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At least 775 records · Page 43

Nitrogen: A promising doping strategy for high-performance ovonic threshold switching selectors

The Ovonic Threshold Switching (OTS) selector serves as an essential component in the development of three-dimensional high-density memory integration technology. Nevertheless, the state-of-the-art high-performance OTS materials usually contain toxic elements such as arsenic (As), posing significant risks to both environmental and human health. Nitrogen (N), which belongs to the same group as arsenic (As), has emerged as a highly promising alternative for As doping. However, the underlying mechanisms that govern N-based OTS materials have not yet been extensively investigated. In this study, we delve into the effects of N doping on the structural, bonding, and electronic properties of amorphous GeSe (a-GeNSe) by ab initio molecular dynamics simulations to bridge the knowledge gap. Our findings indicate that upon N doping in a-GeSe, the formation of robust Ge-N bonds, along with N-centered tetrahedral and triangular structures, resulting in the sluggish atomic movement that enhances the thermal stability and endurance of a-GeNSe. The OTS characteristics are significantly influenced by the material’s electronic band structure, and thus the relatively slow performance drift can be attributed to the stabilization of mid-gap states, a result of N doping which effectively slows down the aging process of chalcogenide glass. Moreover, the increased mobility gap in a-GeNSe raises the threshold voltage (V th ), making it more compatible with commercially available phase-change memory materials. Furthermore, our findings reveal the extensive impact of the N element on a typical OTS material and offer valuable perspectives for alternative doping strategies that could potentially supplant As practices.

36 MATERIALS SCIENCE↗

Thermodynamic properties and enhancement of diamagnetism in nitrogen doped lutetium hydride synthesized at high pressure

Nitrogen doped lutetium hydride has drawn global attention in the pursuit of room-temperature superconductivity near ambient pressure and temperature. However, variable synthesis techniques and uncertainty surrounding nitrogen concentration have contributed to extensive debate within the scientific community about this material and its properties. We used a solid-state approach to synthesize nitrogen doped lutetium hydride at high pressure and temperature (HPT) and analyzed the residual starting materials to determine its nitrogen content. High temperature oxide melt solution calorimetry determined the formation enthalpy of LuH 1.96 N 0.02 (LHN) from LuH 2 and LuN to be −28.4 ± 11.4 kJ/mol. Magnetic measurements indicated diamagnetism which increased with nitrogen content. Ambient pressure conductivity measurements observed metallic behavior from 5 to 350 K, and the constant and parabolic magnetoresistance changed with increasing temperature. High pressure conductivity measurements revealed that LHN does not exhibit superconductivity up to 26.6 GPa. We compressed LHN in a diamond anvil cell to 13.7 GPa and measured the Raman signal at each step, with no evidence of any phase transition. Despite the absence of superconductivity, a color change from blue to purple to red was observed with increasing pressure. Thus, our findings confirm the thermodynamic stability of LHN, do not support superconductivity, and provide insights into the origins of its diamagnetism.

Science & Technology - Other Topics↗

The sensitive surface chemistry of Co-free, Ni-rich layered oxides: identifying experimental conditions that influence characterization results

Recent studies have suggested that Co-free, Ni-rich layered cathodes (e.g., doped LiNiO2) can provide promising battery performance for practical applications. However, these layered cathodes suffer from significant surface instability during various stages of the sample history, which generates inherent challenges for achieving stable battery performance and obtaining statistically representative characterization results. To reliably report the surface chemistry of these materials, delicate controls of stepwise sample preparation are required. In this study, we aim to reveal how the surface chemistry of LiNiO2 based materials changes with various environments, including human exhalation, sample storage, sample preparation, electrochemistry cycling, and surface doping. Our results demonstrate that the surface of these materials is highly reactive and prone to alter at various stages of sample handling and characterization. The sensitive surface could impact the interpretation of the surface chemical and structural information, including surface carbonate formation, transition metal reduction and dissolution, and surface reconstruction. Importantly, the heterogeneity of the surface degradation calls for a consolidation of nanoscale, high-resolution characterization, and ensemble-averaged methods in order to improve statistical representation. Furthermore, the doping chemistry can effectively mitigate the surface degradation and improve overall battery performance due to the enhanced surface oxygen retention. Our study highlights the necessity of strict measurements through complementary characterizations at multiple length scales to eliminate unintentional biased conclusions.

surface chemistry, Co-free Ni-rich cathodes, Istab↗

Unraveling Na and F coupling effects in stabilizing Li, Mn-rich layered oxide cathodes via local ordering modification

Regardless of the prevailing capacity and energy density of lithium, manganese-rich layered oxide (LMR-NMC) cathodes, continuous decay of voltage and overall energy density during cycling hinders this material from commercialization in Li-ion batteries. Although significant work focuses on single doping of Na and F, analysis in portraying the benefit of these ions in diminishing the structural distortion during activation cycle is in doubt. In this study, the effects of co-doping Na and F into the LMR-NMC structure in stabilizing the structure and mitigating oxygen loss during the first cycle are closely examined via in situ x-ray measurements. Na and F co-doping shows a 30% lower degree of Li + /Ni 2+ mixing in the Li layer (C2/m structure), 50% reduced Debye-Waller factor of Mn-O bonding, increase reversible TM migration, and faster Li diffusion relative to the pristine material. Due to the utilization of Ni redox chemistry below 4.4 V, less oxygen redox is required for charge compensation at high voltage. This study offers the first instance to quantitatively evaluate the effects of co-doping Na and F in LMR-NMC cathode in order to minimize voltage degradation by altering the local ordering of O3-type structure, which may rationalize strategies to overcome the issues of the material.

25 ENERGY STORAGE↗

Influence of doping and thickness on domain avalanches in lead zirconate titanate thin films

In undoped lead zirconate titanate films of 1–2 μm thick, domain walls move in clusters with a correlation length of approximately 0.5–2 μm. Band excitation piezoresponse force microscopy mapping of the piezoelectric nonlinearity revealed that niobium (Nb) doping increases the average concentration or mobility of domain walls without changing the cluster area of correlated domain wall motion. In comparison, manganese (Mn) doping reduces the contribution of mobile domain walls to the dielectric and piezoelectric responses without changing the cluster area for correlated motion. In both Nb and Mn doped films, the cluster area increases and the cluster density drops as the film thickness increases from 250 to 1250 nm. This is evident in spatial maps generated from the analysis of irreversible to reversible ratios of the Rayleigh coefficients.

36 MATERIALS SCIENCE↗

Crystallographic Insight of Reduced Lattice Volume Expansion in Mesoporous Cu 2+ -Doped TiNb 2 O 7 Microspheres during Li + Insertion

TiNb 2 O 7 represents a promising anode material for lithium-ion batteries (LIBs), but its practical applications are currently hampered by the non-negligible volumetric expansion and contraction during the charge/discharge process and the sluggish ion/electron kinetics. Here a combination technique is reported by systematically optimizing the porous and spherical morphology, crystal structure, and surface decoration of mesoporous Cu 2+ -doped TiNb 2 O 7 microspheres to enhance the electrochemical Li + storage performance and stability simultaneously. The Cu 2+ dopants preferentially replace Ti 4+ in crystal lattices, which decreases the Li + diffusion barrier and increases the electronic conductivity, as confirmed by density functional theory (DFT) calculation and demonstrated by diverse electrochemical characterizations. The successful Cu 2+ doping significantly reduces the lattice expansion coefficient from 7.26% to 4.61% after Li + insertion along the b-axis of TiNb 2 O 7 , as visualized from in situ and ex situ XRD analysis. The optimal 5% Cu 2+ -doped TiNb 2 O 7 with surface coating of N-doped carbon exhibits significantly enhanced specific capacity and rate and cyclic performances in both half- and full-cell configurations, demonstrating an excellent electrochemical behavior for fast-charging LIB applications.

36 MATERIALS SCIENCE↗

Fe 1+ y Te x Se1- x : A Delicate and Tunable Majorana Material

Here, we report the observation for the p z electron band and the band inversion in Fe 1 + y Te x Se 1–x with angle-resolved photoemission spectroscopy. Furthermore, we found that excess Fe (y > 0) inhibits the topological band inversion in Fe 1 + y Te x Se 1 – x , which explains the absence of Majorana zero modes in previous reports for Fe 1+y Te x Se 1 – x with excess Fe. Based on our analysis of different amounts of Te doping and excess Fe, we propose a delicate topological phase in this material. Thanks to this delicate phase, one may be able to tune the topological transition via applying lattice strain or carrier doping.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Solution-Based, Anion-Doping of Li 4 Ti 5 O 12 Nanoflowers for Lithium-Ion Battery Applications

Solution–based, anionic doping represents a convenient strategy with which to improve upon the conductivity of candidate anode materials such as Li 4 Ti 5 O 12 (LTO). As such, novel synthetic hydrothermally–inspired protocols have primarily been devised herein, aimed at the large–scale production of unique halogen–doped, micron–scale, three–dimensional, hierarchical LTO flower–like motifs. Although fluorine (F) doping has been explored, the use of chlorine (Cl) dopants is the primary focus here. Several experimental variables, such as dopant amount, lithium hydroxide concentration, and titanium butoxide purity, were probed and perfected. Furthermore, the Cl doping process did not damage the intrinsic LTO morphology. The analysis, based on interpreting a compilation of SEM, XRD, XPS, and TEM–EDS results, was used to determine an optimized dopant concentration of Cl. Electrochemical tests demonstrated an increased capacity via cycling of 12 % for a Cl–doped sample as compared with pristine LTO. Moreover, the Cl–doped LTO sample described in this study exhibited the highest discharge capacity yet reported at an observed rate of 2C for this material at 143mAh g –1 . Overall, these data suggest that the Cl dopant likely enhances not only the ion transport capabilities, but also the overall electrical conductivity of our as–prepared structures. Furthermore, to help explain these favorable findings, theoretical DFT calculations were used to postulate that the electronic conductivity and Li diffusion were likely improved by the presence of increased Ti 3+ ion concentration coupled with widening of the Li migration channel.

25 ENERGY STORAGE↗

Reversible writing of high-mobility and high-carrier-density doping patterns in two-dimensional van der Waals heterostructures

A key feature of two-dimensional materials is that the sign and concentration of their carriers can be externally controlled with techniques such as electrostatic gating. However, conventional electrostatic gating has limitations, including a maximum carrier density set by the dielectric breakdown, and ionic liquid gating and direct chemical doping also suffer from drawbacks. In this work, we show that an electron-beam-induced doping technique can be used to reversibly write high-resolution doping patterns in hexagonal boron nitride-encapsulated graphene and molybdenum disulfide (MoS 2 ) van der Waals heterostructures. The doped MoS 2 device exhibits an order of magnitude decrease of subthreshold swing compared with the device before doping, whereas the doped graphene devices demonstrate a previously inaccessible regime of high carrier concentration and high mobility, even at room temperature. We also show that the approach can be used to write high-quality p–n junctions and nanoscale doping patterns, illustrating that the technique can create nanoscale circuitry in van der Waals heterostructures.

36 MATERIALS SCIENCE↗

Direct Visualization of Defect‐Controlled Diffusion in van der Waals Gaps

Abstract Diffusion processes govern fundamental phenomena such as phase transformations, doping, and intercalation in van der Waals (vdW) bonded materials. Here, the diffusion dynamics of W atoms by visualizing the motion of individual atoms at three different vdW interfaces: hexagonal boron nitride (BN)/vacuum, BN/BN, and BN/WSe 2 , by recording scanning transmission electron microscopy movies is quantified. Supported by density functional theory (DFT) calculations, it is inferred that in all cases diffusion is governed by intermittent trapping at electron beam‐generated defect sites. This leads to diffusion properties that depend strongly on the number of defects. These results suggest that diffusion and intercalation processes in vdW materials are highly tunable and sensitive to crystal quality. The demonstration of imaging, with high spatial and temporal resolution, of layers and individual atoms inside vdW heterostructures offers possibilities for direct visualization of diffusion and atomic interactions, as well as for experiments exploring atomic structures, their in situ modification, and electrical property measurements of active devices combined with atomic resolution imaging.

Chemistry↗

Impact of SO 2 on NiFe Nanoparticle Exsolution and Dissolution from LaFe 0.9 Ni 0.1 O 3 Perovskite Oxides

Ni-doped LaFeO 3 perovskite oxide is a promising cathode material for solid oxide electrolysis cells (SOECs) designed for CO 2 /H 2 O coelectrolysis. Here, the performance of LaFe 0.9 Ni 0.1 O 3 is being investigated under real-world conditions that include exposure to acid gases, such as SO 2 , relevant to SOEC operation. Experiments show that LaFe 0.9 Ni 0.1 O 3 exsolves NiFe nanoparticles, along with the formation of surface SO 4 2– and SO 3 2– after being exposed to 200 ppm of SO 2 . This suggests that the ionic diffusion of Ni 3+ and Fe 3+ between the bulk and the surface remains unaffected throughout the exsolution–dissolution–exsolution cycle. Thermochemical water splitting has been employed as a probe reaction to evaluate the catalytic properties of the exsolved NiFe nanoparticles. These nanoparticles demonstrated improved hydrogen production compared to bare perovskite oxide substrates. However, after exposure to SO 2 , the formation of Fe-rich NiFe nanoparticles led to poor thermocatalytic performance and rapid deactivation of the perovskite at elevated temperatures. Density functional theory (DFT) analysis was utilized to validate the experimental findings, indicating a significantly negative reaction energy for water splitting over exsolved Fe, as well as stronger binding of SO 2 to Fe than to Ni. Computational analysis further suggests that the presence of surface sulfate promotes the formation of Fe-rich NiFe nanoparticles, aligning with the experimental results. Overall, this study clarifies how SO 2 affects the structure of SOEC perovskite oxide candidate materials. Future engineering efforts should focus on enhancing nanoparticle exsolution and sulfur resistance, which is crucial for improving the hydrogen production capacity of La-based perovskite oxides for electro- and thermocatalytic water splitting in real environments containing acid gases.

Najimu, Musa [Univ. of Southern California, Los An↗

Broken Symmetry Optical Transitions in (6,5) Single-Walled Carbon Nanotubes Containing sp 3 Defects Revealed by First-Principles Theory

We present a first-principles many-body perturbation theory study of nitrophenyl-doped (6,5) single-walled nanotubes (SWCNTs) to understand how sp 3 doping impacts the excitonic properties. sp 3 -doped SWCNTs are promising as a class of optoelectronic materials with bright tunable photoluminescence, long spin coherence, and single-photon emission (SPE), motivating the study of spin excitations. We predict that the dopant results in a single unpaired spin localized around the defect site, which induces multiple low-energy excitonic peaks. By comparing optical absorption and photoluminescence from experiment and theory, we identify the transitions responsible for the red-shifted, defect-induced E 11 * peak, which has demonstrated SPE for some dopants; the presence of this state is due to both the symmetry-breaking associated with the defect and the presence of the defect-induced in-gap state. Furthermore, we find an asymmetry between the contribution of the two spin channels, suggesting that this system has potential for spin-selective optical transitions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Effect of heat treatments on superconducting properties and connectivity in K-doped BaFe2As2

Abstract Fe-based superconductors and in particular K-doped BaFe 2 As 2 (K-Ba122) are materials of interest for possible future high-field applications. However the critical current density ( J c ) in polycrystalline Ba122 is still quite low and connectivity issues are suspected to be responsible. In this work we investigated the properties of high-purity, carefully processed, K-Ba122 samples synthesized with two separate heat treatments at various temperatures between 600 and 825 °C. We performed specific heat characterization and T c -distribution analysis up to 16 T and we compared them with magnetic T c and J c characterizations, and transmission-electron-microscopy (TEM) microstructures. We found no direct correlation between the magnetic T c and J c , whereas the specific heat T c -distributions did provide valuable insights. In fact the best J c -performing sample, heat treated first at 750 °C and then at 600 °C, has the peak of the T c -distributions at the highest temperatures and the least field sensitivity, thus maximizing H c2 . We also observed that the magnetic T c onset was always significantly lower than the specific heat T c : although we partially ascribe the lower magnetization T c to the small grain size (< λ , the penetration depth) of the K-Ba122 phase, this behaviour also implies the presence of some grain-boundary barriers to current flow. Comparing the T c -distribution with J c , our systematic synthesis study reveals that increasing the first heat treatment above 750 °C or the second one above 600 °C significantly compromises the connectivity and suppresses the vortex pinning properties. We conclude that high-purity precursors and clean processing are not yet enough to overcome all J c limitations. However, our study suggests that a higher temperature T c -distribution, a larger H c2 and a better connectivity could be achieved by lowering the second heat treatment temperature below 600 °C thus enhancing, as a consequence, J c .

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Computational Fermi Level Engineering and Doping-Type Conversion of Mg:Ga 2 O 3 via Three-Step Synthesis Process

Gallium oxide (Ga 2 O 3 ) is being actively explored for electronics that can operate at high power, temperature, and frequency as well as for deep-ultraviolet optoelectronics and other applications due to its ultra-wide bandgap (UWBG) and low projected fabrication cost of large-size and high-quality crystals. Efficient n-type doping of monoclinic beta-phase of Ga 2 O 3 has been achieved, but p-type doping faces fundamental obstacles due to compensation, deep acceptor levels, and the polaron transport mechanism of free holes. However, aside from the challenges of achieving p-type conductivity, plenty of opportunity exists to engineer the position of the Fermi level for improved design of Ga 2 O 3 -based devices. We use first-principles defect theory and defect equilibrium calculations to simulate a three-step growth-annealing-quench synthesis protocol for hydrogen-assisted Mg doping in ß-Ga 2 O 3 . The simulations take into account the gas phase equilibrium between H 2 , O 2 , and H 2 O, which determines the H chemical potential. We predict Ga 2 O 3 doping-type conversion to a net p-type regime after growth under reducing conditions in the presence of H2 followed by O-rich annealing, which is a similar process to Mg acceptor activation by H removal in GaN. For equilibrium annealing with re-equilibration of compensating O vacancies, there is an optimal temperature that maximizes the Ga 2 O 3 net acceptor density for a given Mg doping level; the acceptor density is further increased in the non-equilibrium annealing scenario without re-equilibration. After quenching to operating temperature, the Ga 2 O 3 Fermi level drops below mid-gap down to about 1.5 eV above the valence band maximum, creating a significant number of uncompensated neutral Mg Ga 0 acceptors. The resulting free hole concentration in Ga 2 O 3 is very low even at elevated operating temperature (~10 8 cm -3 at 400°C) due to the deep energy level of these Mg acceptors, and hole conductivity is further impeded by the polaron hopping mechanism. However, the Fermi-level reduction and suppression of free electron density in this doping-type converted (NA>ND) Ga 2 O 3 material are important for improved designs of Ga 2 O 3 electronic devices. These results illustrate the power of computational predictions not only for new materials but also for their synthesis science.

36 MATERIALS SCIENCE↗

Local lattice distortions and dynamics in extremely overdoped superconducting YSr 2 Cu 2.75 Mo 0.25 O 7.54

A common characteristic of many “overdoped” cuprates prepared with high-pressure oxygen is T c values ≥ 50 K that often exceed that of optimally doped parent compounds, despite O stoichiometries that place the materials at the edge or outside of the conventional boundary between superconducting and normal Fermi liquid states. X-ray absorption fine-structure (XAFS) measurements at 52 K on samples of high-pressure oxygen (HPO) YSr 2 Cu 2.75 Mo 0.25 O 7.54 , T c = 84 K show that the Mo is in the (VI) valence in an unusually undistorted octahedral geometry with predominantly Mo neighbors that is consistent with its assigned substitution for Cu in the chain sites of the structure. Perturbations of the Cu environments are minimal, although the Cu X-ray absorption near-edge structure (XANES) differs from that in other cuprates. The primary deviation from the crystal structure is therefore nanophase separation into Mo- and Cu-enriched domains. There are, however, indications that the dynamical attributes of the structure are altered relative to YBa 2 Cu 3 O 7 , including a shift of the Cu-apical O two-site distribution from the chain to the plane Cu sites. Another effect that would influence T c is the possibility of multiple bands at the Fermi surface caused by the presence of the second phase and the lowering of the Fermi level.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Analysis of GaAs Solar Cells Grown on 50 mm Wafers at 700 degrees C by Dynamic Hydride Vapor Phase Epitaxy

We grew and analyzed GaAs photovoltaics devices grown by dynamic hydride vapor phase epitaxy (D-HVPE) on 50 mm GaAs substrates. These were grown at 700 degrees C in a kinetically-limited growth regime. These devices exhibited nearly identical performance to our previous single-junction GaAs devices (>25% efficiency) that were grown at 650 degrees C in a transport-limited growth regime. We determined that the relatively low non-uniformity in device efficiency was not related to variations in structural characteristics, such as GaAs base thickness or Ga x In 1-x P composition or thickness, but rather uniformity of the absorber doping. These results show that growth of high quality material is possible in multiple growth regimes by D-HVPE.

14 SOLAR ENERGY↗

Improved quantitation of SIMS depth profile measurements of niobium via sample holder design improvements and characterization of grain orientation effects

The importance of SIMS analyses for “N-doped” impurity alloyed niobium and other surface-alloyed materials continues to increase. A major hurdle is the uncertainty of instrument calibration due to changes in sample height either from sample surface topography or from the sample holder itself. The CAMECA sample holder design allows for many types of samples to be analyzed. However, a drawback is that the holder faceplate can bend, contributing an uncertainty in the relative sensitivity factor (RSF) used to quantify the SIMS results. Here, we describe an improved sample holder having a reinforced faceplate, which prevents deflection and reduces uncertainty. Simulations show that the new design significantly reduces deflection from 10 μm to 5 nm. Sample measurements show a reduction of RSF uncertainty from this source from 4.1% to 0.95%. Grain orientation has long been suspected to affect RSF measurement as well. A bicrystal implant standard, consisting of randomly oriented and [001] grains, was successively rotated 15° between analyses. It was observed that 20% of the analyses performed on the randomly oriented grain exhibited anomalously high RSF values as well as slow sputter rates. These features were associated with the changing grain normal orientation with respect to the primary Cs + beam. The grain orientation associated with the rise in RSF was simulated and determined to be the [101] crystallographic plane, thus indicating that ion channeling was responsible for the significantly increased RSF. Focused ion beam analysis confirmed slower sputter rates for the cardinal crystallographic orientations, indicating that ion channeling occurred for each.

43 PARTICLE ACCELERATORS↗

Scaling, rotation, and channeling behavior of helical and skyrmion spin textures in thin films of Te-doped Cu 2 OSeO 3

Topologically nontrivial spin textures such as vortices, skyrmions, and monopoles are promising candidates as information carriers for future quantum information science. Their controlled manipulation including creation and annihilation remains an important challenge toward practical applications and further exploration of their emergent phenomena. Here, we report controlled evolution of the helical and skyrmion phases in thin films of multiferroic Te-doped Cu 2 OSeO 3 as a function of material thickness, dopant, temperature, and magnetic field using in situ Lorentz phase microscopy. We report two previously unknown phenomena in chiral spin textures in multiferroic Cu 2 OSeO 3 : anisotropic scaling and channeling with a fixed-Q state. The skyrmion channeling effectively suppresses the recently reported second skyrmion phase formation at low temperature. Our study provides a viable way toward controlled manipulation of skyrmion lattices, envisaging chirality-controlled skyrmion flow circuits and enabling precise measurement of emergent electromagnetic induction and topological Hall effects in skyrmion lattices.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗