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At least 55 records · Page 3

Self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars

Oxide-metal-based hybrid materials have gained great research interest in recent years owing to their potential for multifunctionality, property coupling, and tunability. Specifically, oxide-metal hybrid materials in a vertically aligned nanocomposite (VAN) form could produce pronounced anisotropic physical properties, e.g., hyperbolic optical properties. Herein, self-assembled HfO 2 -Au nanocomposites with ultra-fine vertically aligned Au nanopillars (as fine as 3 nm in diameter) embedded in a HfO 2 matrix were fabricated using a one-step self-assembly process. The film crystallinity and pillar uniformity can be obviously improved by adding an ultra-thin TiN-Au buffer layer during the growth. Here, the HfO 2 -Au hybrid VAN films show an obvious plasmonic resonance at 480 nm, which is much lower than the typical plasmonic resonance wavelength of Au nanostructures, and is attributed to the well-aligned ultra-fine Au nanopillars. Coupled with the broad hyperbolic dispersion ranging from 1050 nm to 1800 nm in wavelength, and unique dielectric HfO 2 , this nanoscale hybrid plasmonic metamaterial presents strong potential for the design of future integrated optical and electronic switching devices.

36 MATERIALS SCIENCE↗

Wavelength-tunable infrared chiral metasurfaces with phase-change materials

Optical phase-change materials exhibit tunable permittivity and switching properties during phase transition, which offers the possibility of dynamic control of optical devices. Here, a wavelength-tunable infrared chiral metasurface integrated with phase-change material GST-225 is demonstrated with the designed unit cell of parallelogram-shaped resonator. By varying the baking time at a temperature above the phase transition temperature of GST-225, the resonance wavelength of the chiral metasurface is tuned in the wavelength range of 2.33 µm to 2.58 µm, while the circular dichroism in absorption is maintained around 0.44. The chiroptical response of the designed metasurface is revealed by analyzing the electromagnetic field and displacement current distributions under left- and right-handed circularly polarized (LCP and RCP) light illumination. Moreover, the photothermal effect is simulated to investigate the large temperature difference in the chiral metasurface under LCP and RCP illumination, which allows for the possibility of circular polarization-controlled phase transition. The presented chiral metasurfaces with phase-change materials offer the potential to facilitate promising applications in the infrared regime, such as chiral thermal switching, infrared imaging, and tunable chiral photonics.

36 MATERIALS SCIENCE↗

Multifunctional Metal–Oxide Nanocomposite Thin Film with Plasmonic Au Nanopillars Embedded in Magnetic La 0.67 Sr 0.33 MnO 3 Matrix

Searching for multifunctional materials with tunable magnetic and optical properties has been a critical task toward the implementation of future integrated optical devices. Vertically aligned nanocomposite (VAN) thin films provide a unique platform for multifunctional material designs. In this work, a new metal–oxide VAN has been designed with plasmonic Au nanopillars embedded in a ferromagnetic La 0.67 Sr 0.33 MnO 3 (LSMO) matrix. Such Au–LSMO nanocomposite presents intriguing plasmon resonance in the visible range and magnetic anisotropy property, which are functionalized by the Au and LSMO phase, respectively. Furthermore, the vertically aligned nanostructure of metal and dielectric oxide results in the hyperbolic property for near-field electromagnetic wave manipulation. Such optical and magnetic response could be further tailored by tuning the composition of Au and LSMO phases.

36 MATERIALS SCIENCE↗

Dynamically controlled random lasing with colloidal titanium carbide MXene

Control of lasing properties through tailorable and dynamically tunable materials and reconfigurable compositions can augment the performance of random lasers for a wide range of applications. Here, a colloid of randomly dispersed weakly scattering single-layer titanium carbide (Ti 3 C 2 T x ) MXene flakes embedded within rhodamine 101 gain medium is experimentally shown to provide feedback for random lasing. Additionally, in contrast to previously reported random laser systems where the optical properties of scatterers are static, the relative permittivity of Ti 3 C 2 T x MXene flakes can be varied under optical pumping due to the saturable absorption properties. Numerical simulations indicate that the observed nonlinear response of Ti 3 C 2 T x MXene flakes enables dynamically tunable random lasing. Thus, pumping the Ti 3 C 2 T x MXene flakes with a second optical source decreases the gain threshold required to obtain random lasing. Also, using numerical simulations, it is shown that the control over the intensity of the second pump enables tuning the field distribution of the random lasing modes. Considering the diversity of the MXenes family, the proposed MXene colloidal metamaterial design opens up a new avenue to advanced control of lasing properties for photonic applications.

36 MATERIALS SCIENCE↗

Confinement of 1D Chain and 2D Layered CuI Modules in K-INA-R Frameworks via Coordination Assembly: Structure Regulation and Semiconductivity Tuning

Herein, we present a new series of CuI-based hybrid materials with tunable structures and semiconducting properties. Furthermore, the CuI inorganic modules can be tailored into a one-dimensional (1D) chain and two-dimensional (2D) layer and confined/stabilized in coordination frameworks of potassium isonicotinic acid (HINA) and its derivatives (HINA-R, R = OH, NO 2 , and COOH). The resulting CuI-based hybrid materials exhibit interesting semiconducting behaviors associated with the dimensionality of the inorganic module; for instance, the structures containing the 2D-CuI module demonstrate significantly enhanced photoconductivity with a maximum increase of five orders of magnitude compared to that of the structures containing the 1D-CuI module. They also represent the first CuI-bearing hybrid chemiresistive gas sensors for NO 2 with boosted sensing performance and sensitivity at multiple orders of magnitude over that of the pristine CuI. Particularly, the sensing ability of CuI-K-INA containing both 1D- and 2D-CuI modules is comparable to those of the best NO 2 chemiresistors reported thus far.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Self-Assembly of a Triblock Copolymer in the Presence of a Rigid Conjugated Polyelectrolyte

The properties of conducting polymers are strongly influenced by structural changes induced by long-range order, which can be achieved by using block copolymers that self-assemble into crystalline structures. These blends result in unique mesophases distinct from the pure components with self-assembly behavior modulated by solution conditions and polymer architectures. High-throughput small-angle X-ray scattering data of aqueous Pluronic P123 (PEO 20 –PPO 70 –PEO 20 ) and conjugated polyelectrolyte poly[3-(potassium-4-butanoate) thiophene-2,5-diyl] (PPBT) blends at various concentrations and temperatures were automatically classified into phase maps by autophasemap, an unsupervised statistical analysis algorithm. The outlined phase boundaries revealed that adding PPBT to high P123 concentrations induced a transition from cubicly ordered spherical micelles to hexagonally packed cylindrical micelles. Shear alignment via rheological small-angle neutron scattering of the blends produced monolithic oriented cubic and hexagonal crystal gels. Furthermore, these insights into the self-assembly of conductive polymer blends will aid in the design of soft materials with tunable structural and electronic properties.

36 MATERIALS SCIENCE↗

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)↗

Antiferromagnetic Ordering in A One‐Dimensional Organic Copper Chloride Hybrid Insulator

Abstract Low dimensional (LD) organic metal halide hybrids (OMHHs) have recently emerged as new generation functional materials with exceptional structural and property tunability. Despite the remarkable advances in the development of LD OMHHs, optical properties have been the major functionality extensively investigated for most of LD OMHHs developed to date, while other properties, such as magnetic and electronic properties, remain significantly under‐explored. Here, we report for the first time the characterization of the magnetic and electronic properties of a 1D OMHH, organic‐copper (II) chloride hybrid (C 8 H 22 N 2 )Cu 2 Cl 6 . Owing to the antiferromagnetic coupling between Cu atoms through chloride bridges in 1D [Cu 2 Cl 6 2− ] ∞ chains, (C 8 H 22 N 2 )Cu 2 Cl 6 is found to exhibit antiferromagnetic ordering with a Néel temperature of 24 K. The two‐terminal (2T) electrical measurement on a (C 8 H 22 N 2 )Cu 2 Cl 6 single crystal reveals its insulating nature. This work shows the potential of LD OMHHs as a highly tunable quantum material platform for spintronics.

Islam, Md Sazedul↗

Polymorphism and Phase Control in Dion–Jacobson 2D 3-(Aminomethyl)piperidinium-Based Metal Iodide Perovskites

Two-dimensional halide perovskites exhibit rich structural diversity and tunable optoelectronic properties, making them promising materials for energy, sensing, and photonic applications. In this work, we report the structural mapping of four distinct polymorphs, γ (P2 1 /c), β (P4/mbm), α (P4/mmm), and δ (Cmcm) in the two-dimensional iodoplumbate, iodostannate, and iodogermanate perovskite so-called Dion-Jacobson series (3AMP)MI4 (M = Sn, Pb, Ge), where 3AMP is 3-(aminomethyl)piperidinium. The phases exhibit systematic evolution in octahedral distortion, lattice symmetry, and metal–halide geometry, enabling structural control over optoelectronic properties. Notably, the α-phase of (3AMP)SnI 4 represents a rare, ambient-stable, high-symmetry structure for Sn-based perovskites, without a phase transition down to 100 K. Variable-temperature single-crystal diffraction, powder x-ray diffraction (PXRD), and calorimetry reveal metal- and temperature-dependent polymorph interconversions, including the emergence of long range supercell reflections in Pb-rich compositions at low temperature. Optical spectroscopy and photoelectron yield spectroscopy confirm band gap tunability and band alignment trends, highlighting symmetry-dependent shifts and anomalous band gap bowing in mixed-metal systems, verified by electronic structure calculations. Calculations additionally indicate that the higher symmetry phases have reduced electron and hole effective masses compared to the lower symmetry phases.

36 MATERIALS SCIENCE↗

Enhanced Selectivity and Stability of Finned Ferrierite Catalysts in Butene Isomerization

Abstract Designing zeolite catalysts with improved mass transport properties is crucial for restrictive networks of either one‐ or two‐dimensional pore topologies. Here, we demonstrate the synthesis of finned ferrierite (FER), a commercial zeolite with two‐dimensional pores, where protrusions on crystal surfaces behave as pseudo nanoparticles. Catalytic tests of 1‐butene isomerization reveal a 3‐fold enhancement of catalyst lifetime and an increase of 12 % selectivity to isobutene for finned samples compared to corresponding seeds. Electron tomography was used to confirm the identical crystallographic registry of fins and seeds. Time‐resolved titration of Brønsted acid sites confirmed the improved mass transport properties of finned ferrierite compared to conventional analogues. These findings highlight the advantages of introducing fins through facile and tunable post‐synthesis modification to impart material properties that are otherwise unattainable by conventional synthesis methods.

Dai, Heng↗

Tunable plasmon-enhanced second-order optical nonlinearity in transition-metal dichalcogenide nanotriangles (Final Report for SC0008712)

The control of light-matter interaction at the nanoscale is a grand challenge that cuts across modern photonics, plasmonics, and optoelectronics. The development of simulation tools for predictive modeling of nanostructured light emitters and absorbers is critical to successfully tackling this grand challenge. Existing state-of-the-art tools are not suitable for the following reasons: a) Phenomenological models of materials, commonly employed in the full-wave solutions to Maxwell’s equations, are fit to experimental data for bulk materials and fall short when attempting to analyze nanostructures. b) Nonlinearities in optical response can arise solely from nanostructuring, and require time-dependent quantum electronic transport techniques to capture. c) Emergent materials with exotic and tunable physical properties are increasingly used, but their properties are very sensitive to the substrate, impurities, and edge termination, and require an accurate description of interband and intraband processes, as well as dissipation. d) Microscopic modeling of electronic transport usually employs simplified electrodynamics, and realistic models that couple full electronic transport with full-wave electrodynamics are needed for accurate photonics simulations. The objective of this project was to computational tools that will overcome the limitations faced by current modeling tools and provide an unprecedented level of accuracy for predictive modeling of light-matter interaction at the nanoscale.

36 MATERIALS SCIENCE↗

Supramolecular Assembly of Multielement Ribbon-like Structures Derived from Halide Perovskites

Halide perovskites are crucial materials with broad applications owing to their exceptional optoelectronic properties. Vacancy-ordered double perovskites, featuring highly tunable transition metal sites, enable controllable optoelectronic properties through multielement compositional design. Here, in this study, we introduced 18-crown-6 into the vacancy-ordered double perovskites system and developed two-dimensional ribbon-like single crystals (18C6@K) 2 {PtSnTeIrRe} 1 Cl 6 via an antisolvent supramolecular assembly method, demonstrating morphology modulation through multielement composition design. The crystals crystallize in the centrosymmetric space group $P\bar{1}$. The dumbbell-shaped structural units (crown ether@A)2MX6 pack along a and b axes to form a 2-dimensional (2D) monolayer, and these monolayers further stack along the c axis to generate the ribbon-like single crystals. Energy-dispersive X-ray spectroscopy (EDX) qualitatively confirmed the uniform distribution of the five transition metals throughout the crystal, while inductively coupled plasma atomic emission spectroscopy (ICP–AES) quantitatively verified their atomic ratios. We further investigated the origin of the morphology, distinct from the previously reported cube-like single crystals with the $R\bar{3}$ space group. When acetonitrile was used as the solvent, three-dimensional crystals with $R\bar{3}$ symmetry were obtained, whereas dimethylformamide (DMF) was essential for forming two-dimensional ribbon-like single crystals. The essential role of DMF could be ascribed to its capability to maintain a higher concentration of the building blocks. Moreover, Ir 4+ and Pt 4+ cations also played critical roles in inducing the two-dimensional ribbon-like morphology. The three-element (18C6@K) 2 {PtSnTe}1Cl 6 single crystals exhibited bright yellow emission under 375 nm laser excitation, demonstrating the tunability of optoelectronic properties of this class of material.

Zhu, Heqing [University of California, Berkeley, C↗

Ionically Active MXene Nanopore Actuators

Reversible electrochemical intercalation of cations into the interlayer space of 2D materials induces tunable physical and chemical properties in them. In MXenes, a large class of recently developed 2D carbides and nitrides, low intercalation energy, high storage capacitance, and reversible intercalation of various cations have led to their improved performance in sensing and energy storage applications. In this work, a coupled nanopore-actuator system where an ultrathin free-standing MXene film serves as a nanopore support membrane and ionically active actuator is reported. In this system, the contactless MXene membrane in the electric field affects the cation movement in the field through their (de)intercalation between individual MXene flakes. This results in reversible swelling and contraction of the membrane monitored by ionic conductance through the nanopore. This unique nanopore coupled to a mechanical actuation system could provide new insights into designing single-molecule biosensing platforms at the nanoscale.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Synthesis and Blending of Two Poly(ethylene- co -vinyl alcohol) Polymers with Mixed 1,2-Diol Stereochemistry

Parallel pathways for the postpolymerization modification of double bonds in a polycyclooctene (PCOE) backbone generate vicinal 1,2-diol-containing polymers with mixed but opposite stereochemistry, depending on the trans:cis ratio of the C═C in PCOE. Beginning from the same batch of PCOE, epoxidation and subsequent ring-opening with sulfuric acid and water produce a polymer with the majority erythro diols, whereas an osmium-catalyzed dihydroxylation results in diols in the majority threo orientations. These postpolymerization modification approaches enable access to previously unexplored polymers with a mixture of erythro and threo diols, offering tunable diol stereochemistry to tailor material properties. The majority erythro diols lead to hexagonal crystallites with higher melting temperatures and overall crystallinity when compared to the majority threo diols that form monoclinic crystallites. When blended, the two diastereomers phase separate as evidenced by distinct melting endotherms and crystal structures corresponding to the two component polymers, suggesting a route to tune the barrier or mechanical properties. Furthermore, this investigation synthesized polymers with mixed stereochemical diols and elucidated the thermal and morphological properties of regioregular linear poly(ethylene-co-vinyl alcohols) and their blends.

1,2-diols↗

Investigating property-porosity relationships for micro-architected lattice structures

Micro-architected structures are increasingly valued for their light weight and tunable mechanical properties; this class of material includes sheet structures like the Schöen gyroid and beam lattices like the octet. For design purposes, it is critical to understand how to tune the relative density (RD) to obtain desired mechanical properties. This study investigates the mechanical response of Ti-6Al-4V gyroid structures, spanning a broad range of RDs (0.03–0.90), unit cell sizes (1–4 cm), and sheet thicknesses (0.2–7.8 mm). Results demonstrate that the classical Gibson-Ashby power law scaling between RD and modulus and yield stress does not adequately capture the response over a wide range of RDs, nor does it extrapolate correctly to the fully dense solid. Analytical models, in concert with experimental results and high-fidelity finite element calculations, show that the deviation from Gibson-Ashby reflects a transition from structure-dominated to material-dominated behavior. Distinctions are drawn between scaling relationships and property-porosity models, and an analytical model is proposed to better capture the evolution of mechanical properties with RD. These observations are mirrored in other architected topologies, like the octet, and highlight the importance of understanding the relationship between mechanical properties and geometry for design purposes.

Materials science↗

Bias-Modulated ALD of ZnO: Insights into Precursor-Surface Interactions for ZnO Films

Atomic layer deposition (ALD) is widely used to deposit conformal thin films but is often limited in the tunability of the resulting material’s properties. Substrate bias and electric fields alter precursor-surface interactions and provide means to tune material properties. To explore this, we performed zinc oxide (ZnO) ALD using diethylzinc (DEZ) and water on silicon native oxide substrates at 150 °C in a sample holder designed to create a static electrical field by biasing one plate of a parallel plate capacitor-style sample holder during deposition. ZnO films prepared in an electric field/on a biased sample holder were thinner, changed relative crystalline composition, and contained more carbon compared to samples grown in identical sample holders without bias. The thickness was independent of the magnitude of the eletric field between plates, indicating that the primary driver for the change was substrate biasing not the electric field between plates of the parallel plate capacitor-style sample holder. Density functional theory calculations showed enhanced electron migration between dissociatively adsorbed DEZ molecules and the ZnO (002) facet with increasing force from an electric field at the substrate surface, which strengthens the electronic interactions between the surface and the adsorbate. These models offer a compelling explanation for the inhibited growth, changes in the crystallinity, and increase in carbon content of films grown in an electric field/on biased plates.

Jones, Jessica C. (ORCID:0000000174754620)↗

Orientation-Controlled Large-Area Epitaxial PbI 2 Thin Films with Tunable Optical Properties

Lead iodide (PbI 2 ) as a layered material has emerged as an excellent candidate for optoelectronics in the visible and ultraviolet regime. Micrometer-sized flakes synthesized by mechanical exfoliation from bulk crystals or by physical vapor deposition have shown a plethora of applications from low-threshold lasing at room temperature to high-performance photodetectors with large responsivity and faster response. However, large-area centimeter-sized growth of epitaxial thin films of PbI 2 with well-controlled orientation has been challenging. Additionally, the nature of grain boundaries in epitaxial thin films of PbI 2 remains elusive. Here, we use mica as a model substrate to unravel the growth mechanism of large-area epitaxial PbI 2 thin films. The partial growth leading to uncoalesced domains reveals the existence of inversion domain boundaries in epitaxial PbI 2 thin films on mica. Combining the experimental results with first-principles calculations, we also develop an understanding of the thermodynamic and kinetic factors that govern the growth mechanism, which paves the way for the synthesis of high-quality large-area PbI 2 on other substrates and heterostructures of PbI 2 on single-crystalline graphene. Here, the ability to reproducibly synthesize high-quality large-area thin films with precise control over orientation and tunable optical properties could open up unique and hitherto unavailable opportunities for the use of PbI 2 and its heterostructures in optoelectronics, twistronics, substrate engineering, and strain engineering.

2D materials↗

A Dual Approach in Direct Ink Writing of Thermally Cured Shape Memory Rubber Toughened Epoxy

Bisphenol A-based epoxies are much used in a wide range of composite and coating applications due to their excellent thermomechanical properties. However, their 3D printability remains a challenge with most reported materials suffering from high brittleness and low toughness. In this work, we have described especially modified epoxy resins that enable 3D printing with both fast and slow curing rates. These materials exhibit greatly enhanced toughness, tunable thermomechanical properties, and excellent shape memory behavior. Two different printing systems, including a two-part static mixing printhead and a single extrusion printhead, were developed for fast- and slow-curing epoxies, respectively. The rheology of inks in both systems has been modified into printable thixotropic fluids with the aid of silica nanoparticles and other additives. Epoxide-functionalized telechelic polybutadiene was added into the resins, which are then introduced inside the epoxy network after cross-linking. The addition of polybutadiene rubber significantly improves the toughness (over 135%), fracture strain (over 200%), and shape memory behavior. By adding different amounts of the rubber telechelic, thermomechanical properties, including modulus, elongation, and Tg of epoxy, can be well controlled in a wide range to satisfy different applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗