as Donnan equilibrium, plays a fundamental role in various contexts such as energy, environment, or water treatment. The linearized Poisson-Boltzmann (PB) equation, capturing the thermal motion of the ions with mean-field electrostatic interactions, is practically useful to understand and predict ion partitioning, despite its limited applicability to conditions of low salt concentrations and surface charge densities. Here, we investigate the Donnan equilibrium of coarse-grained dilute electrolytes confined in charged slit-pores in equilibrium with a reservoir of ions and solvent. We introduce and use an extension to confined systems of a recently developed hybrid nonequilibrium molecular dynamics/grand canonical Monte Carlo simulation method ("H4D"), which enhances the efficiency of solvent and ion-pair exchange via a fourth spatial dimension. We show that the validity range of linearized PB theory to predict the Donnan equilibrium of dilute electrolytes can be extended to highly charged pores by simply considering renormalized surface charge densities. We compare with simulations of implicit solvent models of electrolytes and show that in the low salt concentrations and thin electric double layer limit considered here, an explicit solvent has a limited effect on the Donnan equilibrium and that the main limitations of the analytical predictions are not due to the breakdown of the mean-field description but rather to the charge renormalization approximation, because it only focuses on the behavior far from the surfaces.

Single-crystalline metal-oxide dielectrics for top-gate 2D transistors.

Two-dimensional (2D) structures composed of atomically thin materials with high carrier mobility have been studied as candidates for future transistors1-4. However, owing to the unavailability of suitable high-quality dielectrics, 2D field-effect transistors (FETs) cannot attain the full theoretical potential and advantages despite their superior physical and electrical properties3,5,6. Here we demonstrate the fabrication of atomically thin single-crystalline Al2O3 (c-Al2O3) as a high-quality top-gate dielectric in 2D FETs. By using intercalative oxidation techniques, a stable, stoichiometric and atomically thin c-Al2O3 layer with a thickness of 1.25 nm is formed on the single-crystalline Al surface at room temperature. Owing to the favourable crystalline structure and well-defined interfaces, the gate leakage current, interface state density and dielectric strength of c-Al2O3 meet the International Roadmap for Devices and Systems requirements3,5,7. Through a one-step transfer process consisting of the source, drain, dielectric materials and gate, we achieve top-gate MoS2 FETs characterized by a steep subthreshold swing of 61 mV dec-1, high on/off current ratio of 108 and very small hysteresis of 10 mV. This technique and material demonstrate the possibility of producing high-quality single-crystalline oxides suitable for integration into fully scalable advanced 2D FETs, including negative capacitance transistors and spin transistors.

Retinal layer thinning for monitoring disease-modifying treatment in relapsing multiple sclerosis-Evidence for applying a rebaselining concept.

Employing a rebaselining concept may reduce noise in retinal layer thinning measured by optical coherence tomography (OCT). From an ongoing prospective observational study, we included patients with relapsing multiple sclerosis (RMS), who had OCT scans at disease-modifying treatment (DMT) start (baseline), 6-12 months after baseline (rebaseline), and ⩾12 months after rebaseline. Mean annualized percent loss (aL) rates (%/year) were calculated both from baseline and rebaseline for peripapillary-retinal-nerve-fiber-layer (aLpRNFLbaseline/aLpRNFLrebaseline) and macular-ganglion-cell-plus-inner-plexiform-layer (aLGCIPLbaseline/aLGCIPLrebaseline) by mixed-effects linear regression models. We included 173 RMS patients (mean age 31.7 years (SD 8.8), 72.8% female, median disease duration 15 months (12-94) median baseline-to-last-follow-up-interval 37 months (18-71); 56.6% moderately effective DMT (M-DMT), 43.4% highly effective DMT (HE-DMT)). Both mean aLpRNFLbaseline and aLGCIPLbaseline significantly increased in association with relapse (0.51% and 0.26% per relapse, p < 0.001, respectively) and disability worsening (1.10% and 0.48%, p < 0.001, respectively) before baseline, but not with DMT class. Contrarily, neither aLpRNFLrebaseline nor aLGCIPLrebaseline was dependent on relapse or disability worsening before baseline, while HE-DMT significantly lowered aLpRNFLrebaseline (by 0.31%, p < 0.001) and aLGCIPLrebaseline (0.25%, p < 0.001) compared with M-DMT. Applying a rebaselining concept significantly improves differentiation of DMT effects on retinal layer thinning by avoiding carry-over confounding from previous disease activity.

Advances in Automated Pigment Mapping for 15th-Century Manuscript Illuminations Using 1-D Convolutional Neural Networks and Hyperspectral Reflectance Image Cubes

Reflectance imaging spectroscopy (RIS) is invaluable in mapping and identifying artists’ materials in paintings. The analysis of the RIS image cube first involves classifying the cube into spatial regions, each having a unique reflectance spectrum (endmember). Second, endmember spectra are analyzed for spectral features useful to identify the pigments present to create labeled classes. The analysis process for paintings remains semi-automated because of the complex diffuse reflectance spectra due to the use of intimate pigment mixtures and optically thin paint layers by the artist. As a result, even when a group of related paintings are analyzed, each RIS cube is analyzed individually, which is time consuming. There is a need for new approaches to more efficiently analyze RIS cubes of related paintings to address the growing interest in the study of related paintings within a group of artists or artistic schools. This work builds upon prior investigations of 1-D spectral convolutional neural networks (CNNs) to address this need in two ways. First, an expanded training set was used—ten illuminated manuscripts created by artists stylistically grouped under the notname “Master of the Cypresses” (15th century Seville, Spain). Second, two 1-D CNN models were trained from the RIS cubes: reflectance and the first derivative. The results showed that the first derivative-trained CNN generally performed better than the reflectance-trained CNN in creating accurate labeled material maps for these illuminated manuscripts.

Accelerated High-Temperature Oxidation Behavior of Ferritic Stainless Steel under Air / H2+H2O Dual Atmosphere

Abstract Improvement in durability is one of the important subjects for utilizing solid oxide electrolyzer cell (SOEC) systems widely. In SOEC stacks, separators are exposed to complexed dual atmosphere (i.e. hydrogen - steam mixed gases and oxygen rich air are on each side). In this study, the degradation phenomena of separator materials (SUS430, ZMG232G10, Crofer22APU) in SOEC dual atmosphere were investigated. The samples were exposed in SOEC dual and simple atmospheres at 700°C for 500 h. Then, their cross sections were analyzed by X-ray diffraction and scanning electron microscopy/energy-dispersive X-ray analysis. The degradation mechanisms of the separator materials in the SOEC stack operating conditions were discussed. ZMG232G10 and Crofer22APU with high Cr content showed thin oxide layer under both the dual or single atmosphere, while SUS430 with low Cr content showed significant oxidation in the H2-steam atmosphere and on the air side under the dual atmosphere condition. The significant oxidation on the air side of the dual atmosphere of SUS430 observed in this study is a unique phenomenon under the dual atmosphere condition and not observed in a single air atmosphere.

Investigation of the impact of environmental conditions on the mechanical properties of thin film copper wafers

Abstract Thin film copper offers excellent film texture for multilevel interconnections in integrated circuits fabrication because of its superior resistivity to electromigration and high electricelectrical conductivity. To perform a semiconductor fabrication of copper during chemical mechanical planarization process, it is necessary to have a thorough understanding of the nanomechanical properties of thin film copper. In this study, thin film copper and reacted passivation layers on silicon substrate wafer are investigated for their nanomechanical properties under various environmental conditions. The results of this study indicate that thin film copper passivation layers have different properties in deionized water and polishing slurry environments compared to thin film copper exposed to ambient air. The insights gained from this study emphasize the significance of considering both the passivation layers and wet environments in semiconductor fabrication processes, contributing to the advancement of copper-based interconnect materials and optimization of the chemical mechanical planarization process in semiconductor manufacturing.

Design and simulation of BeSiP2-based high-performance solar cell and photosensor

This research composition provides a novel as well as non-toxic chalcopyrite-category BeSiP2 (BSP) compound-based structure that is inspected by a solar cell capacitance simulator software (SCAPS-1D) and this structure can be used for both solar cell (SC) and photosensor (PS) industries. In this structure, indium sulphide (In2S3) and molybdenum sulphide (MoS2) are exploited as window and back surface field (BSF) layers. By arranging the BSP-based photonic (photosensor and solar cell) structure, the optimized condition of different layers has been determined. Without the MoS2 layer, the value of SC and PS performance parameters are JSC of 29.75 mA/cm2, VOC of 0.84 V, FF of 83.96 %, PCE of 20.97 %, R of 0.51 AW−1 and D* of 1.68 × 1015 Jones. But with a thin MoS2 layer, the SC and PS performance parameters of the BSP compound-based photonic gadget (PG) progress meaningfully. The progress of SC and PS parameters are JSC of 34.44 mA/cm2, VOC of 0.99 V, FF of 87.45 %, PCE of 29.83 %, R of 0.64 AW−1 and D∗ of 3.63 × 1016 Jones, separately. These findings exhibit that BSP-based structure can be used for both solar cell and photodetector devices, which could be highly efficient and cost-effective fabrication in photonic industries.

Inverted optical functionality of phase change material surfaces through Mie resonances of VO2@Si core–shell structures

Vanadium dioxide (VO2) has attracted extensive attention due to its reversible transition from the insulator to metal phase at a critical temperature of 68°C. Below the critical temperature VO2 transmits the infrared radiation in the insulator phase, whereas above the critical temperature VO2 reflects the infrared portion of the incident radiation. However, smart surface interfaces for high-temperature emitter surfaces require the opposite functionality within the 1–3 µm spectral range. Here, we demonstrate that a core–shell structure, composed of VO2@Si, which is deposited on a thin layer of Ag, achieves the inverted optical functionality within the 1–3 µm spectral range, making it ideal as smart interfaces for radiative heat applications as high-temperature emitters. The proposed material architecture also increases the thermal stability of VO2 in addition to enhancing its optical properties in near-infrared region. The results were obtained using numerical simulations. Our results indicate that in its metallic state, the core–shell structure with metallic underlayer promotes efficient absorption in the near-infrared spectrum. On the other hand, in its insulating state dielectric resonances within the core–shell structure along with the metallic underlayer, resulting in increased reflection, offer inverse optical functionalities. Our findings present a significant step toward designing dynamic filters that can efficiently capture and respond to changing conditions in the near-infrared spectrum.

Thin channel Ga2O3 MOSFET with 55 GHz fMAX and &amp;gt;100 V breakdown

This Letter reports a highly scaled 90 nm gate length β-Ga2O3 (Ga2O3) T-gate MOSFET with a power gain cutoff frequency (fMAX) of 55 GHz. The 60 nm thin epitaxial Ga2O3 channel layer was grown by molecular beam epitaxy, while the highly doped (n++) source/drain regions were regrown using metal organic chemical vapor deposition. Maximum on current (IDS,MAX) of 160 mA/mm and trans-conductance (gm) around 36 mS/mm were measured at VDS = 10 V for LSD = 1.5 μm device. Transconductance and on current are limited by high channel sheet resistance (Rsheet). Gate/drain breakdown voltage of 125 V was measured for LGD = 1.2 μm. We extracted 27 GHz current gain cutoff frequency (fT) and 55 GHz fMAX for 20 V drain bias for unpassivated devices. While no current collapse was seen initially for both drain and gate lag measurements for 500 ns pulse, moderate current collapse was observed after DC, RF measurements caused by electrical stressing. We calculated a high fT. VBR product of 3.375 THz V, which is comparable to the state-of-the-art GaN HEMTs. This figure of merit suggests that Ga2O3 could be a potential candidate for X-band application.

AlN reinforced Fe activated sintered tungsten matrix composites: Mechanical properties, fracture behaviors and reinforcement mechanisms

In this study, AlN particles were proposed as the reinforcement to prepare Fe activated sintered tungsten matrix composites. The results indicated that the AlN particles stably existed inside the W(Fe) matrix and exhibited a significant strengthening and toughening effect. Compared with the W(Fe) material, the maximum microhardness, flexural strength and fracture toughness of the composites were increased by 101.42%, 66.29% and 64.63%, respectively. An AlN content-AlN particle size-composite fracture mode map was constructed to classify the four fracture modes of the composites. In addition to the fine grain strengthening and residual stress strengthening, a novel “oxygen purification strengthening effect” was found, which resulted from the thin (Fe,Al)2O3 reaction layer formed at the AlN/W(Fe) matrix interface.

Dynamic phase change materials with extended surfaces

Phase change materials (PCMs) present opportunities for efficient thermal management due to their high latent heat of melting. However, a fundamental challenge for PCM cooling is the presence of a growing liquid layer of relatively low thermal conductivity melted PCM that limits heat transfer. Dynamic phase change material (dynPCM) uses an applied pressure to pump away the melt layer and achieve a thin liquid layer, ensuring high heat transfer for extended periods. This paper investigates heat transfer during dynPCM cooling when the heated surface has extended features made from high thermal conductivity copper (Cu). Using experiments and finite element simulations, we investigate the heat transfer performance of dynPCM paraffin wax on finned Cu surfaces. A total of 102 transient temperature measurements characterize the performance of dynPCM with extended surfaces and compare the performance with other cooling methods including hybrid PCM and air cooling. The study examines the effects of fin geometry, applied power (20–65 W), and pressure (0.97–12.5 kPa). For dynPCM on a finned surface and a heating power of 65 W, the thermal conductance is 0.45 W/cm2-K, compared to 0.22 W/cm2-K for dynPCM on a flat surface and 0.10 W/cm2-K for hybrid PCM. The heat transfer is highest at the fin tips where the melt layer is thinnest, providing valuable design guidelines for future high performance dynPCM cooling technologies.

Self‐Assembly of MnS Shell on CdTe Nanoparticles Induced by Thermohydrolysis: Synthesis and Characterization

Herein, CdTe/MnS core/shell nanoparticles dispersed in an aqueous solution have been synthesized. The formation of MnS semiconductor shell occurs by spontaneous self‐assembly. This process is activated by thermal hydrolysis that removes the excess of thiol and releases S2− ions. In this process, Mn2+ ions on the surface of the CdTe nanoparticles bind to S2− ions to produce a fine semiconducting layer of MnS. Measurements of Raman spectroscopy, optical absorption, and electrochemical measurements are performed. The Raman spectrum shows CdTe characteristic bands at 141 and 163 cm−1. Bands at 221 and 444 cm−1 are associated with the MnS structure. Cyclic voltammetry and differential pulse voltammetry are used to estimate the electrochemical gap at ≈2.47 eV. Absorption optical measurements show tree absorption bands. A broad band between 460 and 520 nm is associated with the first transition in CdTe nanoparticle. The absorption spectrum reveals an optical gap in the range of 2.41–2.33 eV for all the refluxed samples. These values are consistent with those obtained with the electrochemical measurements. The results evidence the formation of a core–shell semiconducting nanostructure made of CdTe nanoparticles coated with a spontaneously self‐assembled thin layer of MnS nanoparticles.

Deciphering the catalytic activity of nickel anchored on Fe3O4@SiO2@3-CPMS@L as a magnetically recoverable nanocatalyst for the efficacious reduction of 4-nitrophenol, nitrobenzene, and methyl orange

In this paper, a versatile heterogeneous nanocatalyst was fabricated employing a self-assembly technique. To commence, Fe3O4 MNPs were coated with a thin layer of SiO2 using the stobbers method. Subsequently, the surface was further functionalized with 3-CPMS, followed by a reaction with a Schiff base. Finally, nickel NPs were deposited on the surface through in situ deposition, forming the Fe3O4@SiO2@3-CPMS@L-Ni magnetic nanocatalyst. The architecture of this magnetic nanocatalyst was meticulously characterized through an array of sophisticated techniques: XRD, FT-IR, SEM, TEM, BET and VSM. The XRD diffraction pattern confirmed the presence of Fe3O4 MNPs, SiO2, and Ni peaks, providing evidence for successful synthesis. Moreover, the successful functionalization with a Schiff base was demonstrated by the presence of an azomethane peak in the FTIR spectra of the synthesized nanocatalyst. The fabricated nanocatalyst was adeptly utilized for the reduction of 4-NP, NB, and MO demonstrating a remarkably elevated rate of catalytic efficacy. Moreover, this catalyst was effortlessly retrievable through the application of an external magnet, and it maintained its catalytic prowess across at least six consecutive cycles. The utilization of water as an environmentally friendly solvent, coupled with the utilization of abundant and cost-effective nickel catalyst instead of the costly Pd or Pt catalysts, along with the successful recovery and scalability of the catalyst, render this method highly advantageous from both environmental and economic perspectives for the reduction of 4-NP, NB, and MO.

Ursolic Acid from Perilla frutescens (L.) Britt. Regulates Zymosan-Induced Inflammatory Signaling in Raw 264.7

Background: Inflammation is considered one of the hallmarks of inflammatory diseases. Ursolic acid (UA) may exert therapeutic effects; however, the anti-inflammatory effects of UA require further study. Objectives: This study evaluated the effects of UA from Perilla frutescens (L.) Britt. leaves on pro-inflammatory activity induced by zymosan. Methods: Ursolic acid was extracted from P.frutescens (L.) Britt. leaves using ethanol, and thin layer chromatography (TLC) and high-performance liquid chromatography (HPLC) were used for UA analysis. The effect of UA on zymosan-induced cytokine production was evaluated by enzyme-linked immunosorbent assay (ELISA). Western blotting detected phosphorylation of extracellular signal-regulated kinases (ERK) 1/2, p38, and p47phox in Raw 264.7 cells. Reactive oxygen species (ROS) were measured using a specific immunofluorescent dye. Nicotinamide adenine dinucleotide phosphate (NADPH) oxidase activities were assayed using a luminometer. Results: Zymosan-induced tumor necrosis factor (TNF)-α, interleukin (IL)-6, and IL-12 p40 in macrophages were significantly inhibited by UA (30 μg/mL, P &lt; 0.001). In addition, UA (30 μg/mL, P &lt; 0.001) significantly inhibited zymosan-induced phosphorylation of ERK1/2, p38, p47phox, ROS, and NADPH oxidase in the cells. Importantly, blockade of Dectin-1 using laminarin, a pure β-glucan, markedly abrogated the UA-mediated inhibition of zymosan-induced production of inflammatory cytokines, ERK1/2, p38, ROS, and p47phox phosphorylation in macrophages. Conclusions: Collectively, these data indicate that UA regulates zymosan-induced inflammatory responses and suggest novel approaches for managing excessive inflammatory responses.

Nonflammable All-Fluorinated Electrolyte Enabling High-Voltage and High-Safety Lithium-Ion Cells.

In this study, a nonflammable all-fluorinated electrolyte for lithium-ion cells with a Li(Ni0.8Mn0.1Co0.1)O2 cathode is investigated under high voltages. This electrolyte, named FT46, consists of fluoroethylene carbonate (FEC) and bis(2,2,2-trifluoroethyl) carbonate (TFEC) in a mass ratio of 4:6. Compared to a commercially available electrolyte and several other fluorinated electrolytes, cells containing FT46 demonstrate significantly better cycling performances under high voltage (3.0-4.5 V). This result may be ascribed to the generation of a stable, smooth, and thin passivation layer and the improved solvation structure formed by FT46. The LiF-rich passivation layer strengthens the electrode/electrolyte interface, inhibits the degradation of the electrode, and suppresses side reactions between the electrodes and electrolytes under high voltage. The solvation structure formed by FT46 is derived from anions, enabling an enhanced Li+ migration rate and inhibiting lithium plating generation. Additionally, due to the nonflammability of the electrolyte and the stable passivation layers, FT46 cells also demonstrate promising safety characteristics when exposed to typical abusive conditions, such as thermal abuse, mechanical abuse, and electrical abuse.

New method for rapid detection and simultaneous determination of prohibited adrenergic drugs in sports using thin layer chromatography and image processing

This study presents a new method for simultaneous determination of fenoterol, procaterol, clenbuterol, terbutaline and isoprenaline drugs using thin-layer chromatography assisted by image analysis (HPTLC-IA) combined with sensitive detection modes. Separation of the selected drugs was obtained using HPTLC Silica gel 60 F254 plates and mixture of isopropyl alcohol, ethyl acetate and ammonia (20:25:1.5 v/v/v) as mobile phase. UV detection mode combined with the use of 2,2-diphenyl-1-picrylhydrazyl (DPPH•) and 2,2'-azino-bis (3-ethylbenzothiazoline)-6-sulfonic acid (ABTS+•) radicals were applied for the first time for sensible detection of the separated drugs. Grey, green, red and blue scales respectively were selected for image analysis and accurate quantification of spot area. According to the obtained result, the use of DPPH• and ABTS+• reagents revealed a higher sensitivity in detection and accurate quantification of the analyzed drugs. Lower limit of detection (LOD = 0.07 ± 0.03 µg/spot; 0.09 ± 0.03 µg/spot and 0.10 ± 0.04 µg/spot) was obtained for fenoterol, procaterol and terbutaline using the ABTS+• radical and red scale selection for image processing. With the exception of isoprenaline, the proposed HPTLC-IA method showed a good separation of fenoterol, procaterol, clenbuterol and terbutaline drugs from other compounds in urine samples. Good recovery was obtained for these drugs in spiked urine samples.

Crustal origin for olivine in the lunar Shioli crater ejecta boulders: Insights from the geological setting of Theophilus crater and Nectaris basin

On the Moon, impact craters and basins expose a wide range of crustal and mantle rocks that provide excellent opportunity for sampling them, understanding their origins and reconstructing spatial and temporal evolution of lunar interior. The previous studies detected olivine-bearing mantle rocks in and around large impact craters and basins. The Japanese SLIM mission landed on the ejecta of a ∼ 280-m-diameter Shioli crater that was emplaced on the ejecta blanket of ∼ 103-km-diameter Theophilus crater, for characterizing potential mantle-derived olivine in the Shioli crater ejecta boulders. To test this hypothesis, we studied the geological setting of Shioli crater, host Theophilus crater and Nectaris multi-ring basin using the orbiter data from Chandrayaan-1 and 2, Lunar Reconnaissance Orbiter, and Kaguya missions and the earth-based Arecibo radar observation. The asymmetrically distributed secondary craters and impact melt ponds around Theophilus crater suggests that a northeast-directed oblique impact produced this crater. Composition of Theophilus crater and surrounding region indicates that the crater excavated a heterogeneous target composed of a thin layer of high-Al olivine basalt (Mare Nectaris) underlain by anorthositic highland rocks possibly intruded by Mg-suite plutons; layers of Cyrillus crater ejecta blanket and Nectaris basin materials (both ejecta and impact melt sheets) were also present beneath the mare basalt flows. Hence, the Theophilus ejecta blanket is a mixture of all these materials. Our dating of Theophilus crater suggests that it is a ∼ 2 Ga Eratosthenian crater. Shioli is a fresh simple crater that was formed at ∼ 1 Ma on the uprange ejecta blanket of Theophilus, where the Arecibo radar data indicated the presence of abundant buried Theophilus ejecta boulders. An ESE-directed hypervelocity oblique impact event produced the elongated Shioli crater and its asymmetrically distributed bright ejecta. Shioli is a primary impact crater indicating the role of impact spallation processes associated with this hyper-velocity impact in producing thousands of ejecta (or spall) boulders around Shioli crater, displaying their asymmetric dispersal pattern and spatial variation of boulder sizes and shapes. The larger and elongated boulders are concentrated near the crater rim, while their size and axial ratio gradually decreases outward from the crater rim. The SLIM mission landed on a thin downrange ejecta of Shioli crater, where fewer large-size boulders are present. Our compositional study suggests that the Shioli ejecta boulders are composed of olivine basalt (Mare Nectaris) mixed with highland anorthositic fragments, including the reworked Cyrillus ejecta and Nectaris basin materials. The Shioli ejecta boulders were produced by complex impact fragmentation of already existing, buried Theophilus ejecta boulders. The regional crustal structure of Nectaris basin and its petrological composition suggest that both Nectaris basin and Theophilus crater did not excavate the lunar mantle. Therefore, the Shioli ejecta boulders are of crustal origin, including the olivine minerals present in them. Our results have important implications for the origin of olivine in the Shioli crater boulders being investigated by the SLIM mission.

New palladium(II) β-ketoesterates for focused electron beam induced deposition: synthesis, structures, and characterization.

We report the synthesis and characterization of new palladium(II) β-ketoesterate complexes [Pd(CH3COCHCO2R)2] with alkyl substituents R = tBu, iPr, Et. These compounds can have potential use in focused electron beam induced deposition (FEBID), which is a direct write method for the growth of structures at the nanoscale. However, it is still a major challenge to obtain deposits with a high metal content, and new precursor molecules are needed to overcome this. Single crystal X-ray diffraction, infrared spectroscopy, nuclear magnetic resonance spectroscopy, and density-functional theory calculations were used to confirm the compounds' composition and structure. Using thermal analysis and sublimation experiments, we investigate their thermal stability and volatility. These studies show that the palladium complexes sublimate over the range 348-353 K under 10-2 mbar pressure. The electron-induced decomposition of the complex molecules in the gas phase and their thin layers on silicon substrates were analysed using electron impact mass spectrometry (EI MS) and microscopy studies (SEM/EDX). They confirm that the precursor electron-induced fragmentation depends on the molecular structure. The obtained results reveal that [Pd(CH3COCHCO2tBu)2] with cis-positioned tert-butyl groups may be a promising FEBID precursor, and we carried out preliminary deposition experiments using this compound.