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At least 289 records · Page 16

Many routes to ferroelectric HfO 2 : A review of current deposition methods

Although 10 years have passed since the initial report of ferroelectricity in hafnia (HfO 2 ), researchers are still intensely fascinated by this material system and the promise it holds for future applications. A wide variety of deposition methods have been deployed to create ferroelectric HfO 2 thin films such as atomic layer deposition, chemical solution deposition, and physical vapor deposition methods such as sputtering and pulsed laser deposition. Process and design parameters such as deposition temperature, precursor choice, target source, vacuum level, reactive gases, substrate strain, and many others are often integral in stabilizing the polar orthorhombic phase and ferroelectricity. We examine processing parameters across four main different deposition methods and their effect on film microstructure, phase evolution, defect concentration, and resultant electrical properties. The goal of this review is to integrate the process knowledge collected over the past 10 years in the field of ferroelectric HfO 2 into a single comprehensive guide for the design of future HfO 2 -based ferroelectric materials and devices.

36 MATERIALS SCIENCE↗

Elasticity of davemaoite as a primary contributor to lower-mantle heterogeneities

Geophysical detection of subducted mid–ocean ridge basalt (MORB) in the lower mantle is hindered by uncertainties in the elasticity of Fe,Al,Mg,Ti–bearing davemaoite, a key MORB component. Using Brillouin spectroscopy and x-ray diffraction, we determined the elasticity of a Ca 0.906(1) Fe 2+ 0.027(1) Fe 3+ 0.042(1) Mg 0.033(1) Al 0.072(1) Ti 0.020(1) Si 0.912(1) O 3 davemaoite up to 113 gigapascals and 2294 K. Here, we found that it exhibited a shear wave velocity 10 to 20% slower than end-member davemaoite, making it the slowest phase among major lower-mantle minerals. Our models show that MORB, containing 20 to 25 volume percent davemaoite, potentially contributes to large low-shear-velocity provinces (LLSVPs), whereas a cumulate layer enriched in davemaoite crystallized from basal magma ocean may comprise ultralow-velocity zones (ULVZs). Davemaoite’s ability to host incompatible and heat-producing elements possibly links LLSVPs and ULVZs to mantle plume initiation and geochemical signatures of ocean island basalts.

Zhou, Wen-Yi [Texas A & M Univ., College Station, ↗

Milestone 1.2.12: The Fate of Oxygen Radical Species in Corroded Aluminum Alloys under Irradiation

The U.S. Department of Energy tasked Idaho National Laboratory to evaluate the feasibility of extended dry storage of aluminum-clad spent nuclear fuel (ASNF) in heliumbackfilled canisters. A significant research effort has been devoted to determining the amount of radiation-induced molecular hydrogen (H 2 ) generation from corrosion layers that would be present on the fuel assembly surfaces. However, limited attention has been directed to the oxygen radical species that are concurrently generated in these H 2 producing radiation environments. This report collates and summarizes the available experimental and computational studies on the fate of these reactive oxygen radicals during the irradiation of aluminum oxyhydroxide and hydroxide polymorphs typically formed on ASNF. Based on this review, it is determined that radiation-induced oxygen-centered radicals do not react to give molecular oxygen gas (O 2 ), but rather remain trapped in the aluminum corrosion layers in their original crystal lattice positions. Overall, O 2 generation will not be a concern for extended storage of ASNF in helium-backfilled canisters. That is, no O 2 contribution to pressurization of sealed dry storage systems or creation of a flammable atmosphere is anticipated.

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEA↗

High Layer Number ( n = 1–6) 2D Ruddlesden–Popper Lead Bromide Perovskites: Nanosheets, Crystal Structure, and Optoelectronic Properties

2D Ruddlesden–Popper (RP) lead halide perovskites have highly tunable structures, compositions, and properties that enable their promising optoelectronic applications. Among various 2D halide perovskites, the materials chemistry and fundamental optoelectronic properties of high layer number (n) lead-bromide RP perovskites, where n refers to the number of inorganic octahedra layers, have been less studied. Here, we report the synthesis of thin nanosheets of (PEA) 2 Cs n–1 Pb n Br 3n+1 (n = 1–6, PEA = phenylethylammonium) perovskites and study the optical properties, assigning photoluminescence emissions of 486, 496, and 505 nm to n = 4–6 phases, respectively, and reporting the photoluminescence lifetimes. Furthermore, the crystal structure of (PEA) 2 Cs 2 Pb 3 Br 10 was determined to reveal minimal octahedral structural distortions. Ultraviolet photoelectron spectroscopy measurements reveal the positioning of the valence and conduction bands for n = 1–3 phases and confirm the type-I band alignment for the (PEA) 2 Cs n–1 Pb n Br 3n+1 series, laying the foundation for rational heterostructure device design in the future.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Field-tunable valley coupling in a dodecagonal semiconductor quasicrystal

Quasicrystals are characterized by atomic arrangements having long-range order without periodicity. Van der Waals bilayers provide an opportunity to controllably vary the atomic alignment between two layers from a periodic moiré crystal to an aperiodic quasicrystal. Here, in this work, we reveal that in a dodecagonal WSe 2 quasicrystal, two separate valleys in separate layers are brought arbitrarily close in momentum space through higher-order Umklapp scatterings. A modest perpendicular electric field is then sufficient to induce strong interlayer valley hybridization, manifested as another hybrid excitonic doublet. Concurrently, we observe the disappearance of the trion that exists at low field, which we attribute to a modified spatial distribution of the wavefunction due to the quasicrystal potential. This is possibly a precursor to localization. Our findings highlight the ability of incommensurate systems to bring any pair of momenta into close proximity, thereby introducing opportunities for valley engineering.

electronic properties and materials↗

Direct Observation of Two-Step, Stratified Crystallization and Morphology in Conjugated Polymer Thin Films

A two-step stratified crystallization process has been directly observed during cooling of poly(3-hexylthiophene) (P3HT) thin films of thickness h = 20-250 nm: a thin (<20 nm) layer at the free surface crystallizes ~25 °C higher than the bulk crystallization temperature (T C,bulk ), whereas the rest of the film (i.e. the underlayer) crystallizes near T C,bulk . In-situ measurements of films with and without a free surface unequivocally ascribe the high-temperature crystallization to a surface-induced process, which correlates with the formation of large birefringent structures and highly oriented edge-on crystallites at the air–polymer interface. In contrast, crystallization of the bulk-like underlayer leads to mostly edge-on-oriented crystallites in thinner films and becomes increasingly isotropic in thicker films. For h < 20 nm, free-surface effects dominate and only high-temperature crystallization is observed. These results highlight the potential of melt crystallization to tailor morphology and orientation across thin film thickness for specific electronic applications.

36 MATERIALS SCIENCE↗

Magnet-in-ferroelectric crystals exhibiting photomultiferroicity

Growing crystallographically incommensurate and dissimilar organic materials is fundamentally intriguing but challenging for the prominent cross-correlation phenomenon enabling unique magnetic, electronic, and optical functionalities. Here, we report the growth of molecular layered magnet-in-ferroelectric crystals, demonstrating photomanipulation of interfacial ferroic coupling. The heterocrystals exhibit striking photomagnetization and magnetoelectricity, resulting in photomultiferroic coupling and complete change of their color while inheriting ferroelectricity and magnetism from the parent phases. Under a light illumination, ferromagnetic resonance shifts of 910 Oe are observed in heterocrystals while showing a magnetization change of 0.015 emu/g. In addition, a noticeable magnetization change (8% of magnetization at a 1,000 Oe external field) in the vicinity of ferro-to-paraelectric transition is observed. The mechanistic electric-field-dependent studies suggest the photoinduced ferroelectric field effect responsible for the tailoring of photo-piezo-magnetism. The crystallographic analyses further evidence the lattice coupling of a magnet-in-ferroelectric heterocrystal system.

42 ENGINEERING↗

Optical, structural and aging properties of Al/Sc-based multilayers for the extreme ultraviolet

This manuscript presents the structural characterization of Al/Sc-based periodic multilayer coatings for the extreme ultraviolet (EUV) spectral range. Based on transmission electron microscopy and electron diffraction as well as grazing-incidence and large-angle x-ray diffraction, a model for the layer structure and the interfacial effects of Al/Sc coatings is built. The onset of crystallization in nanoscale Al and Sc layers as a function of thickness is also revealed in these characterizations. The Al/Sc layer model is validated and further refined by fitting in-band and out-of-band EUV reflectance measurements across 5 orders of magnitude in an extended wavelength range from 17 to 80 nm. Here, the same type of EUV reflectance measurements is used to test the Al/Sc aging properties and to demonstrate the spectral response of optimized two- and tri-material multilayers including Al/Sc, Al/Sc/SiC and Mo/Al/Sc.

36 MATERIALS SCIENCE↗

Stacking Fault Induced Symmetry Breaking in van der Waals Nanowires

While traditional ferroelectrics are based on polar crystals in bulk or thin film form, two-dimensional and layered materials can support mechanisms for symmetry breaking between centrosymmetric building blocks, e.g., by creating low-symmetry interfaces in van der Waals stacks. Here, we introduce an approach toward symmetry breaking in van der Waals crystals that relies on the spontaneous incorporation of stacking faults in a nonpolar bulk layer sequence. The concept is realized in nanowires consisting of Se-rich group IV monochalcogenide (GeSe 1–x S x ) alloys, obtained by vapor–liquid–solid growth. The single crystalline wires adopt a layered structure in which the nonpolar A-B bulk stacking along the nanowire axis is interrupted by single-layer stacking faults with local A-A' stacking. Density functional theory explains this behavior by a reduced stacking fault formation energy in GeSe (or Se-rich GeSe 1–x S x alloys). Computations demonstrate that, similar to monochalcogenide monolayers, the inserted A-layers should show a spontaneous electric polarization with a switching barrier consistent with a Curie temperature above room temperature. Second-harmonic generation signals are consistent with a variable density of stacking faults along the wires. Here, our results point to possible routes for designing ferroelectrics via the layer stacking in van der Waals crystals.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Theoretical phase diagram of two-component composite fermions in double-layer graphene

Theory predicts that double layer systems realize “two-component composite fermions,” which are formed when electrons capture both intra- and inter-layer vortices, to produce a wide variety of new strongly correlated liquid and crystal states as a function of the layer separation. Recent experiments in double layer graphene have revealed a large number of layer-correlated fractional quantum Hall states in the lowest Landau level, many of which have not been studied quantitatively in previous theoretical works. We consider the competition between various liquid and crystal states at several of these filling factors (specifically, the states at total filling factors ν = 3/7, 4/9, 6/11, 4/7, 3/5, 2/3, and 4/5) to determine the theoretical phase diagram as a function of the layer separation. We compare our results with experiments and identify various observed states. In particular, we show that at small layer separations the states at total fillings ν = 3/7 and ν = 3/5 are partially pseudospin polarized, where pseudospin refers to the layer index. For certain fractions, such as ν = 3/7, interlayer correlations are predicted to survive to surprisingly large interlayer separations.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Opportunities in electrically tunable 2D materials beyond graphene: Recent progress and future outlook

The interest in two-dimensional and layered materials continues to expand, driven by the compelling properties of individual atomic layers that can be stacked and/or twisted into synthetic heterostructures. The plethora of electronic properties as well as the emergence of many different quasiparticles, including plasmons, polaritons, trions, and excitons with large, tunable binding energies that all can be controlled and modulated through electrical means, has given rise to many device applications. In addition, these materials exhibit both room-temperature spin and valley polarization, magnetism, superconductivity, piezoelectricity that are intricately dependent on the composition, crystal structure, stacking, twist angle, layer number, and phases of these materials. Initial results on graphene exfoliated from single bulk crystals motivated the development of wide-area, high purity synthesis and heterojunctions with atomically clean interfaces. Now by opening this design space to new synthetic two-dimensional materials “beyond graphene,” it is possible to explore uncharted opportunities in designing novel heterostructures for electrically tunable devices. To fully reveal the emerging functionalities and opportunities of these atomically thin materials in practical applications, this review highlights several representative and noteworthy research directions in the use of electrical means to tune these aforementioned physical and structural properties, with an emphasis on discussing major applications of beyond graphene 2D materials in tunable devices in recent years and an outlook of what is to come in the next decade.

Vincent, Tom (ORCID:0000000159749137)↗

Virtual Substrates for Wide Bandgap AlyX1-yN Growth

Lattice-matched substrates are critical for growth of high quality, compositionally-targeted ternary AlyX1-yN compounds with properties suitable for a wide variety of next-generation opto- and power electronic applications. [DOI:10.1149/2.0111702jss] We have identified the (111) plane of transition metal carbides and nitrides as lattice matched "virtual" substrate layers that have additional benefits of electrical conductivity and appropriate coefficients of thermal expansion for nitride layer at both growth and operating temperatures. [arXiv:2208.11769 2022] In this work, (111)-oriented TaC and ZrN are grown by RF sputtering and optimized as substrate layers for AlyGa1-yN and AlyGd1-yN, respectively. TaC is demonstrated as a full proof of concept. (111)-stabilized TaC layers with a rock-salt crystal structure are annealed to improve surface crystal quality and surface morphology and then used as a template for growth of an Al0.7Ga0.3N layer by molecular beam epitaxy. X-ray diffraction (XRD) demonstrates epitaxial registry of the grown layer to the substrate. High resolution transmission electron microscopy (TEM) is used to investigate interface behavior, showing regions of abrupt interface transitions and nitrogen polar termination of the Al0.7Ga0.3N. We also grew (111)-oriented ZrN on Ti-Zr-N graded buffer layers as a lattice-matched virtual substrate for AlyGd1-yN. Structure, morphology, and strain are analyzed using XRD and atomic force microscopy. Structure and quality of initial Al0.8Gd0.2N thin films are investigated for both in-situ and ex-situ growths.

AlyX1-yN↗

Azimuthal Anchoring Strength in Photopatterned Alignment of a Nematic

Spatially-varying director fields have become an important part of research and development in liquid crystals. Characterization of the anchoring strength associated with a spatially-varying director is difficult, since the methods developed for a uniform alignment are seldom applicable. Here we characterize the strength of azimuthal surface anchoring produced by the photoalignment technique based on plasmonic metamsaks. The measurements used photopatterned arrays of topological point defects of strength +1 and −1 in thin layers of a nematic liquid crystal. The integer-strength defects split into pairs of half-integer defects with lower elastic energy. The separation distance between the split pair is limited by the azimuthal surface anchoring, which allows one to determine the strength of the latter. The strength of the azimuthal anchoring is proportional to the UV exposure time during the photoalignment of the azobenzene layer.

36 MATERIALS SCIENCE↗

Unconventional crystal-field splitting in noncentrosymmetric BaTiO 3 thin films

Understanding the crystal-field splitting and orbital polarization in noncentrosymmetric systems such as ferroelectric materials is fundamentally important. In this work, taking BaTiO 3 as a representative material, we investigate titanium crystal-field splitting and orbital polarization in noncentrosymmetric TiO 6 octahedra with resonant x-ray linear dichroism at the Ti L 2,3 edge. The high-quality BaTiO 3 thin films were deposited on DyScO 3 (110) single crystal substrates in a layer-by-layer way by pulsed laser deposition. The reflection high-energy electron diffraction and element specific x-ray absorption spectroscopy were performed to characterize the structural and electronic properties of the films. In sharp contrast to conventional crystal-field splitting and orbital configuration (d xz /d yz < d xy < d 3z 2 -r 2 < d x 2 -y 2 or d xy < d xz /d yz < d x 2 -y 2 < d 3z 2 -r 2 ) expected from compressive or tensile epitaxial strain, respectively, it is revealed that d xz , d yz , and d xy orbitals are nearly degenerate, whereas d 3z 2 -r 2 and d x 2 -y 2 orbitals are split with an energy gap ~100 meV in the epitaxial BaTiO 3 films. We find that the unexpected degenerate orbitals d xz /d yz /d xy result from the competition between the orbital splitting induced by epitaxial strain and that induced by polar distortions of BaTiO 3 films. Our results provide a route to manipulate orbital degree of freedom by switching electric polarization in ferroelectric materials.

36 MATERIALS SCIENCE↗

Stern layers on RuO2 (100) and (110) in electrolyte: Surface X-ray scattering studies

Electrochemical Stern layers are observed on the surfaces of RuO 2 single crystals in 0.1 M CsF electrolyte. The Stern layers formed at the interfaces of RuO 2 (110) and (100) are compared to the previously reported Stern layer on Pt (111) [Liu et al., J. Phys. Chem. Lett., 9 (2018) 1265]. While the Cs + density profiles at the potentials close to hydrogen evolution reactions are similar, the hydration layers intervening the surface and the Cs + layer are significantly denser on RuO 2 surfaces than that on Pt(111) surface, reflecting the oxygen termination of RuO 2 surfaces. The overall similarities between Stern layers on ruthenium surfaces and platinum surface suggest the universal presence of Stern layers in all well-defined solid-electrolyte interfaces.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Helfrich-Hurault elastic instabilities driven by geometrical frustration

Here, the Helfrich-Hurault (HH) elastic instability is a well-known mechanism behind patterns that form as a result of strain upon liquid crystal systems with periodic ground states. In the HH model, layered structures undulate and buckle in response to local, geometric incompatibilities in order to maintain the preferred layer spacing. Classic HH systems include cholesteric liquid crystals under electromagnetic field distortions and smectic liquid crystals under mechanical strains, where both materials are confined between rigid substrates. However, richer phenomena are observed when undulation instabilities occur in the presence of deformable interfaces and variable boundary conditions. Understanding how the HH instability is affected by deformable surfaces is imperative for applying the instability to a broader range of materials. In this review, the HH mechanism is reexamined and special focus is given to how the boundary conditions influence the response of lamellar systems to geometrical frustration. Lamellar liquid crystals confined within a spherical shell geometry are used as the model system. Made possible by the relatively recent advances in microfluidics within the past 15 years, liquid crystal shells are composed entirely of fluid interfaces and have boundary conditions that can be dynamically controlled at will. Past and recent work that exemplifies how topological constraints, molecular anchoring conditions, and boundary curvature can trigger the HH mechanism in liquid crystals with periodic ground states is examined. The review ends by identifying similar phenomena across a wide variety of materials, both biological and synthetic. The fact that the HH mechanism is a generic and often overlooked response of periodic materials to geometrical frustration is highlighted.

42 ENGINEERING↗

XFEL Microcrystallography of Self-Assembling Silver n -Alkanethiolates

New synthetic hybrid materials and their increasing complexity have placed growing demands on crystal growth for single-crystal X-ray diffraction analysis. Unfortunately, not all chemical systems are conducive to the isolation of single crystals for traditional characterization. Here, small-molecule serial femtosecond crystallography (smSFX) at atomic resolution (0.833 Å) is employed to characterize microcrystalline silver n-alkanethiolates with various alkyl chain lengths at X-ray free electron laser facilities, resolving long-standing controversies regarding the atomic connectivity and odd–even effects of layer stacking. smSFX provides high-quality crystal structures directly from the powder of the true unknowns, a capability that is particularly useful for systems having notoriously small or defective crystals. We present crystal structures of silver n-butanethiolate (C4), silver n-hexanethiolate (C6), and silver n-nonanethiolate (C9). We show that an odd–even effect originates from the orientation of the terminal methyl group and its role in packing efficiency. We also propose a secondary odd–even effect involving multiple mosaic blocks in the crystals containing even-numbered chains, identified by selected-area electron diffraction measurements. Finally, we conclude with a discussion of the merits of the synthetic preparation for the preparation of microdiffraction specimens and compare the long-range order in these crystals to that of self-assembled monolayers.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Achieving Flat-on Primary Crystals by Nanoconfined Crystallization in High-Temperature Polycarbonate/Poly(vinylidene fluoride) Multilayer Films and Its Effect on Dielectric Insulation

To meet the stringent requirements of next-generation film capacitors for power electronics, multilayer films (MLFs) are fabricated with the advantage of achieving high temperature rating, high energy density, and reasonably low loss simultaneously. In this study, a high permittivity polar polymer, poly(vinylidene fluoride) (PVDF), is multilayered with a linear, low loss dielectric polymer such as high-temperature polycarbonate (HTPC). However, the dielectric loss of these MLFs was still high as compared with current state-of-the-art biaxially oriented polypropylene (BOPP) films. The goal of this work is to decrease the dielectric loss and enhance dielectric insulation by achieving flat-on primary PVDF crystals in MLFs via nanoconfined melt-recrystallization. Based on simultaneous small- and wide-angle X-ray scattering experiments, edge-on lamellar crystals were observed for all as-extruded MLFs, regardless of different PVDF layer thicknesses. However, after melting at 180 °C followed by recrystallization, flat-on primary crystals were successfully achieved when the PVDF layer thickness was below 39 nm. Above 78 nm for the PVDF layer, major edge-on primary crystals with minor flat-on secondary crystals were observed. Furthermore, from leakage current, breakdown, lifetime, and electric displacement-electric field loop studies, MLFs with the flat-on primary crystals exhibited reduced loss and enhanced dielectric insulation as compared to as-extruded MLFs and those with edge-on primary/flat-on secondary crystals. This was attributed to the effective blockage of charge carriers by the flat-on PVDF primary crystals and their reduced ferroelectric switching.

36 MATERIALS SCIENCE↗