Mixed Enthalpy-Entropy Descriptor for the Rational Design of Synthesizable High-Entropy Materials Over Vast Chemical Spaces.

The practically unlimited high-dimensional composition space of high-entropy materials (HEMs) has emerged as an exciting platform for functional material design and discovery. However, the identification of stable and synthesizable HEMs and robust design rules remains a daunting challenge. Here, we propose a mixed enthalpy-entropy descriptor (MEED) that enables highly efficient, robust, high-throughput prediction of synthesizable HEMs across vast chemical spaces from first-principles. The MEED is based on two parameters: the relative formation enthalpy with respect to the most stable competing compound and the spread of the point-defect formation energy spectrum. The former measures the relative synthesizability of an HEM to its most stable competing phase, going beyond the conventional thermodynamic understanding. The latter gauges the relative entropy forming ability of an HEM, entailing no sampling over numerous alloy configurations. By applying the MEED to two structurally distinct representative material systems (i.e., 3D rocksalt carbides and 2D layered sulfides), we not only successfully identify all experimentally reported HEMs within these systems but also reveal a cutoff criterion for assessing their relative synthesizability within each system. By the MEED, tens of new high-entropy carbides and 2D high-entropy sulfides are also predicted, which have the potential for a wide variety of applications such as coating in aerospace devices, energy conversion and storage, and flexible electronics.

Moiré Skyrmions and Chiral Magnetic Phases in Twisted CrX3 (X = I, Br, and Cl) Bilayers.

We present a comprehensive theory of the magnetic phases in twisted bilayer chromium trihalides through a combination of first-principles calculations and atomistic simulations. We show that the stacking-dependent interlayer exchange leads to an effective moiré field that is mostly ferromagnetic with antiferromagnetic patches. A wide range of noncollinear magnetic phases can be stabilized as a function of the twist angle and Dzyaloshinskii-Moriya interaction as a result of the competing interlayer antiferromagnetic coupling and the energy cost for forming domain walls. In particular, we demonstrate that for small twist angles various skyrmion crystal phases can be stabilized in both CrI3 and CrBr3. Our results provide an interpretation for the recent observation of noncollinear magnetic phases in twisted bilayer CrI3 and demonstrate the possibility of engineering further nontrivial magnetic ground states in twisted bilayer chromium trihalides.

Sensing of Gunshot Residue components from real sample using Fluorescence Resonance Energy Transfer.

The present work represents a Fluorescence Resonance Energy Transfer (FRET) based sensing method for detecting Gunshot Residue (GSR) components. Two laser dyes Acf and RhB have been used as donor and acceptor respectively in the FRET pair. The real sample was collected after test firing in a forensic science laboratory. On the other hand, a standard GSR solution has been prepared in the laboratory. For the preparation of standard GSR solutions, we used the water solutions of the salts BaCl2, SbCl3, and Pb(NO3)2. The FRET efficiency was measured between Acf and RhB to sense the presence of GSR components (Pb+2, Ba+2, and Sb+3) in both real sample and standard solution by mixing the salts in aqueous solution. It has been observed that the FRET efficiency systematically decreases in the presence of GSR components. To amplify the FRET efficiency of the dye pair, inorganic clay dispersion (laponite) was used. The enhancement in FRET efficiency represents a better sensitivity of the proposed sensor. The current sensor is useful for the quantification of concentrations of the GSR components in a real sample.

Integrated all-optical infrared switchable plasmonic quantum cascade laser.

We report a type of infrared switchable plasmonic quantum cascade laser, in which far field light in the midwave infrared (MWIR, 6.1 µm) is modulated by a near field interaction of light in the telecommunications wavelength (1.55 µm). To achieve this all-optical switch, we used cross-polarized bowtie antennas and a centrally located germanium nanoslab. The bowtie antenna squeezes the short wavelength light into the gap region, where the germanium is placed. The perturbation of refractive index of the germanium due to the free carrier absorption produced by short wavelength light changes the optical response of the antenna and the entire laser intensity at 6.1 µm significantly. This device shows a viable method to modulate the far field of a laser through a near field interaction.

Development of a DNA sensor using a molecular logic gate.

This communication reports the increase in fluorescence resonance energy transfer (FRET) efficiency between two laser dyes in the presence of deoxyribonucleic acid (DNA). Two types of molecular logic gates have been designed where DNA acts as input signal and fluorescence intensity of different bands are taken as output signal. Use of these logic gates as a DNA sensor has been demonstrated.

Optomechanical nanoantenna.

We introduce optomechanical nanoantennae, which show dramatic changes in scattering properties by minuscule changes in geometry. These structures are very compact, with a volume 500 times smaller than free-space optical wavelength volume. This deep subwavelength geometry leads to high speed and low switching power. The bandwidth of the device is about 4.4 GHz, with a switching energy of only 35 pJ. Such antenna structures could lead to compact and high-speed all-optical nanoswitches.

Opto-mechanical force mapping of deep subwavelength plasmonic modes.

We present spatial mapping of optical force generated near the hot spot of a metal-dielectric-metal bowtie nanoantenna at a wavelength of 1550 nm. Maxwell's stress tensor method has been used to simulate the optical force and it agrees well with the experimental data. This method could potentially produce field intensity and optical force mapping simultaneously with a high spatial resolution. Detailed mapping of the optical force is crucial for understanding and designing plasmonic-based optical trapping for emerging applications such as chip-scale biosensing and optomechanical switching.

Reaching the Excitonic Limit in 2D Janus Monolayers by In Situ Deterministic Growth.

Named after the two-faced Roman god of transitions, transition metal dichalcogenide (TMD) Janus monolayers have two different chalcogen surfaces, inherently breaking the out-of-plane mirror symmetry. The broken mirror symmetry and the resulting potential gradient lead to the emergence of quantum properties such as the Rashba effect and the formation of dipolar excitons. Experimental access to these quantum properties, however, hinges on the ability to produce high-quality 2D Janus monolayers. Here, these results introduce a holistic 2D Janus synthesis technique that allows real-time monitoring of the growth process. This prototype chamber integrates in situ spectroscopy, offering fundamental insights into the structural evolution and growth kinetics, that allow the evaluation and optimization of the quality of Janus monolayers. The versatility of this method is demonstrated by synthesizing and monitoring the conversion of SWSe, SNbSe, and SMoSe Janus monolayers. Deterministic conversion and real-time data collection further aid in conversion of exfoliated TMDs to Janus monolayers and unparalleled exciton linewidth values are reached, compared to the current best standard. The results offer an insight into the process kinetics and aid in the development of new Janus monolayers with high optical quality, which is much needed to access their exotic properties.

Quantum-cascade laser integrated with a metal-dielectric-metal-based plasmonic antenna.

Optical nanoantennas are capable of enhancing the near-field intensity and confining optical energy within a small spot size. We report a novel metal-dielectric-metal coupled-nanorods antenna integrated on the facet of a quantum-cascade laser. Finite-difference time-domain simulations showed that, for dielectric thicknesses in the range from 10 to 30 nm, peak optical intensity at the top of the antenna gap is 4000 times greater than the incident field intensity. This is 4 times higher enhancement compared to a coupled metal antenna. The antenna is fabricated using focused ion-beam milling and measured using modified scanning probe microscopy. Such a device has potential applications in building mid-IR biosensors.

Rapid Visual Detection of Amines by Pyrylium Salts for Food Spoilage Taggant.

Amines are ubiquitous in biological world, but are toxic and harmful in nature. Detection of biogenic amines that are released from spoiled seafood, meat, or dairy products is an important task to maintain the quality and safety of these packaged foods. To this endeavor, herein we report pyrylium salts that are capable of sensing various amines by rapid change of fluorescence color or intensity. In molecular level, this change of fluorescence is rooted to the formation of pyridine or analogous product that have distinct optical property. The pyrylium salts are capable of efficiently sensing amine vapors or amine solutions both in solid state and in solution state and thus demonstrating a multiphase sensing platform. Utilizing the excellent sensing property, we have employed our pyrylium compounds as spoilage indicator for food products such as fish, meat or cheese which relies on sensing biogenic amines released from these spoiled foods and provide optical response. Prominent change in visible and luminescence color was observed within 4-18 h of packaging at room temperature (∼33 °C). Considering the rapid response for biogenic amines, these molecular sensors have great potential to be utilized for food packaging industry, medical diagnostics, or other sensory devices.

Nature of spiral state and absence of electric polarisation in Sr-doped YBaCuFeO5 revealed by first-principle study.

Experimental results on YBaCuFeO5, in its incommensurate magnetic phase, appear to disagree on its ferroelectric response. Ambiguity exists on the nature of the spiral magnetic state too. Using first-principles density functional theory (DFT) calculations for the parent compound within LSDA + U + SO approximation, we reveal the nature of spiral state. The helical spiral is found to be more stable below the transition temperature as spins prefer to lie in ab plane. Dzyaloshinskii-Moriya (DM) interaction turns out to be negligibly small and the spin current mechanism is not valid in the helical spiral state, ruling out an electric polarisation from either. These results are in very good agreement with the recent, high quality, single-crystal data. We also investigate the magnetic transition in YBa1-xSrxCuFeO5 for the entire range (0 ≤ x ≤ 1) of doping. The exchange interactions are estimated as a function of doping and a quantum Monte Carlo (QMC) calculation on an effective spin Hamiltonian shows that the paramagnetic to commensurate phase transition temperature increases with doping till x = 0.5 and decreases beyond. These observations are consistent with experimental findings.

First-Principles Correlated Approach to the Normal State of Strontium Ruthenate.

The interplay between multiple bands, sizable multi-band electronic correlations and strong spin-orbit coupling may conspire in selecting a rather unusual unconventional pairing symmetry in layered Sr2RuO4. This mandates a detailed revisit of the normal state and, in particular, the T-dependent incoherence-coherence crossover. Using a modern first-principles correlated view, we study this issue in the actual structure of Sr2RuO4 and present a unified and quantitative description of a range of unusual physical responses in the normal state. Armed with these, we propose that a new and important element, that of dominant multi-orbital charge fluctuations in a Hund's metal, may be a primary pair glue for unconventional superconductivity. Thereby we establish a connection between the normal state responses and superconductivity in this system.

Effect of Zinc oxide nanoparticle on Fluorescence Resonance Energy transfer between Fluorescein and Rhodamine 6G.

Fluorescence Resonance Energy Transfer between two dyes Fluorescein and Rhodamine 6G were investigated in solution in the presence and absence of Zinc oxide nanoparticle. Zinc oxide nanostructure is used as the fluorescence enhancing agent for the present study since donor (Fluorescein) fluorescence increase significantly in presence of nanoparticle. Accordingly, the energy transfer efficiency in the presence of nanoparticle increases. The maximum efficiency was 69% for acceptor (Rhodamine 6G) concentration of 0.75×10-5M. The energy transfer efficiency was found to be pH sensitive and it varies from 4.15% to 90.00% in mixed dye solution for a change in pH from 1.5 to 10.0. With proper calibration it is possible to use the present system under investigation to sense pH which is better with respect to our previous reported results [Spectrochim. Acta Part A. 149 (2015) 143-149] as it can sense a wide range of pH and with better sensitivity.

Development of a sensor to study the DNA conformation using molecular logic gates.

This communication reports our investigations on the Fluorescence Resonance Energy Transfer (FRET) between two laser dyes Acriflavine and Rhodamine B in absence and presence of DNA at different pH. It has been observed that energy transfer efficiency is largely affected by the presence of DNA as well as the pH of the system. It is well known that with increase in pH, DNA conformation changes from double stranded to single stranded (denaturation) and finally form random coil. Based on our experimental results two different types of molecular logic gates namely, XOR and OR logic have been demonstrated which can be used to have an idea about DNA conformation in solution.

Investigation of Fluorescence Resonance Energy Transfer between Fluorescein and Rhodamine 6G.

Fluorescence Resonance Energy Transfer between two organic dyes Fluorescein and Rhodamine 6G was investigated in aqueous solution in presence and absence of synthetic clay laponite. Spectroscopic studies suggest that both the dyes were present mainly as monomer in solution. Fluorescence Resonance Energy Transfer occurred from Fluorescein to Rhodamine 6G in solutions. Energy transfer efficiency increases in presence of laponite and the maximum efficiency was 72.00% in aqueous laponite dispersion. Energy transfer efficiency was found to be pH sensitive. It has been demonstrated that with proper calibration it is possible to use the present system under investigation to sense pH over a wide range from 1.5 to 8.0.