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At least 451 records · Page 25

Tunable Nanoscale Evolution and Topological Phase Transitions of a Polar Vortex Supercrystal

Here, understanding the phase transitions and domain evolutions of mesoscale topological structures in ferroic materials is critical to realizing their potential applications in next-generation high-performance storage devices. Here, the behaviors of a mesoscale supercrystal are studied with 3D nanoscale periodicity and rotational topology phases in a PbTiO 3 /SrTiO 3 (PTO/STO) superlattice under thermal and electrical stimuli using a combination of phase-field simulations and X-ray diffraction experiments. A phase diagram of temperature versus polar state is constructed, showing the formation of the supercrystal from a mixed vortex and α-twin state and a temperature-dependent erasing process of a supercrystal returning to a classical α-twin structure. Under an in-plane electric field bias at room temperature, the vortex topology of the supercrystal irreversibly transforms to a new type of stripe-like supercrystal. Under an out-of-plane electric field, the vortices inside the supercrystal undergo a topological phase transition to polar skyrmions. These results demonstrate the potential for the on-demand manipulation of polar topology and transformations in supercrystals using electric fields. The findings provide a theoretical understanding that may be utilized to guide the design and control of mesoscale polar structures and to explore novel polar structures in other systems and their topological nature.

P=phase-field simulations↗

Optical Control of Adaptive Nanoscale Domain Networks

Adaptive networks can sense and adjust to dynamic environments to optimize their performance. Understanding their nanoscale responses to external stimuli is essential for applications in nanodevices and neuromorphic computing. However, it is challenging to image such responses on the nanoscale with crystallographic sensitivity. Here, the evolution of nanodomain networks in (PbTiO 3 ) n /(SrTiO 3 ) n superlattices (SLs) is directly visualized in real space as the system adapts to ultrafast repetitive optical excitations that emulate controlled neural inputs. The adaptive response allows the system to explore a wealth of metastable states that are previously inaccessible. Their reconfiguration and competition are quantitatively measured by scanning x-ray nanodiffraction as a function of the number of applied pulses, in which crystallographic characteristics are quantitatively assessed by assorted diffraction patterns using unsupervised machine-learning methods. The corresponding domain boundaries and their connectivity are drastically altered by light, holding promise for light-programable nanocircuits in analogy to neuroplasticity. Phase-field simulations elucidate that the reconfiguration of the domain networks is a result of the interplay between photocarriers and transient lattice temperature. The demonstrated optical control scheme and the uncovered nanoscopic insights open opportunities for the remote control of adaptive nanoscale domain networks.

36 MATERIALS SCIENCE↗

Decoding THz‐Driven Dynamic Fingerprints of Ferroelectric Nanotwin Networks

Ultrafast polarization dynamics in ferroelectrics are of considerable interest for high-speed tunable dielectrics and electro-optics. Extended domain wall networks formed in ferroelectric twin nanodomains can support collective dynamics in the terahertz regime but require techniques that track polarization and strain evolution driven by ultrafast stimulus. Here, we use multi-modal probing of THz-pulse-driven excitations in PbTiO 3 /SrTiO 3 superlattices by combining X-ray free electron laser measurements that directly tracks lattice changes, with optical second harmonic generation that tracks the electronic potential coupled with the lattice potential. Dynamical phase-field modeling enables fingerprinting of these collective modes as superpositions of domain “breathing” through wall oscillations and polarization “rotations” with still walls. Ultrafast domain wall motion at 0.1–0.5 THz is observed at practical fields of 100 kV/cm with wall velocities of >4000 m/s, approaching typical speed of sound in PbTiO 3 . A unique “charging” mode is discovered that can electrically charge and discharge domain walls on ∼4 ps time scale thus dynamically tuning wall conductivity. Integrated experimental and theoretical fingerprinting of the dynamical landscape presented here enables ultrafast control of ferroics for high-speed microelectronics and optical applications.

THz dynamics↗

Orientated Growth of Ultrathin Tellurium by van der Waals Epitaxy

Abstract Tellurium, as an elemental van der Waals semiconductor, has intriguing anisotropic physical properties owing to its inherent 1D crystal structure. To exploit the anisotropic and thickness‐dependent behavior, it is important to realize orientated growth of ultrathin tellurium. Here, van der Waals epitaxial growth of Te on the surface of 2D transition metal dichalcogenides is systematically investigated. Orientated growth of Te with a thickness down to 5 nm is realized on three‐fold symmetric substrates (WSe 2 , WS 2 , MoSe 2 , and MoS 2 ), where the atomic chains of Te are aligned with the armchair directions of substrates. 1D/2D moiré superlattices are observed for the Te/WSe 2 heterostructure. This method is extended to the growth of SeTe alloys, providing flexibility for band engineering. Finally, growth of textured Te film is demonstrated on the lower‐symmetry surface of WTe 2 .

Zhao, Chunsong↗

Electronic Coupling of Metal–to–Insulator Transitions in Nickelate–Based Heterostructures

In rare earth nickelates, the metal-to-insulator transition observed as a function of temperature can be described using an electronic and a structural order parameter. The electronic one is linked to the electronic disproportionation observed below the transition temperature and the structural one characterizes the breathing mode that develops in the low temperature phase. Here SmNiO 3 /NdNiO 3 superlattices are grown with insulating LaAlO 3 spacer layers to study the unusual coupling of metal-to- insulator transitions observed at SmNiO 3 /NdNiO 3 interfaces and determine the role of the two order parameters. Temperature-dependent transport measurements reveal that a single unit cell of LaAlO 3 inserted between SmNiO 3 and NdNiO 3 leads to a complete decoupling of the metal-to-insulator transitions suggesting that the order parameter controlling the coupling is the electronic one.

36 MATERIALS SCIENCE↗

Importance of Superstructure in Stabilizing Oxygen Redox in P3‐Na 0.67 Li 0.2 Mn 0.8 O 2

Abstract Activation of oxygen redox represents a promising strategy to enhance the energy density of positive electrode materials in both lithium and sodium‐ion batteries. However, the large voltage hysteresis associated with oxidation of oxygen anions during the first charge represents a significant challenge. Here, P3‐type Na 0.67 Li 0.2 Mn 0.8 O 2 is reinvestigated and a ribbon superlattice is identified for the first time in P3‐type materials. The ribbon superstructure is maintained over cycling with very minor unit cell volume changes in the bulk while Li ions migrate reversibly between the transition metal and Na layers at the atomic scale. In addition, a range of spectroscopic techniques reveal that a strongly hybridized Mn 3d–O 2p favors ligand‐to‐metal charge transfer, also described as a reductive coupling mechanism, to stabilize reversible oxygen redox. By preparing materials under three different synthetic conditions, the degree of ordering between Li and Mn is varied. The sample with the maximum cation ordering delivers the largest capacity regardless of the voltage windows applied. These findings highlight the importance of cationic ordering in the transition metal layers, which can be tuned by synthetic control to enhance anionic redox and hence energy density in rechargeable batteries.

36 MATERIALS SCIENCE↗

Probing the Consequences of Cubic Particle Shape and Applied Field on Colloidal Crystal Engineering with DNA

Abstract In a magnetic field, cubic Fe 3 O 4 nanoparticles exhibit assembly behavior that is a consequence of a competition between magnetic dipole–dipole and ligand interactions. In most cases, the interactions between short hydrophobic ligands dominate and dictate assembly outcome. To better tune the face‐to‐face interactions, cubic Fe 3 O 4 nanoparticles were functionalized with DNA. Their assembly behaviors were investigated both with and without an applied magnetic field. Upon application of a field, the tilted orientation of cubes, enabled by the flexible DNA ligand shell, led to an unexpected crystallographic alignment of the entire superlattice, as opposed to just the individual particles, along the field direction as revealed by small and wide‐angle X‐ray scattering. This observation is dependent upon DNA length and sequence and cube dimensions. Taken together, these studies show how combining physical and chemical control can expand the possibilities of crystal engineering with DNA.

Urbach, Zachary J.↗

Probing the Consequences of Cubic Particle Shape and Applied Field on Colloidal Crystal Engineering with DNA

In a magnetic field, cubic Fe 3 O 4 nanoparticles exhibit assembly behavior that is a consequence of a competition between magnetic dipole-dipole and ligand interactions. In most cases, the interactions between short hydrophobic ligands dominate and dictate assembly outcome. To better tune the face-to-face interactions, cubic Fe3O4 nanoparticles were functionalized with DNA. Their assembly behaviors were investigated both with and without an applied magnetic field. Upon application of a field, the tilted orientation of cubes, enabled by the flexible DNA ligand shell, led to an unexpected crystallographic alignment of the entire superlattice, as opposed to just the individual particles, along the field direction as revealed by small and wide-angle X-ray scattering. This observation is dependent upon DNA length and sequence and cube dimensions. Taken together, these studies show how combining physical and chemical control can expand the possibilities of crystal engineering with DNA.

36 MATERIALS SCIENCE↗

Reconfiguration of Amorphous Complex Oxides: A Route to a Broad Range of Assembly Phenomena, Hybrid Materials, and Novel Functionalities

This work demonstrate that reconfiguration of amorphous oxide layers drives the assembly of oxide-based and freestanding nanomembranes into 3D structures with a radius of a few hundred nanometers. Reconfiguration-driven assembly is a versatile approach to impart large strains and strain gradients in a broad palette of complex oxides. This capability allows for manipulating and enhancing ferroelectricity, flexoelectricity, piezoelectricity, superconductivity, and ferromagnetism in complex oxides. Moreover, by the approach presented in this work, strain-engineered oxides are obtained in the form of 3D structures that can be fabricated in parallel on any substrate, including large-area and single crystalline semiconductor substrates. This approach will create a vast expanse of possibilities to investigate and leverage strain-tunable effects in amorphous, poly-crystalline, and single-crystalline complex oxides. Reconfiguration-driven assembly of NMs also allows combining different materials in a radial geometry and through scalable processes. For example, radial superlattices of Si (or GaAs) and various complex oxides or alternating layers of different complex oxides (e.g., SrTiO 3 and LaAlO 3 ) could be fabricated by release and heating of bilayer NMs. Here, a broad palette of electronic band structures and spin–orbit interactions could then be obtained by tailoring the curvature of the self-assembled NMs and the materials that the heterostructure comprises.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Selective Catalytic Behavior Induced by Crystal–Phase Transformation in Well–Defined Bimetallic Pt–Sn Nanocrystals

The Pt-Sn bimetallic system is a much studied and commercially used catalyst for propane dehydrogenation. The traditionally prepared catalyst, however, suffers from inhomogeneity and phase separation of the active Pt–Sn phase. Colloidal chemistry offers a route for the synthesis of Pt–Sn bimetallic nanoparticles (NPs) in a systematic, well-defined, tailored fashion over conventional methods. Here, the successful synthesis of well-defined ≈2 nm Pt, PtSn, and Pt 3 Sn nanocrystals with distinct crystallographic phases is reported; hexagonal close packing (hcp) PtSn and fcc Pt 3 Sn show different activity and stability depending on the hydrogen-rich or poor environment in the feed. Moreover, face centred cubic (fcc) Pt 3 Sn/Al 2 O 3 , which exhibited the highest stability compared to hcp PtSn, shows a unique phase transformation from an fcc phase to an L1 2 -ordered superlattice. Contrary to PtSn, H 2 cofeeding has no effect on the Pt 3 Sn deactivation rate. Finally, the results reveal structural dependency of the probe reaction, propane dehydrogenation, and provide a fundamental understanding of the structure–performance relationship on emerging bimetallic systems.

36 MATERIALS SCIENCE↗

Anomalous X-Ray Scattering and Extended X-Ray Absorption Fine Structure Study of the Local Structure of CrFeCoNiMo x (x = 0.11, 0.18, and 0.23) High-Entropy Alloys

Anomalous x-ray scattering (AXS) and extended x-ray absorption fine structure (EXAFS) were used to determine the local structure of Mo in CrFeCoNiMo x (x = 0.11, 0.18, and 0.23), a high-entropy alloy with a face-centered cubic (FCC) lattice. No superlattice peaks were observed down to the 10 -4 intensity level. This observation along with the nearly constant decrease of the FCC diffraction peaks above the Mo K absorption edge suggests that Mo atoms have no preferred site occupancy in the FCC lattice. Modeling of the EXAFS data suggests a local chemical order in CrFeCoNiMo x , where in Mo-rich samples (e.g., x = 0.23), Mo atoms are preferably surrounded by lighter atoms, such as Cr.

46 INSTRUMENTATION RELATED TO NUCLEAR SCIENCE AND ↗

The exceedingly strong two-dimensional ferromagnetism in bi-atomic layer SrRuO 3 with a critical conduction transition

In recent years, few-layer or even monolayer ferromagnetic materials have drawn a great deal of attention due to the promising integration of two-dimensional (2D) magnets into next-generation spintronic devices. The SrRuO 3 monolayer is a rare example of stable 2D magnetism under ambient conditions, but only weak ferromagnetism or antiferromagnetism has been found. The bi-atomic layer SrRuO3 as another environmentally inert 2D magnetic system has been paid less attention heretofore. Here we study both the bi-atomic layer and monolayer SrRuO 3 in (SrRuO 3 ) n /(SrTiO 3 ) m (n = 1, 2) superlattices in which the SrTiO 3 serves as a non-magnetic and insulating space layer. Although the monolayer exhibits arguably weak ferromagnetism, we find that the bi-atomic layer exhibits exceedingly strong ferromagnetism with a T c of 125 K and a saturation magnetization of 1.2 μ B /Ru, demonstrated by both superconducting quantum interference device (SQUID) magnetometry and element-specific X-ray circular dichroism. Moreover, in the bi-atomic layer SrRuO 3 , we demonstrate that random fluctuations and orbital reconstructions inevitably occurring in the 2D limit are critical to the electrical transport, but are much less critical to the ferromagnetism. Our study demonstrates that the bi-atomic layer SrRuO 3 is an exceedingly strong 2D ferromagnetic oxide which has great potentials for applications of ultracompact spintronic devices.

36 MATERIALS SCIENCE↗

Novel self-assembled two-dimensional layered oxide structure incorporated with Au nanoinclusions towards multifunctionalities

Two-dimensional (2D) layered oxides have recently attracted wide attention owing to the strong coupling among charges, spins, lattice, and strain, which allows great flexibility and opportunities in structure designs as well as multifunctionality exploration. In parallel, plasmonic hybrid nanostructures exhibit exotic localized surface plasmon resonance (LSPR) providing a broad range of applications in nanophotonic devices and sensors. A hybrid material platform combining the unique multifunctional 2D layered oxides and plasmonic nanostructures brings optical tuning into the new level. Here, a novel self-assembled Bi 2 MoO 6 (BMO) 2D layered oxide incorporated with plasmonic Au nanoinclusions has been demonstrated via one-step pulsed laser deposition (PLD) technique. Comprehensive microstructural characterizations, including scanning transmission electron microscopy (STEM), differential phase contrast imaging (DPC), and STEM tomography, have demonstrated the high epitaxial quality and particle-in-matrix morphology of the BMO-Au nanocomposite film. DPC-STEM imaging clarifies the magnetic domain structures of BMO matrix. Three different BMO structures including layered supercell (LSC) and superlattices have been revealed which is attributed to the variable strain states throughout the BMO-Au film. Owing to the combination of plasmonic Au and layered structure of BMO, the nanocomposite film exhibits a typical LSPR in visible wavelength region and strong anisotropy in terms of its optical and ferromagnetic properties. This study opens a new avenue for developing novel 2D layered complex oxides incorporated with plasmonic metal or semiconductor phases showing great potential for applications in multifunctional nanoelectronics devices.

36 MATERIALS SCIENCE↗

Differences in Sb 2 Te 3 growth by pulsed laser and sputter deposition

High quality van der Waals chalcogenides are important for phase change data storage, thermoelectrics, and spintronics. Using a combination of statistical design of experiments and density functional theory, we clarify how out-of-equilibrium van der Waals epitaxial deposition methods can improve the crystal quality of Sb 2 Te 3 films. We compare films grown by radio frequency sputtering and pulsed laser deposition (PLD). The growth factors that influence the crystal quality for each method are different. For PLD grown films a thin amorphous Sb 2 Te 3 seed layer most significantly influences the crystal quality. In contrast, the crystalline quality of films grown by sputtering is rather sensitive to the deposition temperature and less affected by the presence of a seed layer. This difference is somewhat surprising as both methods are out-of-thermal-equilibrium plasma-based methods. Non-adiabatic quantum molecular dynamics simulations show that this difference originates from the density of excited atoms in the plasma. The PLD plasma is more intense and with higher energy than that used in sputtering, and this increases the electronic temperature of the deposited atoms, which concomitantly increases the adatom diffusion lengths in PLD. In contrast, the adatom diffusivity is dominated by the thermal temperature for sputter grown films. These results explain the wide range of Sb 2 Te 3 and superlattice crystal qualities observed in the literature. Finally, these results indicate that, contrary to popular belief, plasma-based deposition methods are suitable for growing high quality crystalline chalcogenides.

36 MATERIALS SCIENCE↗

Anisotropic structure and optical engineering of strontium titanate and zirconia responding to sequential hydrogen and helium irradiation

Unraveling the correlation between strain engineering with anisotropic optical properties via nanoscale defects gradually evolved into a strategy for fundamental studies and technological applications, yet it remains understudied in functional complex oxides compared to metals and semiconductors. Here, the methodology of strain engineering for the determination of the lattice parameters, parallel/normal to the sample surface, in the individual layers of single-crystalline superlattices is derived, which is based on analysis of high-angle X-ray diffraction measurements in combination with diffraction reciprocal space mapping. With modeling that takes into account the effect of elastic properties, two elastically anisotropic materials, SrTiO 3 and ZrO 2 , have been compared in terms of defect-induced elastic strain caused by individual and sequential H + and He 2+ irradiation. The anisotropic lattice swelling with corresponding refractive index, and obstructive behavior of elastic strain recovery are demonstrated in SrTiO 3 , while approaching strain behaviors accompanied by isotropic refractive index distribution in both orientations are confirmed in ZrO 2 . Under sequential He 2+ /H + irradiation, pre-existing He-vacancy complexes acted as vacancy traps, preferentially capturing H + clusters to induce lattice distortion and enhance absorption. Nanohardness increments (ΔH) calculated by the DBH model matched nanoindentation results, confirming that sequential irradiation generated higher indentation yield stress than individual irradiations.

Anisotropic expansion↗

Colloidal phenomena reflect the interplay between interfacial solution structure, interparticle forces, and dynamical response

The physical and chemical properties of colloidal systems are central to both natural and synthetic processes that enable a wide range of energy and environmental applications. These properties are an emergent outcome of the structure that colloidal systems adopt in response to the interplay of electrical, van der Waals, hydration, and steric forces coupled to the inherent fluctuations of the system. Here, in this study, we review the nature of those forces and show how variations in their relative importance lead to distinct free energy landscapes and consequent dynamic behaviors, illustrated for colloidal dispersions, nanocrystal superlattices, and mesocrystlline solids formed through oriented attachment. We end by discussing the challenges to future progress arising from the need to seamless couple from molecular to particle to ensemble scales.

42 ENGINEERING↗

Nanocrystal programmable assembly beyond hard spheres (or shapes) and other (simple) potentials

Ligands are the key to almost any strategy in the assembly of programmable nanocrystals (or nanoparticles) and must be accurately considered in any predictive model. Hard Spheres (or Shapes) provide the simplest and yet quite successful approach to assembly, with remarkable sophisticated predictions verified in experiments. There are, however, many situations where hard spheres/shapes predictions fail. This prompts three important questions: In what situations should hard spheres/shapes models be expected to work? and when they do not work, Is there a general model that successfully corrects hard sphere/shape predictions? and given other successful models where ligands are included explicitly, and of course, numerical simulations, can we unify hard sphere/shape models, explicit ligand models and all atom simulations? . Further, the Orbifold Topological Model (OTM) provides a positive answer to these three questions. In this paper, I give a detailed review of OTM, describing the concept of ligand vortices and how it leads to spontaneous valence and nanoparticle “eigenshapes” while providing a prediction of the lattice structure, without fitting parameters, which accounts for many body effects not captured by (two-body) potentials. I present a thorough survey of experiments and simulations and show that, to this date, they are in full agreement with the OTM predictions. I conclude with a discussion on whether NC superlattices are equilibrium structures and some significant challenges in structure prediction.

36 MATERIALS SCIENCE↗

Two-dimensional assembly of gold nanoparticles grafted with charged-end-group polymers

We introduced charged terminal groups to polymers that graft nanoparticles enable Coulombic control over their assembly by tuning the pH and salinity of their aqueous suspensions. Gold nanoparticles (AuNPs) are grafted with poly (ethylene glycol) (PEG) terminated with CH 3 (charge-neutral), COOH (negatively charged) or NH 2 groups (positively charged), and characterized with dynamic light scattering, ζ-potential, and thermal gravimetric analysis. Liquid surface X-ray reflectivity (XR) and grazing incidence small-angle X-ray scattering (GISAXS) are used to determine the density profile and in-plane structure of the AuNPs assembly at the aqueous surface. Assembly of PEG-AuNPs at the liquid/vapor interface is tunable by adjusting pH or salinity for COOH but less for NH 2 terminals. The distinct assembly behaviors are attributed to the overall charge of PEG-AuNPs as well as PEG conformation. COOH-PEG corona is more compact than those of the other terminal groups, leading to a crystalline structure with a smaller superlattice. The net charge per particle depends not only on the PEG terminal groups but also on the cation sequestration of PEG and the intrinsic negative charge of the AuNP surface. The closeness to overall charge neutrality, and hydrogen bonding in play, brought by NH 2 -PEG, drive NH 2 -PEG-AuNPs to assembly and crystallinity without additives to the suspensions.

36 MATERIALS SCIENCE↗