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At least 127 records · Page 7

Large exciton binding energy in a bulk van der Waals magnet from quasi-1D electronic localization

Excitons, bound electron-hole pairs, influence the optical properties in strongly interacting solid-state systems and are typically most stable and pronounced in monolayer materials. Bulk systems with large exciton binding energies, on the other hand, are rare and the mechanisms driving their stability are still relatively unexplored. Here, we report an exceptionally large exciton binding energy in single crystals of the bulk van der Waals antiferromagnet CrSBr. Utilizing state-of-the-art angle-resolved photoemission spectroscopy and self-consistent ab-initio GW calculations, we present direct spectroscopic evidence supporting electronic localization and weak dielectric screening as mechanisms contributing to the amplified exciton binding energy. Furthermore, we report that surface doping enables broad tunability of the band gap offering promise for engineering of the optical and electronic properties. Our results indicate that CrSBr is a promising material for the study of the role of anisotropy in strongly interacting bulk systems and for the development of exciton-based optoelectronics.

36 MATERIALS SCIENCE↗

Two-dimensional diamonds from sp 2 -to- sp 3 phase transitions

The ability to change material properties through phase engineering has long been sought, with the goal of ad hoc tunability of the physical and chemical properties of the transformed phases. The synthesis and study of graphene have made it possible to explore the mechanisms of 2D phase transformations, opening up paths towards the formation of 2D diamond and diamond thin films. This Review examines the state-of-the-art phase transformations in 2D graphitic systems and beyond. The theoretical models formulated to describe the sp2-to-sp3 transitions from graphene to 2D diamond and the experimental processes developed to induce the transition to 2D diamond are discussed, focusing on the transformations induced by chemical functionalization and pressure. The effects of different structural and environmental factors on the evolution of the phase transformations and on the properties of the transformed diamond phases are explored. Without comprehensively reviewing phase transitions in all 2D materials, we briefly mention hexagonal boron nitride, phosphorene, transition metal dichalcogenides and MXenes systems. Lastly, the Review delves into the technologies and applications of phase transformations in 2D materials and the opportunities for this field.

36 MATERIALS SCIENCE↗

Atomic structural mechanism for ferroelectric-antiferroelectric transformation in perovskite NaNbO 3

Sodium niobate (NaNbO 3 or NN) is described as “the most complex perovskite system,” which exhibits transitions between, as well as coexistence of, several ferroelectrics (FE) and antiferroelectric (AFE) phases at different temperatures. Recently, solid solutions of NN with stabilized AFE phases(s) have gained attention for energy-related applications, such as high-density energy storage and electrocaloric cooling. A better understanding of the atomic mechanisms responsible for AFE/FE phase transitions in NaNbO 3 can enable a more rational design of its solid-solution systems with tunable functional properties. In this work, we have investigated changes in the average and local atomic structure of NN using a combination of x-ray/neutron diffraction and neutron pair-distribution function (PDF) analyses. The Rietveld refinement of the x-ray/neutron-diffraction patterns indicates a coexistence of the FE Q (P2 1 ma) and AFE P (Pbma) phases in the temperature range of 300 K ≤ T ≤ 615K, while PDF analysis indicated that the local structure (r < 8Å) is better described by a P2 1 ma symmetry. Above 615 K, the average structure transitions to an AFE R phase (Pmmn or Pnma), while PDF analysis shows an increased disordering of the octahedral distortions and Na displacements at the local scale. These results indicate that the average P/Q/R phase transitions in NN can be described as a result of complex ordering of distorted octahedral tilts at the nanoscale and off-centered displacements of the Na atoms.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Strain-insensitive intrinsically stretchable transistors and circuits

An all-elastomer strain engineering approach, which uses patterned elastomer layers with tunable stiffnesses, can be used to create intrinsically stretchable transistor arrays with a device density of 340 transistors cm -2 and strain insensitivity of less than 5% performance variation when stretched to 100% strain. Intrinsically stretchable electronics can form intimate interfaces with the human body, creating devices that could be used to monitor physiological signals without constraining movement. However, mechanical strain invariably leads to the degradation of the electronic properties of the devices. Here we show that strain-insensitive intrinsically stretchable transistor arrays can be created using an all-elastomer strain engineering approach, in which the patterned elastomer layers with tunable stiffnesses are incorporated into the transistor structure. By varying the cross-linking density of the elastomers, areas of increased local stiffness are introduced, reducing strain on the active regions of the devices. This approach can be readily incorporated into existing fabrication processes, and we use it to create arrays with a device density of 340 transistors cm -2 and a strain insensitivity of less than 5% performance variation when stretched to 100% strain. We also show that it can be used to fabricate strain-insensitive circuit elements, including NOR gates, ring oscillators and high-gain amplifiers for the stable monitoring of electrophysiological signals.

42 ENGINEERING↗

Dynamic Interfacial Design in Adaptive Hybrid Materials Enables Reversible and Tunable Mechano-Optic Smart Responses

Next-generation polymeric materials are shifting toward adaptive and interactive behaviors of living systems; however, designing materials that can reversibly modulate optical properties under mechanical deformation while maintaining mechanical robustness remains a key challenge. Here, we report a mechanically robust vitrimer-based adaptive hybrid material (AHM) that exhibits a stretch-induced reversible transparency-to-opacity transition, enabled by the integration of dynamic interactions at the polymer–silica nanoparticle interface and controlled nanoparticle self-assembly. The AHM combines boronic ester–functionalized polystyrene-b-poly(ethylene-co-butylene)-b-polystyrene (S-Bpin) with diol-functionalized silica nanoparticles (diol-SiNPs) to form a hybrid network hosting both dynamic boronic ester and hydrogen-bonding interactions. These reversible linkages facilitate controlled nanoparticle self-assembly and enable strain-induced nanoparticle alignment/aggregation. Upon stretching, SiNP-rich domains align and aggregate within the polymer matrix, while local modulus mismatch between stiff aggregated SiNP/borylated-styrene-rich regions and the softer elastomeric midblock induces surface microwrinkle formation. These internal aggregates and surface wrinkles cooperatively enhance light scattering, producing the opaque state under strain. Furthermore, the tailored AHM exhibits high toughness, thermomechanical stability, reprocessability, and programmable shape-memory behavior. This work presents a dynamic interfacial design strategy for mechanically robust, optically reconfigurable, and reusable soft materials for adaptive optics, smart windows, sensing, soft robotics, and circular smart-material platforms.

adaptive hybrid materials↗

Intrinsic thermal expansion and tunability of thermal expansion coefficient in Ni-substituted Co 2 V 2 O 7

Abstract Framework oxide materials are well-known for exhibiting not only negative thermal expansion (NTE), but also demonstrating thermal expansion that can be controlled using composition as a tuning parameter. In this work, we study the intrinsic thermal expansion properties of Co 2 V 2 O 7 , which has shown bulk linear NTE, and attempt to understand how substituting Ni 2+ for Co 2+ will affect the thermal expansion. The isomorphic solid solution is synthesized through solid-state methods and characterized using x-ray diffraction (XRD), diffuse reflectance spectroscopy, and neutron diffraction. The size difference between Ni 2+ and Co 2+ as well as the polyhedral volume of each Co 2+ metal coordination environment in the crystal structure allows Ni 2+ to partially be directed toward one crystallographic site over the other. Variable temperature synchrotron XRD data are employed to understand intrinsic thermal expansion. Across the solid solution, no intrinsic NTE is observed at the microscopic level, yet a degree of tunability in the thermal expansion coefficient with Ni substitution is demonstrated. The disparities between the intrinsic and bulk thermal expansion properties suggest that a morphological mechanism may have resulted in NTE in the bulk.

Materials Science↗

Dynamic Bottlebrush Polymer Networks: Self-Healing in Super-Soft Materials

Here, we introduce a design strategy to expand the range of accessible mechanical properties in covalent adaptable networks (CANs) using bottlebrush polymer building blocks. Well-defined bottlebrush polymers with rubbery poly(4-methylcaprolactone) side-chains were crosslinked in formulations that include a bislactone and strong Lewis acid (tin ethylhexanoate). The resulting materials exhibit tunable stress relaxation rates at elevated temperatures (160–180 °C) due to dynamic ester crosslinks that undergo transesterification with residual hydroxy groups. Varying the crosslinker loading or bottlebrush backbone degree of polymerization yields predictable low-frequency shear moduli ca. 10–100 kPa, well below values typical of linear polymer CANs (1 MPa). These extensible networks can be stretched to strains as large as 350% before failure and undergo efficient self-healing to recover >85% of their original toughness upon repeated fracture and melt processing. In summary, molecular architecture creates new opportunities to tailor the mechanical properties of CANs in ways that are otherwise difficult to achieve.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Super‐Resolution Lifetime Imaging of Single Molecules Near Gold Bowtie Nanoparticles

Interactions between light and matter serve as the basis of many technologies, but the quality of these devices is inherently limited by the optical properties of their constituents. Plasmonic nanoparticles are a highly versatile and tunable platform for the enhancement of such optical properties. However, the near-field nature of these effects has made thorough study and understanding of these mechanisms difficult. In this work, we introduce a fully confocal technique combining photoswitching super-resolution microscopy with fluorescence lifetime imaging microscopy to study single-molecule decay rate enhancement. We demonstrate that the technique combines a spatial resolution better than 20 nm, and a 16 ps temporal resolution. Simultaneously, an autocorrelation measurement is also performed to confirm that the data indeed originates from single molecules. This work provides insight into the various mechanisms of plasmon-enhanced emission, and allows the study of the correlation between emission intensity and lifetime enhancement. This complicated relationship is shown to be dependent upon the relative influence of various radiative and nonradiative decay pathways. Here, we provide a platform for further study of emission mislocalization, the position-dependent prominence of different decay pathways, and the direct super-resolved measurement of the local density of states.

36 MATERIALS SCIENCE↗

Chiral Perovskite Nanoplatelets with Tunable Circularly Polarized Luminescence in the Strong Confinement Regime

Chiral perovskite nanocrystals have emerged as an interesting chiral excitonic platform that combines both structural flexibility and superior optoelectronic properties. Despite several recent demonstrations of optical activity in various chiral perovskite nanocrystals, efficient circularly polarized luminescence (CPL) with tunable energies remains a challenge. The chirality imprinting mechanism as a function of perovskite nanocrystal dimensionality remains elusive. Here, in this study, atomically thin inorganic perovskite nanoplatelets (NPLs) are synthesized with precise control of layer thickness and are functionalized by chiral surface ligands, serving as a unique platform to probe the chirality transfer mechanism at the organic/perovskite interface. It is found that chirality is successfully imprinted into mono-, bi-, and tri-layer inorganic perovskite NPLs, exhibiting tunable circular dichroism (CD) and CPL responses. However, chirality transfer decreases in thicker NPLs, resulting in decreased CD and CPL dissymmetry factors for thicker NPLs. Aided by large-scale first-principles calculations, it is proposed that chirality transfer is mainly mediated through a surface distortion rather than a hybridization of electronic states, giving rise to symmetry breaking in the perovskite lattice and spin-split conduction bands. The findings described here provide an in-depth understanding of chirality transfer and design principles for distorted-surface perovskites for chiral photonic applications.

36 MATERIALS SCIENCE↗

Strain-Modulated Exciton Localization and Enhanced Emission in Multilayer GaSe

Strain engineering is one of the most effective routes for tuning the electrical and optical properties of two-dimensional layered materials. Besides reproducing the results of other groups on the tunability and photoluminescence (PL) enhancement of free and bound excitons under mechanical deformation or thermal effects, we systematically studied the mechanical strain (wrinkle) and local thermal strain (laser heating) effects on the PL lifetime and polarization in GaSe multilayers and their interplay, revealing their coupled impact on excitonic dynamics. Here, the PL intensity of localized excitons in the wrinkle region of GaSe increases superlinearly with the excitation laser power. The polarization effect has been observed for the bound exciton in GaSe under mechanical strain, but not in GaSe under thermal strain. Fluorescence lifetime imaging (FLIM) measurements reveal strain-tunable lifetimes for both free and bound excitons, and the lifetime of the bound exciton is longer than the free exciton in the mechanical strain region, correlating with the enhanced emission of the bound exciton. These results highlight previously uncharacterized optoelectronic tunability in GaSe and broaden the design space for strain (or thermally)-controlled 2D layered devices.

, GaSe, Exciton localization↗

Tunable structure and reinforcement of polyvinyl alcohol (PVA) hydrogels using fungal chitin particles

Polysaccharides, including chitin, are one of the most abundant biopolymers in nature and are increasingly recognized as a sustainable alternative to petroleum-derived plastics and synthetic fillers in polymer composites. Traditionally sourced from crustacean shells, chitin offers mechanical strength and biocompatibility with limitations also in processability and functionality. Fungal-derived chitin material represents a promising alternative, with advantages including scalable fermentation on low-cost substrates, absence of shellfish allergens, and tunable molecular architectures that vary by species, developmental stage, and growth environment. Here, in this study, we systematically examined chitinous materials obtained from taxonomically and functionally distinct fungi, Laccaria bicolor, Trichoderma reesei and Rhizopus oryzae, to assess their structural, chemical, and morphological properties as reinforcement agents in polymer composites. Mild alkaline pretreatment was employed to obtain mycelium chitin particles, thereby improving accessibility to chitin and co-occurring β-D-glucans while maintaining microparticle integrity. Comprehensive FTIR and solid-state NMR analyses revealed species-specific differences in chemical composition and microstructure, with R. oryzae exhibiting a unique spectral signature. These fungal-derived chitin were then incorporated into poly(vinyl alcohol) (PVA) hydrogels, where they acted as reinforcing fillers without the need for additional chemical crosslinkers. Comparative evaluation of hydrogel properties demonstrated that fungal chitin significantly enhanced mechanical performance, with all mycelium fillers mitigating the water weakening in PVA hydrogels. R. oryzae-derived composites tripled the hydrogel tensile strength while the submicron fibrous morphology in L. bicolor contributes to over 45 % tensile improvement in dry PVA composites. Our findings highlight the potential of fungal biomass as a tunable, sustainable platform for producing chitin-based reinforcing agents.

Chitin↗

Controlling phonon lifetimes via sublattice disordering in AgBiSe 2

Understanding and controlling microscopic heat transfer mechanisms in solids is critical to material design in numerous technological applications. Yet, the current understanding of thermal transport in semiconductors and insulators is limited by the difficulty in directly measuring individual phonon lifetimes and mean free paths, and studying their dependence on the microscopic state of the material. Here in this paper, we report our measurements of microscopic phonon scattering rates in AgBiSe 2 , which exhibits a controllable, reversible change directly linked to microstructure evolution near a reversible structural phase transition, that directly impacts the thermal conductivity. We demonstrate a steplike doubling of phonon scattering rates resultant from the cation disordering at the structural transition. To rationalize the neutron scattering data, we leverage a stepwise approach to account for alterations to the thermal conductivity that are imparted by distinct scattering mechanisms. These results highlight the potential of tunable microstructures housed in a stable crystal matrix to provide a practical route to tailor phonon scattering to optimize thermal transport properties.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Luminescence mechanism in hydrogenated silicon quantum dots with a single oxygen ligand

Though photoluminescence (PL) of Si quantum dots (QDs) has been known for decades and both theoretical and experimental studies have been extensive, their luminescence mechanism has not been elaborated. Several models have been proposed to explain the mechanism. A deep insight into the origin of light emissions in Si QDs is necessary. This work calculated the ground- and excited state properties of hydrogenated Si QDs with various diameters, including full hydrogen passivation, single Si=O ligands, single epoxide and coexisting Si=O and epoxide structures in order to investigate the dominant contribution states for luminescence. The results revealed that even a single oxygen atom in hydrogenated Si QDs can dramatically change their electronic and optical properties. Intriguingly, we found that a size-independent emission, the strongest among all possible emissions, was induced by the single Si=O passivated Si-QDs. In non-oxidized Si-QDs exhibiting a core-related size-tunable emission, the luminescence properties can be modulated by the ligands of Si QDs, and a very small number of oxygen ligands can strongly influence the luminescence of nanocrystalline silicon. Our findings deepen the understanding of the PL mechanism of Si QDs and can further promote the development of silicon-based optoelectronic devices.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Crystal Chemistry, Band-Gap Red Shift, and Electrocatalytic Activity of Iron-Doped Gallium Oxide Ceramics

This work for the first time unfurls the fundamental mechanisms and set the stage for an approach to derive electrocatalytic activity, which is otherwise not possible, in a traditionally known wide band gap oxide material. Specifically, we report on the tunable optical properties, in terms of wide spectral selectivity and red-shifted band gap, and electrocatalytic behavior of iron (Fe) doped gallium oxide (ß-Ga 2 O 3 ) model system. X-ray diffraction (XRD) studies of sintered Ga 2-x Fe x O 3 (GFO) (0.0 ≤ x ≤ 0.3) compounds provide evidence for the Fe 3+ substitution at Ga 3+ site without any secondary phase formation. Rietveld refinement of XRD patterns reveal that the GFO compounds crystallize in monoclinic crystal symmetry with C2/m space group. The electronic structure of the GFO compounds probed using X-ray photoelectron spectroscopy data reveals that, at lower concentrations of Fe exhibits mixed chemical valence states (Fe 3+ , Fe 2+ ), whereas single chemical valence state (Fe 3+ ) is evident for higher Fe content (x = 0.20-0.30). The optical absorption spectra reveal a significant red shift in the optical band gap with Fe doping. The origin of the significant red shift even at low concentrations of Fe (x = 0.05) is attributed to the strong sp-d exchange interaction originated from the 3 d 5 electrons of Fe 3+ . The optical absorption edge observed at ˜450 nm with lower intensity is the characteristic of Fe doped compounds associated with Fe 3+ - Fe 3+ double excitation process. Coupled with optical band gap red shift, electrocatalytic studies of GFO compounds reveals that, interestingly, Fe doped Ga 2 O 3 compound exhibits electrocatalytic activity in contrast to intrinsic Ga 2 O 3 . Fe doped samples (GFO) demonstrated appreciable electrocatalytic activity towards the generation of H 2 through electrocatalytic water splitting. An onset potential and tafel slope of GFO compounds includes: ~900 mV, ~210 mVdec -1 (x = 0.15) and ~1036 mV, ~290 mVdec-1 (x = 0.30). The electrocatalytic activity of Fe doped Ga-oxide compounds is attributed to cumulative effect of different mechanisms such as; doping resulted new catalytic centers, enhanced conductivity and electron mobility. Hence, in this report, for the first time, we explored a new pathway; electrocatalytic behavior of Fe doped Ga 2 O 3 resulted due to Fe chemical states, red shift in optical band gap. The implications derived from this work may be applicable to a large class of compounds and further options may be available to design functional materials for electrocatalytic energy production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Utilizing Site Disorder in the Development of New Energy-Relevant Semiconductors

We report controlling site disorder in ternary and multinary compounds enables tuning optical and electronic properties at fixed lattice constants and stoichiometries, moving beyond many of the challenges facing binary alloy systems. Here, we consider possible enhancements to energy-related applications through the integration of disorder-tunable materials in devices such as light-emitting diodes, photonics, photovoltaics, photocatalytic materials, batteries, and thermoelectrics. However, challenges remain in controlling and characterizing disorder. Focusing primarily on II–IV–V 2 materials, we identify three metrics for experimentally characterizing cation site disorder. Complementary to these experiments, we discuss simulation methods to understand disordered materials. Nonidealities, such as off-stoichiometry and oxygen incorporation, can occur while synthesizing metastable disordered materials. While nonidealities may seem undesirable, we describe how if harnessed they could provide another knob for tuning disorder and subsequently properties. To illustrate the effects of disorder on device-relevant properties, we provide case examples of disordered materials and their potential in device applications.

36 MATERIALS SCIENCE↗

Text-mined dataset of gold nanoparticle synthesis procedures, morphologies, and size entities

Abstract Gold nanoparticles are highly desired for a range of technological applications due to their tunable properties, which are dictated by the size and shape of the constituent particles. Many heuristic methods for controlling the morphological characteristics of gold nanoparticles are well known. However, the underlying mechanisms controlling their size and shape remain poorly understood, partly due to the immense range of possible combinations of synthesis parameters. Data-driven methods can offer insight to help guide understanding of these underlying mechanisms, so long as sufficient synthesis data are available. To facilitate data mining in this direction, we have constructed and made publicly available a dataset of codified gold nanoparticle synthesis protocols and outcomes extracted directly from the nanoparticle materials science literature using natural language processing and text-mining techniques. This dataset contains 5,154 data records, each representing a single gold nanoparticle synthesis article, filtered from a database of 4,973,165 publications. Each record contains codified synthesis protocols and extracted morphological information from a total of 7,608 experimental and 12,519 characterization paragraphs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Development of Antimicrobial PLA Composites for Fused Filament Fabrication

In addition to possessing the desirable properties of being a biodegradable and biocompatible polymer fabricated from renewable resources, poly (lactic acid) (PLA) has useful mechanical and thermal attributes that has enabled it to be one of the most widely-used plastics for medicine, manufacturing, and agriculture. Yet, PLA composites have not been heavily explored for use in 3D-printing applications, and the range of feasible materials for the technology is limited, which inhibits its potential growth and industry adoption. In this study, tunable, multifunctional antimicrobial PLA composite filaments for 3D-printing have been fabricated and tested via chemical, thermal, mechanical, and antimicrobial experiments. Thermally stable antimicrobial ceramics, ZnO and TiO2, were used as fillers up to 30 wt%, and poly (ethylene glycol) (PEG) was used as a plasticizer to tune the physical material properties. Results demonstrate that the PLA composite filaments exhibit the thermal phase behaviors and thermal stability suitable for 3D-printing. Additionally, PEG can be used to tune the mechanical properties while not affecting the antimicrobial efficacy that ZnO and TiO2 imbue.

TiO2↗

Direct Synthesis of Layer-Tunable and Transfer-Free Graphene on Device-Compatible Substrates Using Ion Implantation Toward Versatile Applications

Direct synthesis of layer-tunable and transfer-free graphene on technologically important substrates is highly valued for various electronics and device applications. State of the art in the field is currently a two-step process: a high-quality graphene layer synthesis on metal substrate through chemical vapor deposition (CVD) followed by delicate layer transfer onto device-relevant substrates. Here, we report a novel synthesis approach combining ion implantation for a precise graphene layer control and dual-metal smart Janus substrate for a diffusion-limiting graphene formation to directly synthesize large area, high quality, and layer-tunable graphene films on arbitrary substrates without the post-synthesis layer transfer process. Carbon (C) ion implantation was performed on Cu–Ni film deposited on a variety of device-relevant substrates. A well-controlled number of layers of graphene, primarily monolayer and bilayer, is precisely controlled by the equivalent fluence of the implanted C-atoms (1 monolayer ~4 × 10 15 C-atoms/cm 2 ). Upon thermal annealing to promote Cu-Ni alloying, the pre-implanted C-atoms in the Ni layer are pushed toward the Ni/substrate interface by the top Cu layer due to the poor C-solubility in Cu. As a result, the expelled C-atoms precipitate into a graphene structure at the interface facilitated by the Cu-like alloy catalysis. After removing the alloyed Cu-like surface layer, the layer-tunable graphene on the desired substrate is directly realized. The layer-selectivity, high quality, and uniformity of the graphene films are not only confirmed with detailed characterizations using a suite of surface analysis techniques but more importantly are successfully demonstrated by the excellent properties and performance of several devices directly fabricated from these graphene films. Molecular dynamics (MD) simulations using the reactive force field (ReaxFF) were performed to elucidate the graphene formation mechanisms in this novel synthesis approach. With the wide use of ion implantation technology in the microelectronics industry, this novel graphene synthesis approach with precise layer-tunability and transfer-free processing has the promise to advance efficient graphene-device manufacturing and expedite their versatile applications in many fields.

36 MATERIALS SCIENCE↗