Showing papers on "Phase (matter) published in 2021"

Smoothing the energy transfer pathway in quasi-2D perovskite films using methanesulfonate leads to highly efficient light-emitting devices.

Abstract: Quasi-two-dimensional (quasi-2D) Ruddlesden–Popper (RP) perovskites such as BA2Csn–1PbnBr3n+1 (BA = butylammonium, n > 1) are promising emitters, but their electroluminescence performance is limited by a severe non-radiative recombination during the energy transfer process. Here, we make use of methanesulfonate (MeS) that can interact with the spacer BA cations via strong hydrogen bonding interaction to reconstruct the quasi-2D perovskite structure, which increases the energy acceptor-to-donor ratio and enhances the energy transfer in perovskite films, thus improving the light emission efficiency. MeS additives also lower the defect density in RP perovskites, which is due to the elimination of uncoordinated Pb2+ by the electron-rich Lewis base MeS and the weakened adsorbate blocking effect. As a result, green light-emitting diodes fabricated using these quasi-2D RP perovskite films reach current efficiency of 63 cd A−1 and 20.5% external quantum efficiency, which are the best reported performance for devices based on quasi-2D perovskites so far. Owing to large exciton binding energy, quasi-2D perovskite is promising for light-emitting application, yet inhomogeneous phases distribution limits the potential. Here, the authors improve the performance by using MeS additive to regulate the phase distribution and to reduce defect density in the films.

Noble-Metal Based Random Alloy and Intermetallic Nanocrystals: Syntheses and Applications.

Abstract: Precise control over the size, shape, composition, structure, and crystal phase of random alloy and intermetallic nanocrystals has been intensively explored in technologically important application...

Chiral flux phase in the Kagome superconductor AV3Sb5

Abstract: We argue that the topological charge density wave phase in the quasi-2D Kagome superconductor AV3Sb5 is a chiral flux phase. Considering the symmetry of the Kagome lattice, we show that the chiral flux phase has the lowest energy among those states which exhibit 2 × 2 charge orders observed experimentally. This state breaks the time-reversal symmetry and displays anomalous Hall effect. The explicit pattern of the density of state in real space is calculated. These results are supported by recent experiments and suggest that these materials are new platforms to investigate the interplay between topology, superconductivity and electron–electron correlations.

Phase transitions in 2D materials

Abstract: The discovery and control of new phases of matter is a central endeavour in materials research. The emergence of atomically thin 2D materials, such as transition-metal dichalcogenides and monochalcogenides, has allowed the study of diffusive, displacive and quantum phase transitions in 2D. In this Review, we discuss the thermodynamic and kinetic features of 2D phase transitions arising from dimensionality confinement, elasticity, electrostatics, defects and chemistry unique to 2D materials. We highlight polymorphic, ferroic and high-temperature diffusive phase changes, and examine the technological potential of controlled 2D phase transitions. Finally, we give an outlook to future opportunities in the study and applications of 2D phase transitions, and identify key challenges that remain to be addressed. Phase transformations in 2D materials have distinct kinetic and thermodynamic features, resulting from their reduced dimensionality and unique interactions. This Review discusses the properties of phase transitions and defects in 2D materials, and examines technological applications and challenges in the study of 2D phase transitions.

Carbon dioxide capture using liquid absorption methods: a review

Abstract: Anthropogenic emissions of greenhouse gases into the atmosphere is inducing global warming, ocean acidification, polar ice melting, rise in sea level, droughts and hurricanes, thus threatening human health and the global economy. Therefore, there is a need to develop cost-effective technologies for CO2 capture. For instance, solution absorption is promising due to a large processing capacity, high flexibility and reliability, and rich experience in engineering applications. Nonetheless, actual commercial solutions, solvents and processes for CO2 capture suffer from slow reaction kinetics, low absorption capacity, high-energy consumption, susceptibility to corrosion, toxicity, low stability and high costs. Therefore, current research focuses on developing more economical, effective, green and sustainable technologies. Here we review 2015–2020 findings on CO2 capture using liquid absorption methods. Methods are based on various solutions, solvents and processes such as carbonate solution, ammonia solution, amine-based solution, ionic liquid, amino acid salt, phase changing absorbent, microcapsulated and membrane absorption, nanofluids and phenoxide salt solution. We discuss absorption performance, absorption mechanism, enhancement pathways and challenges. Amine- and NH3-based absorbents are widely used, yet they are limited by high regeneration energy, corrosiveness and degradation, reagent loss and secondary pollution caused by NH3 escape. Phase changing absorbents are getting more attention due to their lower cost and lower energy penalty. The incorporation of membrane and microencapsulation technologies to absorbing solvents could enhance CO2 absorption performance by reducing corrosion and increasing selectivity. Adding nanoparticles to solvents could improve CO2 absorption performance and reduce energy requirement. Besides, solvent blends and promoter-improved solvents performed better than single and non-promoted solvents because they combine the benefits of individual solvents and promoters.

Quantum Criticality in Twisted Transition Metal Dichalcogenides

Abstract: In moir\'e heterostructures, gate-tunable insulating phases driven by electronic correlations have been recently discovered. Here, we use transport measurements to characterize the gate-driven metal-insulator transitions and the metallic phase in twisted WSe$_2$ near half filling of the first moir\'e subband. We find that the metal-insulator transition as a function of both density and displacement field is continuous. At the metal-insulator boundary, the resistivity displays strange metal behaviour at low temperature with dissipation comparable to the Planckian limit. Further into the metallic phase, Fermi-liquid behaviour is recovered at low temperature which evolves into a quantum critical fan at intermediate temperatures before eventually reaching an anomalous saturated regime near room temperature. An analysis of the residual resistivity indicates the presence of strong quantum fluctuations in the insulating phase. These results establish twisted WSe$_2$ as a new platform to study doping and bandwidth controlled metal-insulator quantum phase transitions on the triangular lattice.

Isospin Pomeranchuk effect in twisted bilayer graphene

Abstract: In condensed-matter systems, higher temperatures typically disfavour ordered phases, leading to an upper critical temperature for magnetism, superconductivity and other phenomena. An exception is the Pomeranchuk effect in 3He, in which the liquid ground state freezes upon increasing the temperature1, owing to the large entropy of the paramagnetic solid phase. Here we show that a similar mechanism describes the finite-temperature dynamics of spin and valley isospins in magic-angle twisted bilayer graphene2. Notably, a resistivity peak appears at high temperatures near a superlattice filling factor of −1, despite no signs of a commensurate correlated phase appearing in the low-temperature limit. Tilted-field magnetotransport and thermodynamic measurements of the in-plane magnetic moment show that the resistivity peak is connected to a finite-field magnetic phase transition3 at which the system develops finite isospin polarization. These data are suggestive of a Pomeranchuk-type mechanism, in which the entropy of disordered isospin moments in the ferromagnetic phase stabilizes the phase relative to an isospin-unpolarized Fermi liquid phase at higher temperatures. We find the entropy, in units of Boltzmann’s constant, to be of the order of unity per unit cell area, with a measurable fraction that is suppressed by an in-plane magnetic field consistent with a contribution from disordered spins. In contrast to 3He, however, no discontinuities are observed in the thermodynamic quantities across this transition. Our findings imply a small isospin stiffness4,5, with implications for the nature of finite-temperature electron transport6–8, as well as for the mechanisms underlying isospin ordering and superconductivity9,10 in twisted bilayer graphene and related systems. An electronic analogue of the Pomeranchuk effect is present in twisted bilayer graphene, shown by the stability of entropy in a ferromagnetic phase compared to an unpolarized Fermi liquid phase at certain high temperatures.

Accurate model of liquid-liquid phase behavior of intrinsically disordered proteins from optimization of single-chain properties.

Abstract: Many intrinsically disordered proteins (IDPs) may undergo liquid-liquid phase separation (LLPS) and participate in the formation of membraneless organelles in the cell, thereby contributing to the regulation and compartmentalization of intracellular biochemical reactions. The phase behavior of IDPs is sequence dependent, and its investigation through molecular simulations requires protein models that combine computational efficiency with an accurate description of intramolecular and intermolecular interactions. We developed a general coarse-grained model of IDPs, with residue-level detail, based on an extensive set of experimental data on single-chain properties. Ensemble-averaged experimental observables are predicted from molecular simulations, and a data-driven parameter-learning procedure is used to identify the residue-specific model parameters that minimize the discrepancy between predictions and experiments. The model accurately reproduces the experimentally observed conformational propensities of a set of IDPs. Through two-body as well as large-scale molecular simulations, we show that the optimization of the intramolecular interactions results in improved predictions of protein self-association and LLPS.

Over 21% Efficiency Stable 2D Perovskite Solar Cells

Abstract: Owing to their insufficient light absorption and charge transport, 2D Ruddlesden-Popper (RP) perovskites show relatively low efficiency. In this work, methylammonium (MA), formamidinum (FA), and FA/MA mixed 2D perovskite solar cells (PSCs) are fabricated. Incorporating FA cations extends the absorption range and enhances the light absorption. Optical spectroscopy shows that FA cations substantially increase the portion of 3D-like phase to 2D phases, and X-ray diffraction (XRD) studies reveal that FA-based 2D perovskite possesses an oblique crystal orientation. Nevertheless, the ultrafast interphase charge transfer results in an extremely long carrier-diffusion length (≈1.98 µm). Also, chloride additives effectively suppress the yellow δ-phase formation of pure FA-based 2D PSCs. As a result, both FA/MA mixed and pure FA-based 2D PSCs exhibit a greatly enhanced power conversion efficiency (PCE) over 20%. Specifically, the pure FA-based 2D PSCs achieve a record PCE of 21.07% (certified at 20%), which is the highest efficiency for low-dimensional PSCs (n ≤ 10) reported to date. Importantly, the FA-based 2D PSCs retain 97% of their initial efficiency at 85 °C persistent heating after 1500 h. The results unambiguously demonstrate that pure-FA-based 2D PSCs are promising for achieving comparable efficiency to 3D perovskites, along with a better device stability.

Hot isostatic pressing of a near α-Ti alloy: Temperature optimization, microstructural evolution and mechanical performance evaluation

Abstract: Hot isostatic pressing (HIP) shows distinct advantages in the manufacture of difficult-to-process materials into components with geometric complexity and high mechanical performance. In this work, a near-α titanium alloy Ti–6Al–2Zr–1Mo–1V (TA15) designed for service temperatures of ~500 °C in the aerospace industry was processed by HIP at three representative temperatures. A systematic study on the phase constitutions, microstructural evolution, and tensile properties measured at 20, 500, 600, and 700 °C was carried out for the assessment of HIP TA15 specimens. The relationships among HIP temperature, crystallographic characteristic, and mechanical performance of HIP TA15 were elucidated in detail. Spark plasma sintering (SPS) was selected to compare with the HIP technique regarding the fabrication of TA15 alloy. The tensile strength and ductility of the HIP specimens at 500 °C were 14.8% and 52.8% higher than those of the SPS counterparts. Furthermore, the high-temperature tensile properties of HIP TA15 specimens were comparable to those of the forged IMI 685 and even better than those of sintered Ti60 parts. These findings can serve as a guideline for the HIP process of TA15 alloy and the HIP parameter optimization for other near-α Ti alloys applied in harsh environments.

Simulation of FUS Protein Condensates with an Adapted Coarse-Grained Model

Abstract: Disordered proteins and nucleic acids can condense into droplets that resemble the membraneless organelles observed in living cells. MD simulations offer a unique tool to characterize the molecular interactions governing the formation of these biomolecular condensates, their physicochemical properties, and the factors controlling their composition and size. However, biopolymer condensation depends sensitively on the balance between different energetic and entropic contributions. Here, we develop a general strategy to fine-tune the potential energy function for molecular dynamics simulations of biopolymer phase separation. We rebalance protein-protein interactions against solvation and entropic contributions to match the excess free energy of transferring proteins between dilute solution and condensate. We illustrate this formalism by simulating liquid droplet formation of the FUS low-complexity domain (LCD) with a rebalanced MARTINI model. By scaling the strength of the nonbonded interactions in the coarse-grained MARTINI potential energy function, we map out a phase diagram in the plane of protein concentration and interaction strength. Above a critical scaling factor of αc ≈ 0.6, FUS-LCD condensation is observed, where α = 1 and 0 correspond to full and repulsive interactions in the MARTINI model. For a scaling factor α = 0.65, we recover experimental densities of the dilute and dense phases, and thus the excess protein transfer free energy into the droplet and the saturation concentration where FUS-LCD condenses. In the region of phase separation, we simulate FUS-LCD droplets of four different sizes in stable equilibrium with the dilute phase and slabs of condensed FUS-LCD for tens of microseconds, and over one millisecond in aggregate. We determine surface tensions in the range of 0.01-0.4 mN/m from the fluctuations of the droplet shape and from the capillary-wave-like broadening of the interface between the two phases. From the dynamics of the protein end-to-end distance, we estimate shear viscosities from 0.001 to 0.02 Pa s for the FUS-LCD droplets with scaling factors α in the range of 0.625-0.75, where we observe liquid droplets. Significant hydration of the interior of the droplets keeps the proteins mobile and the droplets fluid.

Generating Dual-Polarized Vortex Beam by Detour Phase: From Phase Gradient Metasurfaces to Metagratings

Abstract: Traditional methods of generating vortex beams based on metasurfaces consist mainly in modulating propagation phase or geometric phase. Here, by introducing detour phase, we propose the construction of dual-polarized vortex beam generators in the form of metasurface and metagrating (MG). The phase is modulated through moving the position of meta-atoms instead of varying the geometrical parameters or rotating the unit cells. To use detour phase, two kinds of unit cells are designed to achieve specific diffraction order. Each unit can arbitrarily and independently adjust the operation frequency and diffraction angle of transverse electric (TE) and transverse magnetic (TM) polarizations. Two vortex beam generators are designed and fabricated with different topological charges carried by orthogonal polarizations. To demonstrate the ability to independently manipulate, two polarizations of the generator based on MG are designed in different frequency bands. Both the simulation and experimental results validate the proposed method, showing great potential for polarization division multiplexing in orbital angular momentum (OAM) communication systems.

Ligand effects on phase separation of multivalent macromolecules

Abstract: Biomolecular condensates enable spatial and temporal control over cellular processes by concentrating biomolecules into nonstoichiometric assemblies. Many condensates form via reversible phase transitions of condensate-specific multivalent macromolecules known as scaffolds. Phase transitions of scaffolds can be regulated by changing the concentrations of ligands, which are defined as nonscaffold molecules that bind to specific sites on scaffolds. Here, we use theory and computation to uncover rules that underlie ligand-mediated control over scaffold phase behavior. We use the stickers-and-spacers model wherein reversible noncovalent cross-links among stickers drive phase transitions of scaffolds, and spacers modulate the driving forces for phase transitions. We find that the modulatory effects of ligands are governed by the valence of ligands, whether they bind directly to stickers versus spacers, and the relative affinities of ligand–scaffold versus scaffold–scaffold interactions. In general, all ligands have a diluting effect on the concentration of scaffolds within condensates. Whereas monovalent ligands destabilize condensates, multivalent ligands can stabilize condensates by binding directly to spacers or destabilize condensates by binding directly to stickers. Bipartite ligands that bind to stickers and spacers can alter the structural organization of scaffold molecules within condensates even when they have a null effect on condensate stability. Our work highlights the importance of measuring dilute phase concentrations of scaffolds as a function of ligand concentration in cells. This can reveal whether ligands modulate scaffold phase behavior by enabling or suppressing phase separation at endogenous levels, thereby regulating the formation and dissolution of condensates in vivo.

Unique surface patterns emerging during solidification of liquid metal alloys

Abstract: It is well-understood that during the liquid-to-solid phase transition of alloys, elements segregate in the bulk phase with the formation of microstructures. In contrast, we show here that in a Bi–Ga alloy system, highly ordered nanopatterns emerge preferentially at the alloy surfaces during solidification. We observed a variety of transition, hybrid and crystal-defect-like patterns, in addition to lamellar and rod-like structures. Combining experiments and molecular dynamics simulations, we investigated the influence of the superficial Bi and Ga2O3 layers during surface solidification and elucidated the pattern-formation mechanisms, which involve surface-catalysed heterogeneous nucleation. We further demonstrated the dynamic nature and robustness of the phenomenon under different solidification conditions and for various alloy systems. The surface patterns we observed enable high-spatial-resolution nanoscale-infrared and surface-enhanced Raman mapping, which reveal promising potential for surface- and nanoscale-based applications. During a liquid-to-solid phase transition, a Bi–Ga alloy forms ordered nanostructured patterns on its surface.

Fe and P Doped 1T-Phase Enriched WS23D-Dendritic Nanostructures for Efficient Overall Water Splitting

Abstract: 1T-WS2 is known for its higher hydrogen evolution reaction (HER) performance than 2H-WS2. However, the lack of thermodynamic stability and absence of large-scale synthesis procedures kept 1T-WS2 significantly ignored to date. In this report, for the first time, we have fabricated 1T-WS2 in 3D-dendritic nanostructures over flexible carbon cloth (CC) following doping and intercalation of Fe and P (1T-Fe/P-WS2@CC). The HER and OER activities of 1T-Fe/P-WS2@CC outperform state-of-the-art electrocatalysts, demonstrating a low overpotential (ηHER =116 mV, ηOER =267 mV @ 10 mA cm−2), small Tafel slope (HER =65 mV dec-1, OER =70.1 mV dec-1), and significant durability. The 1T-Fe/P-WS2@CC (+,−) alkaline elctrolyzer also shows exceptional high performance, required only 1.53 V cell voltage at the current density of 10 mA cm−2. Overall, this work opens up a new dimension for simple and scalable fabrication of highly efficient and low-cost electrocatalyst based on WS2.

High-Entropy Atomic Layers of Transition-Metal Carbides (MXenes)

Abstract: High-entropy materials (HEMs) have great potential for energy storage and conversion due to their diverse compositions, and unexpected physical and chemical features. However, high-entropy atomic layers with fully exposed active sites are difficult to synthesize since their phases are easily segregated. Here, it is demonstrated that high-entropy atomic layers of transition-metal carbide (HE-MXene) can be produced via the selective etching of novel high-entropy MAX (also termed Mn+1 AXn (n = 1, 2, 3), where M represents an early transition-metal element, A is an element mainly from groups 13-16, and X stands for C and/or N) phase (HE-MAX) (Ti1/5 V1/5 Zr1/5 Nb1/5 Ta1/5 )2 AlC, in which the five transition-metal species are homogeneously dispersed into one MX slab due to their solid-solution feature, giving rise to a stable transition-metal carbide in the atomic layers owing to the high molar configurational entropy and correspondingly low Gibbs free energy. Additionally, the resultant high-entropy MXene with distinct lattice distortions leads to high mechanical strain into the atomic layers. Moreover, the mechanical strain can efficiently guide the nucleation and uniform growth of dendrite-free lithium on HE-MXene, achieving a long cycling stability of up to 1200 h and good deep stripping-plating levels of up to 20 mAh cm-2 .