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At least 631 records · Page 35

Coupling of magnetism, crystal lattice, and transport in EuCuP and EuCuAs

EuCuP and EuCuAs are members of a family of materials with candidates for realizing magnetically tuned electronic topology. Here, in this work, the magnetic phase transitions and magnetoelastic coupling of EuCuP and EuCuAs have been investigated. Around the Curie temperature, the thermal expansion coefficient and specific-heat capacity of EuCuP are found to have two closely spaced features, at approximately 30 and 31.3 K, which may indicate a cascading magnetic transition or perhaps an electronic transition closely coupled to the magnetic ordering. The zero-field magnetoelastic coupling appears to be stronger in EuCuP than in EuCuAs, and field-dependent measurements suggest this is due to the dominant ferromagnetic interaction in EuCuP as opposed to antiferromagnetic order in EuCuAs below T N =13.5 K. Thermal expansion is anisotropic around T N in EuCuAs, with a maximum expansion along [001] occurring above T N prior to a stiffening of this c -axis component on cooling through T N ; the expansion of the basal plane has a lambda-like peak centered slightly above T N . Matching these behaviors, the ac susceptibility data for EuCuAs suggest the presence of strong ferromagnetic correlations above T N in the vicinity where the c-axis expansion peaks. Both compounds possess similar electrical and thermoelectric transport behaviors, with short-range magnetic order likely playing an important role above T C or T N . Transport properties suggest these are predominantly hole doped due to intrinsic defects, and narrow-gap semiconducting or semimetallic behavior may be achievable if the underlying defects can be tuned.

36 MATERIALS SCIENCE↗

Manipulating topological properties in Bi 2 Se 3 / BiSe /transition metal dichalcogenide heterostructures with interface charge transfer

Heterostructures of topological insulator Bi 2 Se 3 on transition metal dichalcogenides (TMDCs) offer a new materials platform for studying novel quantum states by exploiting the interplay among topological orders, charge orders and magnetic orders. Here, the diverse interface attributes, such as material combination, charge re-arrangement, defect and strain, can be utilized to manipulate the quantum properties of this class of materials. Recent experiments of Bi 2 Se 3 /NbSe 2 heterostructures show signatures of strong Rashba band splitting due to the presence of a BiSe buffer layer, but the atomic level mechanism is not fully understood. We conduct first-principles studies of the Bi 2 Se3/BiSe/TMDC heterostructures with five different TMDC substrates (1T phase VSe 2 , MoSe 2 , TiSe 2 , and 2H phase NbSe 2 , MoSe 2 ). We find significant charge transfer at both BiSe/TMDC and Bi 2 Se 3 /BiSe interfaces driven by the work function difference, which stabilizes the BiSe layer as an electron donor and creates interface dipole. The electric field of the interface dipole breaks the inversion symmetry in the Bi 2 Se 3 layer, leading to the giant Rashba band splitting in two quintuple layers and the recovery of the Dirac point in three quintuple layers, with the latter otherwise only occurring in thicker samples with at least six Bi 2 Se 3 quintuple layers. Besides, we find that strain can significantly affect the charge transfer at the interfaces. Our study presents a promising avenue for tuning topological properties in heterostructures of two-dimensional materials, with potential applications in quantum devices.

36 MATERIALS SCIENCE↗

Semiconducting to Metallic Electronic Landscapes in Defects-Controlled 2D π-d Conjugated Coordination Polymer Thin Films

Two-dimensional coordination polymers (2DCPs) have been predicted to exhibit exotic properties such as superconductivity, topological insulating behavior, catalytic activity, and superior ion transport for energy applications; experimentally, these materials have fallen short of their expectation due to the lack of synthesis protocols that yield continuous, large crystallite domains, and highly ordered thin films with controllable physical and chemical properties. Herein, the fabrication of large-area, highly ordered 2DCP thin films with large crystallite domains using chemical vapor deposition (CVD) approaches is described. It is demonstrated that defects and the packing motifs of 2DCP thin films may be controlled by adjusting the vapor–vapor and vapor–solid interactions of the metal and organic linker precursors during the CVD fabrication process. Such control allows for the fabrication of defects-controlled 2DCP thin films that show either semiconducting or metallic behavior. The findings provide the first demonstration of tuning the electrical properties of sub 100 nm-thick continuous 2DCP thin films by controlling their electronic landscape through defect engineering. As such, it is determined that large-area, highly ordered 2DCP thin films may undergo a semiconducting to metallic transition that is correlated to changes in morphology, crystalline domain sizes, crystallite orientation, defect interactions, and electronic structure.

2D coordination polymers↗

Defects in Layered van der Waals Heterostructures: Implications for Thermoelectrics

Layered van der Waals heterostructures provide extraordinary opportunities for applications such as thermoelectrics and allow for tunability of optical and electronic properties. The performance of devices made from these heterostructures will depend on their properties, which are sensitive to the nanoarchitecture (constituent layer thicknesses, layer sequence, etc.). However, performance will also be impacted by defects, which will vary in concentration and identity with the nanoarchitecture and preparation conditions. Here, we identify several types of defects and propose mechanisms for their formation, focusing on compounds in the ([SnSe] 1+δ ) m (TiSe 2 ) n system prepared using the modulated elemental reactants method. The defects were observed by atomic resolution high-angle annular dark-field scanning transmission electron microscopy and can be broadly categorized into those that form domain boundaries as a result of rotational disorder from the self-assembly process and those that are layer-thickness-related and result from local or global deviations in the amount of material deposited. Furthermore, defect type and density were found to depend on the nanoarchitecture of the heterostructure. Categorizing the defects provides insights into defect formation in these van der Waals layered heterostructures and suggests strategies for controlling their concentrations. Strategies for controlling defect type and concentration are proposed, which would have implications for transport properties for applications in thermoelectrics.

36 MATERIALS SCIENCE↗

Theoretical insights into the surface physics and chemistry of redox-active oxides

Redox active oxides are ubiquitous in materials applications, including catalysis, photovoltaics, self-cleaning glasses, chemical sensors, and electronic components. Their utility derives from their unique ability to access multiple metal charge states within a finite energy window. However, this property also confounds our ability to study reducible oxides, because it leads to structural, compositional, and electronic complexities that elude simplistic models of materials structure and function. Oxygen vacancies play a critical role in shaping the functional properties of such oxides; most notably, they lead to mobile charge imbalances that impact surface processes at significant distances from the originating defect. Atomistic simulations are inherently equipped to illuminate these phenomena at a fundamental level; however, reducible oxides pose great challenges due to the high level of electron correlation needed to correctly describe them. Knowing how defects form, couple, propagate, agglomerate, or repel each other and influence the surface properties of reducible oxides is only now coming into the grasp of modern theory and simulation capabilities. This knowledge is also key to discovering and controlling emergent materials processes at nanometer scale and beyond. The manuscript was written with support of all three authors from U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. Work by RR and VG was performed at Pacific Northwest National Laboratory (PNNL), which is a multi-program laboratory operated by Battelle for DOE under Contract DE AC05 76RL01830. AS was supported under Award DE-SC0007347.

Rousseau, Roger J.↗

Digital Image Correlation Strain Field Analysis of Materials for Target Systems

Many accelerator facilities are currently being limited in beam power by their target facilities. When exposed to high-energy proton beams, target systems experience radiation damage, mechanical stress, and extreme temperatures, altering their physical properties.For example, due to defects induced in materials by high-energy protons, the physical properties of materials will change during irradiation. Conducting PIEs (Post Irradiation Examinations) can help us understand how the materials can change.Analyzing the strain field across an irradiated sample can help identify where defects have been created, how the hardness of materials have changed, and where they will experience failure.

Ayyildiz, Onat↗

Investigation of Oxidation Mechanisms in HfS 2 and ZrS 2 via In Situ Electron Microscopy

Transition metal dichalcogenides (TMD) combine semiconducting properties with stability and are therefore widely studied for future microelectronic devices. However, applications require integration with a suitable dielectric at a planar, defect-free interface. For Hf- and Zr-based TMDs, the good dielectric properties of hafnia and zirconia imply that direct oxidation is a promising strategy, provided that a high-quality interface and suitable oxide morphology can be formed. Here, in this study, we investigate HfS 2 and ZrS 2 oxidation, aiming to understand pathways toward planar oxide layer formation and the mechanisms that determine the characteristics of the semiconductor/dielectric interface. We use conventional and environmental transmission electron microscopy to reveal changes in morphology and composition of the TMDs under different gaseous environments. We show that oxidation at ambient conditions causes compositional heterogeneities, with local replacement of S by O in both materials. Thermal oxidation causes desulfurization and formation of a smooth but defective oxide layer. In contrast, plasma oxidation appears the best-suited to forming a controlled TMD/dielectric interface with a smooth oxide layer and without major defects. These results provide insight into the opportunities available from HfS 2 and ZrS 2 through oxidation and suggest a materials processing strategy for electronic device fabrication.

HfS2↗

Identifying Decoherence Mechanisms in Superconducting Qubits through Advanced Materials Characterization

Although superconducting qubits have emerged as a leading technology platform for quantum computing through large improvements in device coherence times and gate fidelity in recent years, the presence of defects and impurities at the interfaces and surfaces in the constituent materials continue to limit performance and serve as a critical barrier in achieving scalable quantum systems. Understanding and eliminating these sources of quantum decoherence in superconducting qubit devices requires dedicated studies aimed at establishing robust structure-property relationships that will enable researchers to target and eliminate defects strategically. As part of the Superconducting Materials and Systems (SQMS) center, we have extensively employed state-of-the-art materials characterization techniques, including scanning/transmission electron microscopy, secondary ion mass spectrometry, atom probe tomography, x-ray diffraction, and x-ray photoelectron spectroscopy in conjunction with device measurements to elucidate such relationships. In this talk, I will discuss some of our recent findings, including linking atomic defects to microwave loss in surface oxides, linking impurities in the Josephson Junction to qubit parameters, and linking low temperature precipitates to device performance. By applying these insights, we have been able to strategically develop and implement mitigation strategies for reliable fabrication of high coherence superconducting qubits.

Murthy, A. [Fermilab] (ORCID:0000000176776866)↗

Identifying Decoherence Mechanisms in Superconducting Qubits through Advanced Materials Characterization

Although superconducting qubits have emerged as a leading technology platform for quantum computing through large improvements in device coherence times and gate fidelity in recent years, the presence of defects and impurities at the interfaces and surfaces in the constituent materials continue to limit performance and serve as a critical barrier in achieving scalable quantum systems. Understanding and eliminating these sources of quantum decoherence in superconducting qubit devices requires dedicated studies aimed at establishing robust structure-property relationships that will enable researchers to target and eliminate defects strategically. As part of the Superconducting Materials and Systems (SQMS) center, we have extensively employed state-of-the-art materials characterization techniques, including scanning/transmission electron microscopy, secondary ion mass spectrometry, atom probe tomography, x-ray diffraction, and x-ray photoelectron spectroscopy in conjunction with device measurements to elucidate such relationships. In this talk, I will discuss some of our recent findings, including linking atomic defects to microwave loss in surface oxides, linking impurities in the Josephson Junction to qubit parameters, and linking low temperature precipitates to device performance. By applying these insights, we have been able to strategically develop and implement mitigation strategies for reliable fabrication of high coherence superconducting qubits.

Murthy, A. [Fermilab] (ORCID:0000000176776866)↗

Laser-Assisted Synthesis of Monolayer 2D MoSe 2 Crystals with Tunable Vacancy Concentrations: Implications for Gas and Biosensing

We report tuning the structural and electronic properties of atomically thin two-dimensional (2D) materials via defect and vacancy engineering is the key to enabling their potential use in various applications, including electronics, energy, and sensing devices. Vacancies are, for instance, becoming highly promising for the enhanced interaction of gases and biomolecules with 2D materials in energy and sensing applications. However, the deterministic generation of desirable vacancies with tunable concentrations remains a challenge in 2D materials due to the limitations in the current growth methods, such as the complex reaction chemistries and gas flow dynamics. Therefore, engineering defects and vacancies in 2D materials have been mainly limited to destructive top-down processes such as heating, ion bombardments, and laser postprocessing. Here, we introduce a single-step bottom-up synthesis approach for the growth of monolayer MoSe 2 crystals with tunable vacancy concentrations. This method utilizes the spatiotemporal properties and adjustable power densities of the lasers to control the vaporization dynamics of the stoichiometric MoSe 2 powders. Such a mechanism in the vaporization allows us to grow tunable stoichiometry monolayer MoSe 2–x crystals on the substrates. The localized and time-controlled (250 ms to 2 s) vaporization of the MoSe 2 powder by a CO 2 laser enables the formation of monolayer crystals with controlled vacancy concentrations ranging from ~1 to 20%. The effects of laser power, laser irradiation time, and background pressure on the tuning range and subsequent properties of the crystals are investigated and quantified using Raman and photoluminescence spectroscopy, scanning transmission electron microscopy (STEM), and time-correlated single-photon counting (TCSPC). This bottom-up synthesis is a promising approach that allows the deterministic vacancy tuning for future electronics and, in particular, gas and biosensing applications without the need for further postprocessing and potential structural disruption of the crystals.

2D materials↗

Absence of long-range magnetic order in Fe 1–δ Te 2 (δ ≈ 0.1) crystals

Transition metal dichalcogenides attract considerable attention due to variety of interesting properties, including long range magnetism in nanocrystals. Here we have investigated magnetic, thermal and electrical properties of FeTe 2 single crystal with iron vacancy defects. Magnetic measurements shows paramagnetic state and the absence of magnetic order with small anisotropy in magnetic susceptibility. Fe 3d orbitals are well hybridized, contributing to bad metal electrical resistivity. Observed thermal conductivity values below room temperature are rather low and comparable to high performance thermoelectric materials. Furthermore, our results indicate that FeTe 2 can form in highly defective marcasite crystal structure which can be exploited in future materials design.

36 MATERIALS SCIENCE↗

Ferroelectric Large Polarons and Defect Tolerance in Multi-Component Lead Halide Perovskites

Solvation plays a pivotal role in chemistry and biology. A solid-state analogy of solvation is polaron formation, but the magnitude of Coulomb screening is typically an order-of-magnitude weaker than that of solvation in aqueous solutions. Here the PI aims to explore a new class of polarons, the ferroelectric large polaron, which allows efficient Coulomb screening of an electron or hole by extended ordering of dipoles from symmetry-broken unit cells. This kind of local ordering is reflected in the ferroelectric-like THz dielectric responses of lead halide perovskites (LHPs) and may be partially responsible for their exceptional optoelectronic performances. A charge carrier may be localized to and/or induce the formation of nanoscale domain boundaries of locally ordered dipoles in a ferroelectric or paraelectric material, i.e., crystal structure with polar unit cells or polar fluctuations. The ability to form ferroelectric large polarons can result in the efficient screening of charge carriers from scattering with other charge carriers, with charged defects, and with longitudinal optical phonons, thus contributing to enhanced optoelectronic properties. During the past funding period, the PI has explored efficient charge carrier screening in three-dimensional (3D) LHP crystals and has developed the ferroelectric large polaron model to explain a range of carrier properties in these materials. The PI has also developed a new experimental tool, two-dimensional optical Kerr effect (2D-OKE), which is particularly powerful in probing photophysical properties with exquisite energy resolution at or near the bandgap. During the next funding periods, the PI aims to establish the applicability of the ferroelectric large polaron proposal as a general principle for the design/search of defect tolerant semiconductors in optoelectronics. Preliminary experiments on model semiconductor systems beyond LHPs have demonstrated the feasibility of the proposed research.

36 MATERIALS SCIENCE↗

The microstructure effects on irradiation response of ferritic – martensitic steels

Microstructural optimization to achieve greater mechanical strength has been one of the focuses in ferritic–martensitic steels development. However, these optimized microstructures’ effects on the radiation response are not well known. In this work, two ferritic–martensitic steels (9Cr-NbMo and 9Cr-Ta) underwent neutron irradiation in the High Flux Isotope Reactor, and their room-temperature post-irradiation tensile properties and microstructure evolutions were investigated and compared. These two steels exhibit similar pre-irradiation tensile behavior, and their yield strengths are higher than that of other ferritic–martensitic steels by about 200–250 MPa. Microstructural characterization on pre-irradiated materials reveals a smaller grain size in 9Cr-Ta (2.8 ± 0.3 μm in 9Cr-Ta versus 4.3 ± 0.5 μm in 9Cr-NbMo) but higher dislocation density and precipitate density in 9Cr-NbMo. As is common for ferritic–martensitic steels at low irradiation temperatures (less than about 0.45T m ), irradiation-induced hardening at 400 °C was observed for both alloys. Irradiation at 490 °C causes the two alloys to exhibit different tensile behavior: 9Cr-Ta softens by 208 MPa in yield stress, whereas 9Cr-NbMo maintains strength. Additionally, microstructural characterizations were performed, including precipitate growth, dislocation, and defect formation. Using the barrier hardening model for microstructure–property correlation, the softening in irradiated 9Cr-Ta is primarily attributed to the significant dislocation recovery, while the strength lost from the slight dislocation recovery in 9Cr-NbMo was compensated by the additional strength from the irradiation-induced cavities. The microstructure effect (primarily precipitate, dislocation and boundary) on the radiation response is discussed herein.

36 MATERIALS SCIENCE↗

Raman signatures from age-dating PuO 2 since last calcination

The self-irradiation of PuO 2 has been shown to affect the attributes of fifteen vibrational bands in the Raman spectrum. The vibrational bands correspond to the Raman allowed vibrational mode T 2g , overtones, defects, and bands from electronic origin. Defects in the crystal lattice from low-calcination temperature and alpha decay origins are responsible for the changes in the band attributes (band position, full-width half maximum (FWHM), intensity). Crystal lattice defects are also responsible for the growth of the defect bands. The temporal behavior of the vibrational bands can be used to estimate the age of the material since last calcination. Laser annealing was used to reset the material to full crystallinity prior to the aging study. 240 PuO 2 , with an alpha decay rate of 3.67 greater than the decay rate of 239 PuO 2 , was primarily used to assess the alpha decay-induced damage within 3 years. The aging study focused on the time-dependent properties of the T 2g band and the growth of defect bands. The FWHM of the T 2g band and the ratio of the areas of the defect bands/T 2g band were measured through a time period in excess of 3 years. The data from this study were found very close to the data describing the temporal evolution of the lattice constant measured with the X-ray diffraction (XRD) technique. The local physical properties of the material measured with Raman spectroscopy and the lattice parameter constant measured with XRD indicates a strong correlation between the two techniques. Although both techniques provide similar age-dating information, in contrast to the few milligram quantities required for XRD, Raman spectroscopy requires a 10 µm diameter PuO 2 particle to provide an estimate of the material age since last calcination.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗

Probing the Effects of the First Atomic Layer on the Dynamic Behavior of Sub-2 nm MgO/Al 2 O 3 Memristors

As electronic devices continue to scale down from the current sub-5 nm range, atomic-scale control of defects becomes increasingly crucial to suppressing their impact on the physical properties of the devices. Memristors present an excellent example as a nonlinear and dynamic device with high speed and endurance required for electronic applications ranging from neuromorphic computing to nonvolatile memories. Herein we investigate the impact of atomic defects in sub-2 nm thick MgO/Al 2 O 3 atomic layer stack (ALS) memristors that use an M1 (switching layer)/M2 (oxygen vacancy reservoir layer) bilayer structure grown using in vacuo atomic layer deposition (iALD). Intriguingly, we revealed a direct correlation of the atomic defects in the M2 layer with the memristor dynamic behavior using a combined analysis of in situ scanning tunneling spectroscopy (iSTS) on the M2 layer and ex situ characterization on the memristors. Specifically, incomplete coverage of the 1st ALD atomic layer of M2 on the electrode yields defects at the M2/electrode interface. Despite the monotonic increase of ALD coverage, by almost three-fold from ~30% to >90%, at completion of the M2 layer of ~ 0.7 nm in thickness, the impact of the defects on the M2/electrode interface has been found detrimental to both memristor switching speed and endurance. Guided by atomistic simulation, we addressed the issue of interface defects via tuning of the Al surface hydroxylation to increase the first atomic layer ALD coverage to ~75%, leading to improved memristor switching speed and endurance by several orders of magnitude. In conclusion, these findings shed light on the correlation between the atomic defects and the dynamic behavior of sub-2 nm memristors and the importance of minimizing the atomic defects in memristors for future electronic applications.

Atomic Layer Deposition↗

Autonomous fabrication of tailored defect structures in 2D materials using machine learning-enabled scanning transmission electron microscopy

Materials with tailored quantum properties can be engineered from atomic-scale assembly techniques, but existing methods often lack the agility and accuracy to precisely and intelligently control the manufacturing process. Here, we demonstrate a fully autonomous approach for fabricating atomic-level defects using electron beams in scanning transmission electron microscopy (STEM) that combines advanced machine learning and automated beam control. As a proof of concept, we achieved controlled fabrication of MoS-nanowire (MoS-NW) edge structures by iterative and targeted exposure of MoS 2 monolayer to a focused electron beam to selectively eject sulfur atoms, utilizing high-angle annular dark-field (HAADF) imaging for feedback-controlled monitoring of structural evolution of defects. A machine learning framework combining a random forest model and a convolutional neural network (CNN) was developed to decode the HAADF image and accurately identify atomic positions and species. This atomic-level information was then integrated into an autonomous decision-making platform, which applied predefined fabrication strategies to instruct beam control about atomic sites to be ejected. The selected sites were subsequently exposed to a localized electron beam using an FPGA-controlled scan routine with precise control over beam positioning and duration. While the MoS-NW edge structures produced exhibit promising mechanical and electronic properties, the proposed methods to build the autonomous fabrication framework is material-agnostic and can be extended to other 2D materials for the creation of diverse defect structures and heterostructures beyond Mo S2 .

Engineering↗

Grain boundary structure of two-dimensional tellurium revealed by 4D STEM

The recent realization of 2D tellurium (tellurene) has allowed scientists to demonstrate an air-stable monoelemental van der Waals material with remarkable potential for applications in electronics and optoelectronics. The chiral-chain structure of ultrathin Te allows controllable electronic and optical properties due to the non-monotonic carrier mobility and an increase in electronic band-gap as the thickness is reduced. Scalable and accurate production of 2D Te-based functional devices will require detailed knowledge of structural defects and strain field distributions that can be linked to transport properties.

36 MATERIALS SCIENCE↗

Rare Earth and Transition Metal Containing Glasses

Transition metal (TM) and rare earth (RE) ions have been incorporated into many glass systems such as silicate, phosphate, and borosilicate-based oxide glasses, as well as in halide and chalcogenide glasses, that find applications ranging from optical, photonic, and magnetic devices, solid-state battery, to nuclear waste disposal. Understanding the structural role of RE and TM in these glasses can help to develop glass compositions for targeted applications with either high-optical emission efficiency, electrical conductivity, or chemical durability. In this chapter, we first provide a general introduction of the applications and structural features of RE and TM in glasses, then the critical aspects of molecular dynamics (MD) simulations of these glasses such as interatomic potentials, structural analysis tools to study RE and TM ions in glasses and their clustering behaviors, Quantitative Structure–Property Analysis (QSPR), diffusion and dynamic property calculations, and electronic structure calculations to understand electronic defects such as charge trapping and radiation effects are introduced. Three representative case studies are presented: the first one is on MD simulations of erbium- and europium-doped silica and silicate glasses, as well as cerium doped aluminophosphate glasses, that revealed the effect of glass composition on RE ion local structure and clustering behavior. Electronic structure calculations of cerium-doped glass show how the existence of multioxidation states help to mediate radiation-induced damages caused by excited electron–hole pairs was also discussed. The second one focuses on alkali vanadophosphate glasses where the existence of two vanadium oxidation states help to provide electronic conduction in the glasses while alkali ions provide ionic conduction. MD simulations were used to understand vanadium environments and other structural aspects in the phosphate glasses, as well as the ionic transport behaviors of alkali ions. The third case study is on zirconium-containing borosilicate and aluminosilicate glasses that find wide applications in nuclear waste disposal. MD simulations help to provide structural details of zirconium ions that are validated by diffraction and EXAFS spectra. The structural information was used to interpret changes of mechanical properties and chemical durability by using QSPR and other analyses-based MD-generated structure models.

Du, Jincheng↗