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At least 487 records · Page 27

Distilling physical origins of hardness in multi-principal element alloys directly from ensemble neural network models

Abstract Despite a plethora of data being generated on the mechanical behavior of multi-principal element alloys, a systematic assessment remains inaccessible via Edisonian approaches. We approach this challenge by considering the specific case of alloy hardness, and present a machine-learning framework that captures the essential physical features contributing to hardness and allows high-throughput exploration of multi-dimensional compositional space. The model, tested on diverse datasets, was used to explore and successfully predict hardness in Al x Ti y (CrFeNi) 1- x - y , Hf x Co y (CrFeNi) 1- x - y and Al x (TiZrHf) 1- x systems supported by data from density-functional theory predicted phase stability and ordering behavior. The experimental validation of hardness was done on TiZrHfAl x . The selected systems pose diverse challenges due to the presence of ordering and clustering pairs, as well as vacancy-stabilized novel structures. We also present a detailed model analysis that integrates local partial-dependencies with a compositional-stimulus and model-response study to derive material-specific insights from the decision-making process.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Strain-affected ferroelastic domain walls in RbMnFe charge-transfer materials undergoing collective Jahn–Teller distortion

Many rubidium manganese hexacyanoferrate materials, with the general formula Rb x Mn[Fe(CN) 6 ] (x+2)/3 ·zH 2 O, exhibit diverse charge-transfer-based functionalities due to the bistability between a high temperature Mn II (S = 5/2)Fe III (S = 1/2) cubic phase and a low-temperature Mn III (S = 2)Fe II (S = 0) tetragonal phase. The collective Jahn–Teller distortion on the Mn sites is responsible for the cubic-to-tetragonal ferroelastic phase transition, which is associated with the appearance of ferroelastic domains. In this study, we use X-ray diffraction to reveal the coexistence of 3 types of ferroelastic tetragonal domains and estimate the spatial extension of the strain around the domain walls, which represents about 30% of the volume of the crystal.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Electronic and optical properties of transition metal impurities in GaN and AlN

The optical properties of Cr(III) impurities are well studied and exploited in 𝛼−Al 2 ⁢O 3 , which enables ruby lasers. Photoluminescence spectra resembling the famous 1.78 eV emission of Cr in 𝛼−Al 2 ⁢O 3 have been observed in other wide-band-gap host materials, in particular AlN. However, it is unclear whether Cr would produce the same emission in the nitrides as in 𝛼−Al 2 ⁢O 3 , especially given the different local environment (tetrahedral vs octahedral coordination). We investigate the electronic and optical properties of transition metal substitutional impurities (Cr, Co, Ni, and Cu) in wurtzite GaN and AlN from first principles, utilizing hybrid density functional theory. We calculate the optical transition energies using a constrained occupation approach that accounts for the multideterminant nature of the excited states. Our results indicate that substitutional Cr(III) is not responsible for the emission near 1.78 eV observed in the nitrides. Among the examined impurities, only substitutional Co(II) produces emission near 1.78 eV. Based on the favorable properties of Co(II) (low formation energy, small Huang-Rhys factor, and an 𝑆 = 3/2 ground state) we propose it as a promising single-photon emitter or spin qubit. We additionally assign the PL peak observed near 1.05 eV in GaN and AlN to the 2 𝐸→ 4 𝐴 2 transition of the Ni(III) substitution.

36 MATERIALS SCIENCE↗

Intrinsic Limits of Charge Carrier Mobilities in Layered Halide Perovskites

Layered halide perovskites have emerged as potential alternatives to three-dimensional (3D) halide perovskites due to their improved stability and larger material phase space, allowing fine tuning of structural, electronic, and optical properties. However, their charge carrier mobilities are significantly smaller than those of 3D halide perovskites, which has a considerable impact on their application in optoelectronic devices. Here, we employ state-of-the-art approaches to unveil the electron-phonon mechanisms responsible for the diminished transport properties of layered halide perovskites. Starting from a prototypical A M X 3 halide perovskite, we model the case of n = 1 and n = 2 layered structures and compare their electronic and transport properties to the 3D reference. The electronic and phononic properties are investigated within density functional theory (DFT) and density functional perturbation theory (DFPT), while transport properties are obtained via the Boltzmann transport equation. The vibrational modes contributing to charge carrier scattering are investigated and associated with polar-phonon scattering mechanisms arising from the long-range Fröhlich coupling and deformation-potential scattering processes. Our investigation reveals that the lower mobilities in layered systems primarily originate from the increased electronic density of states at the vicinity of the band edges, while the electron-phonon coupling strength remains similar. Such an increase is caused by the dimensionality reduction and the break in octahedra connectivity along the stacking direction. Our findings provide a fundamental understanding of the electron-phonon coupling mechanisms in layered perovskites and highlight the intrinsic limitations of the charge carrier transport in these materials. Published by the American Physical Society 2024

Cucco, Bruno (ORCID:0000000331564143)↗

Dual-step photocarrier injection by mixture layer of ZnO QDs and MoS 2 NPs on hybrid PdAu NPs

Hybrid UV-photodetector (PD) design consisted of various compatible nano-material systems are drawing significant research interests due to their improved device tunability and functionality. A hybrid ZnO–MoS 2 /HNP UV-PD design is demonstrated by the mixture layer of zinc oxide (ZnO) quantum dot (QD) and molybdenum di-sulfate (MoS 2 ) nanoparticles (NPs) on the plasmonic hybrid PdAu NP template. The proposed design exhibits an excellent photocurrent of 1.45×10 -3 A under the 54.9 mW/mm2 at ± 10 V due to a dual step enhancement of photo-carrier injection. It then leads to the significantly improved performance factors of photo-responsivity 1430 mA/mm 2 and detectivity 4.50 × 10 10 jones at 0.34 mW/mm 2 . The rise time (T r ) and fall time (T f ) of 3.37 and 0.35 s are obtained for the ZnO–MoS 2 /HNP PD. Finally, the demonstrated performance factors indicate that the hybrid ZnO–MoS 2 /HNP UV-PD platform is one of the best UV-PDs as summarized in Table 1.

36 MATERIALS SCIENCE↗

Emergent Inductance from Chiral Orbital Currents in a Bulk Ferrimagnet

Here, we report the discovery of a new form of inductance in the bulk ferrimagnet Mn 3 ⁢Si 2 ⁢Te 6 , which features strong spin-orbit coupling, large magnetic anisotropy, and pronounced magnetoelastic interactions. Below its Curie temperature (𝑇 𝐶 ≈ 78 K), Mn 3 ⁢Si 2 ⁢Te 6 hosts chiral orbital currents (COC) that circulate within the crystal lattice and give rise to collective electronic behavior [Control of chiral orbital currents in a colossal magnetoresistance material, Nature (London) 611, 467 (2022).]. By applying a magnetic field along the hard 𝑐 axis and driving the system with low-frequency currents, we uncover a giant inductive response up to millhenry scale, originating from first-order reconfigurations of COC domains. These domains act as coherent mesoscopic inductive elements that resist reversal upon current reduction, producing a large electromotive force and sharply increasing voltage. This emergent inductance defies classical models, occurs without superconductivity or engineered nanostructures, and opens a new frontier in orbital-based quantum functionality and device concepts.

complex materials↗

On the bulk compaction of brittle granular materials, part I: SeS analysis of axial compression to 4000 MPa

The bulk compaction of granular materials has been studied for decades to interpret and manage responses for soils and powder-based component fabrication, and geophysical, celestial, and ballistic impact. Their bulk or macroscopic compaction response is limited by what occurs at the granular or microstructural scale. Motivation existed to more closely examine that association specific to granular brittle materials (e.g., ceramics and glasses). That examination is offered in a series of three companion papers where Part I describes a new supplemental analysis adopted to bulk compaction response involving relatively high compaction stresses (4000 MPa). Bulk compactions of vitreous silicates and crystalline quartzes were interpreted in three ways, including that of a new analysis that considers the product of void ratio (e) and stress (S) as a function of S, hereafter referred to as “SeS analysis”. In conclusion, the SeS analysis was found to be an informative supplement to conventional bulk compaction analyses because it provides more consistent higher sensitivity for the identification of bulk density rate increase with increasing compaction (softening); a rate increase that arises from the cumulative effect of the onsets and progression of compaction-induced yielding, fracture or comminution, densification, phase change, or combinations thereof occurring at the granular or microstructural scale.

compaction↗

Oil-Pressure Based Apparatus for In-Situ High-Energy Synchrotron X-Ray Diffraction Studies During Biaxial Deformation

Background: Understanding biaxial loading response at the microstructural level is crucial in helping better design sheet manufacturing processes and calibrate/validate material deformation models. Objective: The objective of this work was to develop a low-cost testing apparatus to probe, with sufficient spatial resolution, the micro-mechanical response of a sheet material in-situ under biaxial loading conditions. Methods: The testing apparatus fabricated as a part of this study operates in a similar fashion to a standard bulge test and uses oil pressure to generate biaxial loading conditions. This biaxial testing apparatus was operated within a synchrotron beamline to characterize the mechanical response of a flash-processed steel sheet using in-situ high-energy X-ray diffraction (XRD) measurements. Further, the GSAS-II package was utilized to develop a workflow for the analysis of the large volume of diffraction data acquired. The workflow was then used to extract the peak position, width, and integrated intensity of the XRD peaks corresponding to the major body-centered cubic phase. Results: The equi-biaxial nature of the loading in the measured area was independently corroborated using experimental (XRD) and simulation (finite element analysis) methods. Furthermore, we discuss the evolution of elastic strain in the major body-centered cubic phase as a function of applied oil pressure and location on the steel sheet. Conclusions: A key advantage of the biaxial apparatus fabricated in this synchrotron study is demonstrated using the results obtained for the flash-processed steel sheet – i.e., mapping the lattice plane-dependent response to biaxial loading for a relatively large sample area in a spatially resolved manner.

36 MATERIALS SCIENCE↗

First-principles insight into all-optical spin switching in the half-metallic Heusler ferrimagnet Mn 2 RuGa

All-optical spin switching (AOS) represents a new frontier in magnetic storage technology—spin manipulation without a magnetic field—but its underlying working principle is not well understood. Many AOS ferrimagnets such as GdFeCo are amorphous and renders the high-level first-principles study unfeasible. The crystalline half-metallic Heusler Mn 2 RuGa presents an opportunity. Here we carry out hitherto the comprehensive density functional investigation into the material properties of Mn 2 RuGa, and introduce two concepts—the spin anchor site and the optical active site—as two pillars for AOS in ferrimagnets. In Mn 2 RuGa, Mn(4a) serves as the spin anchor site, whose band is below the Fermi level and has a strong spin moment, while Mn(4c) is the optical active site whose band crosses the Fermi level. Our magneto-optical Kerr spectrum and band structure calculation jointly reveal that the delicate competition between the Ru-4d and Ga-4p states is responsible for the creation of these two sites. Furthermore these two sites found here not only present a unified picture for both Mn 2 RuGa and GdFeCo, but also open the door for future applications. Specifically, we propose a Mn 2 Ru x Ga-based magnetic tunnel junction where a single laser pulse can control magnetoresistance.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗

Modification of the MTS model for high strain-rate behavior of TI-6AL-4V

The Mechanical Threshold Stress (MTS) model provides excellent predictive capabilities for the material constitutive response for a wide range of temperatures and strain rates. However, the MTS model fails to capture the rapidly increasing yield stress at high strain rate behavior as the deformation controlling mechanism transitions from thermal activation to drag mechanisms, only capturing the linear behavior. Further, the model typically over predicts the flow stress behavior at yield and post yield due to its use of a constant work hardening rate parameter derived from the stress–strain response at constant saturation stress. An alternative approach to fitting portions of the MTS model is investigated and mathematical models are developed to address these issues. The results show that with appropriate experimental data, the mechanical threshold stress and work hardening rate parameters within the MTS model can quite easily and accurately be modified to extend applicability to high strain rate behavior and more accurately model the initial flow stress behavior at early work hardening rates without modification of the functions core to the MTS model itself.

36 MATERIALS SCIENCE↗

Revisiting two thiophosphate compounds constituting d 0 transition metal HfP 2 S 6 and d 10 transition metal α-Ag 4 P 2 S 6 as multifunctional materials for combining second harmonic generation response and photocurrent response

Two acentric thiophosphate compounds, HfP 2 S 6 and α-Ag 4 P 2 S 6 , are revisited and studied as infrared nonlinear optical materials. HfP 2 S 6 and α-Ag 4 P 2 S 6 were structurally characterized without any property measurements. Here, in this work, HfP 2 S 6 and α-Ag 4 P 2 S 6 were synthesized via high temperature salt flux reactions. Low-temperature polymorph acentric α-Ag 4 P 2 S 6 was purified and grown as mm-sized crystals with the aid of AgBr flux. The AgBr flux was revealed to play an important role in stabilizing the acentric α-Ag 4 P 2 S 6 . The acentric α-Ag 4 P 2 S 6 transforms to centrosymmetric β-Ag 4 P 2 S 6 at 850(5) K, which is revealed by differential scanning calorimetry (DSC) analysis and powder X-ray diffraction experiments. HfP 2 S 6 and α-Ag 4 P 2 S 6 are discovered by UV-vis spectrum measurements as indirect bandgap semiconductors with bandgaps of 2.2(1) eV and 2.5(1) eV, respectively, which is supported by DFT calculations and TB-LMTO-ASA calculations. The bonding pictures of α-Ag 4 P 2 S 6 were studied by crystal orbital Hamilton population calculations (COHP) coupled with electron localization function (ELF) analysis. DFT calculations predict that HfP 2 S 6 and α-Ag 4 P 2 S 6 would exhibit different optical performances regardless of being constructed from identical [P 2 S 6 ] motifs. HfP 2 S 6 exhibits a low second harmonic generation (SHG) response, ~0.21 × AGS (for the sample of particle size of 25 μm). α-Ag 4 P 2 S 6 possesses moderate SHG response, ~0.61 × AGS (for the sample of particle size of 225 μm) coupled with a high laser damage threshold (LDT) of ~3.2 × AGS. Characteristics of high ambient stability, moderate bandgap and SHG response, type-I phase-matching capability, and high LDT together with the easy growth of large crystals make α-Ag 4 P 2 S 6 attractive for future infrared nonlinear optical applications. Photocurrent measurements found that α-Ag 4 P 2 S 6 and β-Ag 4 P 2 S 6 have high photocurrent response, 165 nA cm -2 and 135 nA cm -2 , respectively. α-Ag 4 P 2 S 6 is a new multifunctional material of the ternary Ag–P–S system, which combines nonlinear optical (NLO) properties and photocurrent response.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Broadband Photoconductive Sampling in Gallium Phosphide

Abstract Direct measurements of the electric field of light enable new observations of light–matter interactions. In the near‐infrared and visible spectral ranges, this typically relies on techniques that exploit nonlinearities in gases or solids, which limits their sensitivity. Here, a method for the detection of broadband near‐infrared fields spanning more than one octave from 110 to 220 THz based on linear absorption in a semiconductor is demonstrated. This technique, which avoids complex vacuum setups and works under ambient conditions, employs linear photoconductive sampling (LPS) in gallium phosphide. Simulations reveal that the response function of LPS is concerned with the intensity envelope of the gate field, in contrast to electro‐optic sampling, relaxing the stringent temporal requirements on the gate pulse.

36 MATERIALS SCIENCE↗

Design of light- and chemically responsive protein assemblies through host-guest interactions

Host-guest (HG) interactions have been widely used to build responsive materials and molecular machines owing to their inherently dynamic nature, interaction specificity, and responsiveness to diverse stimuli. Here, in this work, we have set out to exploit these advantages of HG chemistry in the design of dynamic protein assemblies, using a C 4 symmetric protein, C98 RhuA, as a building block. We show that a C98 RhuA variant individually modified with β-cyclodextrin (βCD) (host) or azobenzene (guest) functionalities can specifically pair with each other to form highly ordered 1D and 2D assemblies. Association and dissociation of βCD RhuA- azo RhuA assemblies can be controlled by UV and visible light as well as by small-molecule modulators of βCD-azobenzene interactions. Kinetics analyses reveal that βCD RhuA- azo RhuA nanotubes assemble without a nucleation barrier, a highly unusual occurrence for helical supramolecular systems. Taken together, our findings provide a compelling example for achieving complex structural and dynamic outcomes in protein assembly through simple chemical design.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge-Density-Specific Response of Grafted Polyelectrolytes to Electric Fields: Bending or Tilting?

The response of polyelectrolytes (PEs) to applied electric fields drive applications in energetics, diagnostics, materials development, and many more. Here we employ all-atom molecular dynamics (MD) simulations to probe the response of grafted PE brushes to axial electric fields. For PEs with large charge densities, the electric field triggers a left-right asymmetric distribution of counterions around the PE backbone: consequently, depending on the location (left or right), there is an unequal screening and an unequal force on the PE functional groups causing a bending-driven brush height reduction. However, for the weakly charged PEs, the electric field causes a uniform distribution of the counterions across the brush enforcing a uniform (without left-right asymmetry) partially unscreened PE brush: therefore, all the brush segments experience similar force causing a brush tilting-driven brush height reduction. As a result, such bending versus tilting responses is commensurate with the electric-field-driven increase (decrease) in the flexibility of strongly (weakly) charged PEs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Reconfigurable droplet networks

Droplet networks stabilized by lipid interfacial bilayers or colloidal particles have been extensively investigated in recent years and are of great interest for compartmentalized reactions and biological functions. However, current design strategies are disadvantaged by complex preparations and limited droplet size. Here, by using the assembly and jamming of cucurbit[8]uril surfactants at the oil-water interface, we show a novel means of preparing droplet networks that are multi-responsive, reconfigurable, and internally connected over macroscopic distances. Openings between the droplets enable the exchange of matter, affording a platform for chemical reactions and material synthesis. Our work requires only a manual compression to construct complex patterns of droplet networks, underscoring the simplicity of this strategy and the range of potential applications.

36 MATERIALS SCIENCE↗

Some Aspects of the Liquid Water Thermodynamic Behavior: From The Stable to the Deep Supercooled Regime

Liquid water is considered to be a peculiar example of glass forming materials because of the possibility of giving rise to amorphous phases with different densities and of the thermodynamic anomalies that characterize its supercooled liquid phase. In the present work, literature data on the density of bulk liquid water are analyzed in a wide temperature-pressure range, also including the glass phases. A careful data analysis, which was performed on different density isobars, made in terms of thermodynamic response functions, like the thermal expansion αP and the specific heat differences C P -C V , proves, exclusively from the experimental data, the thermodynamic consistence of the liquid-liquid transition hypothesis. The study confirms that supercooled bulk water is a mixture of two liquid “phases”, namely the high density (HDL) and the low density (LDL) liquids that characterize different regions of the water phase diagram. Furthermore, the C P -C V isobars behaviors clearly support the existence of both a liquid–liquid transition and of a liquid–liquid critical point.

59 BASIC BIOLOGICAL SCIENCES↗

Spin-Controllable Dynamics in Defect-Engineered Carbon Nanotubes as Single Photon Emitters: Data-Driven Modeling and Computations

Quantum technologies, such as quantum computing and sensing, require efficient single-photon emission (SPE) sources that operate at room temperature in telecom wavelengths. While several materials can serve as SPE sources, no single platform meets all the criteria for efficiency, ambient operation, and scalability. Single-walled carbon nanotubes (SWCNTs) with covalently attached molecules offer a promising solution. Their SPE can be easily tuned via modifications of the SWCNT's diameter, chirality, and bonded molecules, enabling emission across near-IR to telecom wavelengths at ambient conditions. However, to fully realize the potential of SWCNTs and unlock their quantum capabilities, a deeper understanding of how structural defects from molecular adducts affect their emission and competing photoexcited processes is essential. To address this gap in our knowledge, this project combined quantum chemistry calculations with data-driven methods of cheminformatics (QSAR) and machine learning (ML). The developed computational approaches have provided several design strategies for covalent functionalization of SWCNTs to improve their optical response. The collaboration with Los Alamos National Lab (LANL) enabled direct comparison of computational and experimental data, facilitating method validation. This partnership was enhanced through access to LANL's Center for Integrated Nanotechnologies (CINT) utilizing User Facility Program and summer internships, which provided three NDSU graduate students with hands-on experience at LANL. The outcomes of this project included (1) Advancing the current stage of computational methods in accurate modeling of non-adiabatic spin-dependent photoexcited dynamics and its applicability to nanosystems consisting of thousands of atoms, realized as open-access codes linked to existing DFT-based software; (2) Establishing the relationship between the structure of adducts and SWCNTs and intrinsic excitonic and spin properties of defect states for guiding novel synthetic strategies and experimental probes of chemically functionalized SWCNTs as near-IR emitting materials; (3) Generating virtual libraries of hypothetical functionalized SWCNTs for virtual screening of their chemical structures and optical properties, leveraging new functionalities of SWCNTs; (4) Offering a unique experience for NDSU graduate students that prepared them for future scientific careers related to materials modeling and big data processing. These results were summarized in 12 published journal papers and 3 recently submitted papers. One of a key finding is that the position of defect sites on the SWCNT surface primarily drives the emission redshift (up to 100 meV), while the polarity of the defect-inducing molecules has a much smaller effect (~10 meV). However, the electron-donating or withdrawing properties of a molecule influence selecting reactivity of defect sites. These insights important for optimizing synthetic protocols for desired emissions in SWCNTs. We also revealed that the interaction between two defects at various positions on the SWCNT enhances the redshift and optical activity of states, favoring strong near-IR emission. This suggests that manipulations in defect concentrations is a promising strategy for controlling efficient emission. Mostly important, the defect position was found controllable by the spin states of photoexcited intermediates: Excited aromatic molecules form ortho defects with SWCNTs at their singlet states in the presence of oxygen, while oxygen-free conditions favor para defects via the triplet-state mechanism. Additionally, a heat-activated [2+2] cycloaddition reaction facilitates divalent defect formation with fewer bonding positions that narrows emission bands. These groundbreaking findings have been experimentally validated and significantly advance our understanding of defect chemistry in SWCNTs. Using a novel encoding technique and 3D-MoRSE descriptors, we developed highly accurate ML/QSAR models to predict both the 3D structure and optical properties of SWCNTs with chemical defects. This model enabled the creation of a virtual library of 125,556 structures, providing new insights into the relationship between SWCNT-defect structure and emission.

77 NANOSCIENCE AND NANOTECHNOLOGY↗

Brittle-to-Ductile Transitions of Polyelectrolyte Complexes: Humidity, Temperature, and Salt

Polyelectrolyte complexation is an entropically driven, associative phase separation that results in a polymer-rich polyelectrolyte complex (PEC) and a polymer-poor supernatant. PECs show promise as a new class of sustainable materials since they can be processed using aqueous solutions rather than organic solvents. Previous reports have looked at the mechanical properties and glass transitions of PECs as a function of temperature, relative humidity (rH), and salt concentration (CS), but establishing a universal understanding of how these parameters affect PEC mechanics has yet to be achieved. We examined the effects of temperature, rH, and CS on the mechanical properties of PECs formed from poly(methacrylic acid) and poly(trimethyl aminoethyl methacrylate) with a goal of establishing design rules for their mechanical response. Relative humidity was shown to have the most dramatic effect on the mechanical properties, with temperature and salt concentration having far less of an impact. Furthermore, we observed that the glass transition of PECs is tied to both temperature and relative humidity, creating a glass transition rH g /T g line that can be modulated by added salt. Finally, we looked at the thermodynamics behind the glass transition of PECs, which yielded similar energies as the condensation of water. Here, we propose the use of water and/or salt as a low energy and efficient method of processing PECs for various applications.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗