Tuning the color of high-karat gold in Au-TiO2 nanoparticle composites all the way to black.

For centuries, artisans have harnessed gold nanoparticles to imbue their creations with the vibrant hues that captivate the eye through interactions with visible light. In modern times, these distinct optoelectronic characteristics have pivoted toward the forefront of innovative technologies, finding their niche in advanced applications from solar energy to medicine, overshadowing their artistic heritage. This investigation reimagines the utilitarian scope of gold by innovating the optical characteristics of gold-titania nanostructures. This allows for an expanded palette of colors that retain the value of the precious metal. We employ nanostructured TiO2 in a high-pressure-high-temperature sintering technique that stabilizes Au nanoparticles, thwarting coalescence, and Oswald ripening. Further refinement is possible by engineering TiO2 color centers through the introduction of oxygen vacancies and Ti3+ ions, which aid in creating an opulent high-karat black-gold, but preserve the mechanical attributes essential to the integrity and function of the final product.

Terahertz emission from diamond nitrogen-vacancy centers.

Coherent light sources emitting in the terahertz range are highly sought after for fundamental research and applications. Terahertz lasers rely on achieving population inversion. We demonstrate the generation of terahertz radiation using nitrogen-vacancy centers in a diamond single crystal. Population inversion is achieved through the Zeeman splitting of the S = 1 state in 15 tesla, resulting in a splitting of 0.42 terahertz, where the middle Sz = 0 sublevel is selectively pumped by visible light. To detect the terahertz radiation, we use a phase-sensitive terahertz setup, optimized for electron spin resonance (ESR) measurements. We determine the spin-lattice relaxation time up to 15 tesla using the light-induced ESR measurement, which shows the dominance of phonon-mediated relaxation and the high efficacy of the population inversion. The terahertz radiation is tunable by the magnetic field, thus these findings may lead to the next generation of tunable coherent terahertz sources.

Origin of Subgap States in Normal-Insulator-Superconductor van der Waals Heterostructures.

Superconductivity in van der Waals materials, such as NbSe2 and TaS2, is fundamentally novel due to the effects of dimensionality, crystal symmetries, and strong spin-orbit coupling. In this work, we perform tunnel spectroscopy on NbSe2 by utilizing MoS2 or hexagonal boron nitride (hBN) as a tunnel barrier. We observe subgap excitations and probe their origin by studying various heterostructure designs. We show that the edge of NbSe2 hosts many defect states, which strongly couple to the superconductor and form Andreev bound states. Furthermore, by isolating the NbSe2 edge we show that the subgap states are ubiquitous in MoS2 tunnel barriers but absent in hBN tunnel barriers, suggesting defects in MoS2 as their origin. Their magnetic nature reveals a singlet- or a doublet-type ground state, and based on nearly vanishing g factors or avoided crossings of subgap excitations, we highlight the role of strong spin-orbit coupling.

Axial-Bonding-Driven Dimensionality Effect on the Charge-Density Wave in NbSe2.

2H-NbSe2 is a prototypical charge-density-wave (CDW) system, exhibiting such a symmetry-breaking quantum ground state in its bulk and down to a single-atomic-layer limit. However, how this state depends on dimensionality and what governs the dimensionality effect remain controversial. Here, we experimentally demonstrate a robust 3 × 3 CDW phase in both freestanding and substrate-supported bilayer NbSe2, far above the bulk transition temperature. We exclude environmental effects and reveal a strong temperature and thickness dependence of Raman intensity from an axially vibrating A1g phonon mode, involving Se ions. Using first-principles calculations, we show that these result from a delicate but profound competition between the intra- and interlayer bonding formed between Se-pz orbitals. Our results suggest the crucial role of Se out-of-plane displacement in driving the CDW distortion, revealing the Se-dominated dimensionality effect and establishing a new perspective on the chemical bonding and mechanical stability in layered CDW materials.

van der Waals π Josephson Junctions.

Proximity-induced superconductivity in a ferromagnet can induce Cooper pairs with a finite center-of-mass momentum and stabilize Josephson junctions (JJs) with π phase difference in superconductor-ferromagnet-superconductor heterostructures. The emergence of two-dimensional layered superconducting and magnetic materials promises a new platform for realizing π JJs with atomically sharp interfaces. Here we demonstrate a thickness-driven 0-π transition in JJs made of NbSe2 (an Ising superconductor) and Cr2Ge2Te6 (a ferromagnetic semiconductor). By systematically increasing the Cr2Ge2Te6 weak link thickness, we observe a vanishing supercurrent at a critical thickness of ∼8 nm, followed by a re-entrant supercurrent. Near the critical thickness, we further observe unusual supercurrent interference patterns with vanishing critical current around zero in-plane magnetic field. They signify the formation of 0-π JJs (with both 0 and π regions), likely induced by the nanoscale magnetic domains in Cr2Ge2Te6.

Hybrid halide perovskite neutron detectors.

Interest in fast and easy detection of high-energy radiation (x-, γ-rays and neutrons) is closely related to numerous practical applications ranging from biomedicine and industry to homeland security issues. In this regard, crystals of hybrid halide perovskite have proven to be excellent detectors of x- and γ-rays, offering exceptionally high sensitivities in parallel to the ease of design and handling. Here, we demonstrate that by assembling a methylammonium lead tri-bromide perovskite single crystal (CH3NH3PbBr3 SC) with a Gadolinium (Gd) foil, one can very efficiently detect a flux of thermal neutrons. The neutrons absorbed by the Gd foil turn into γ-rays, which photo-generate charge carriers in the CH3NH3PbBr3 SC. The induced photo-carriers contribute to the electric current, which can easily be measured, providing information on the radiation intensity of thermal neutrons. The dependence on the beam size, bias voltage and the converting distance is investigated. To ensure stable and efficient charge extraction, the perovskite SCs were equipped with carbon electrodes. Furthermore, other types of conversion layers were also tested, including borated polyethylene sheets as well as Gd grains and Gd2O3 pellets directly engulfed into the SCs. Monte Carlo N-Particle (MCNP) radiation transport code calculations quantitatively confirmed the detection mechanism herein proposed.

Chromophore of an Enhanced Green Fluorescent Protein Can Play a Photoprotective Role Due to Photobleaching.

Under stress conditions, elevated levels of cellular reactive oxygen species (ROS) may impair crucial cellular structures. To counteract the resulting oxidative damage, living cells are equipped with several defense mechanisms, including photoprotective functions of specific proteins. Here, we discuss the plausible ROS scavenging mechanisms by the enhanced green fluorescent protein, EGFP. To check if this protein could fulfill a photoprotective function, we employed electron spin resonance (ESR) in combination with spin-trapping. Two organic photosensitizers, rose bengal and methylene blue, as well as an inorganic photocatalyst, nano-TiO2, were used to photogenerate ROS. Spin-traps, TMP-OH and DMPO, and a nitroxide radical, TEMPOL, served as molecular targets for ROS. Our results show that EGFP quenches various forms of ROS, including superoxide radicals and singlet oxygen. Compared to the three proteins PNP, papain, and BSA, EGFP revealed high ROS quenching ability, which suggests its photoprotective role in living systems. Damage to the EGFP chromophore was also observed under strong photo-oxidative conditions. This study contributes to the discussion on the protective function of fluorescent proteins homologous to the green fluorescent protein (GFP). It also draws attention to the possible interactions of GFP-like proteins with ROS in systems where such proteins are used as biological markers.

Fighting Health Hazards in Lead Halide Perovskite Optoelectronic Devices with Transparent Phosphate Salts.

Organic-inorganic lead halide perovskite (CH3NH3PbI3) solar cells have surpassed 25% power conversion efficiency, being ready for industrial-scale production of cheap photovoltaic (PV) panels. In this action, the major hurdle is its lead content, which in case of device failure, could be washed into the soil, entering the food chain. Since there is a zero tolerance on lead in the human organism, this health hazard is a critical obstacle for commercialization. Here, we propose a solution to this problem by incorporating phosphate salts (e.g., (NH4)2HPO4) in PV and other perovskite-based optoelectronic devices in various architectures. Phosphate salts do not react with CH3NH3PbI3 and do not alter its advantageous optoelectronic properties, but in a wet environment, they react immediately with lead, forming a highly insoluble compound, precluding this way the spread of lead into the environment. It is expected that this study will stimulate research, enabling lead halide perovskite solar cells to reach a similar environmental risk category as the commercially available, nonwater-soluble heavy metal-containing CdTe and gallium diselenide technologies.

Ultrasensitive 3D Aerosol-Jet-Printed Perovskite X-ray Photodetector.

X-ray photon detection is important for a wide range of applications. The highest demand, however, comes from medical imaging, which requires cost-effective, high-resolution detectors operating at low-photon flux, therefore stimulating the search for novel materials and new approaches. Recently, hybrid halide perovskite CH3NH3PbI3 (MAPbI3) has attracted considerable attention due to its advantageous optoelectronic properties and low fabrication costs. The presence of heavy atoms, providing a high scattering cross-section for photons, makes this material a perfect candidate for X-ray detection. Despite the already-successful demonstrations of efficiency in detection, its integration into standard microelectronics fabrication processes is still pending. Here, we demonstrate a promising method for building X-ray detector units by 3D aerosol jet printing with a record sensitivity of 2.2 × 108 µC Gyair-1 cm-2 when detecting 8 keV photons at dose rates below 1 µGy/s (detection limit 0.12 µGy/s), a 4-fold improvement on the best-in-class devices. An introduction of MAPbI3-based detection into medical imaging would significantly reduce health hazards related to the strongly ionizing X-rays' photons.

Kilogram-Scale Crystallogenesis of Halide Perovskites for Gamma-Rays Dose Rate Measurements.

Gamma-rays (γ-rays), wherever present, e.g., in medicine, nuclear environment, or homeland security, due to their strong impact on biological matter, should be closely monitored. There is a need for simple, sensitive γ-ray detectors at affordable prices. Here, it is shown that γ-ray detectors based on crystals of methylammonium lead tribromide (MAPbBr3) ideally meet these requirements. Specifically, the γ-rays incident on a MAPbBr3 crystal generates photocarriers with a high mobility-lifetime product, allowing radiation detection by photocurrent measurements at room temperatures. Moreover, the MAPbBr3 crystal-based detectors, equipped with improved carbon electrodes, can operate at low bias (≈1.0 V), hence being suitable for applications in energy-sparse environments, including space. The γ-ray detectors reported herein are exposed to radiation from a 60Co source at dose rates up to 2.3 Gy h-1 under ambient conditions for over 100 h, without any sign of degradation. The excellent radiation tolerance stems from the intrinsic structural plasticity of the organic-inorganic halide perovskites, which can be attributed to a defect-healing process by fast ion migration at the nanoscale level. The sensitivity of the γ-ray detection upon volume is tested for MAPbBr3 crystals reaching up to 1000 cm3 (3.3 kg in weight) grown by a unique crystal growth technique.

High-Pressure Synthesis of Rare-Earth Borate-Nitrate Crystals for Second Harmonic Generation.

The crystals of a novel family of rare-earth borate-nitrate compounds, Ln7(BO3)3(NO3)N3O (Ln = Pr, Nd), were grown at high-pressure in KAs flux and their crystal structure was determined. The new type of the crystalline structure consists of parallel chains of Ln6 octahedra connected by common faces and forming the channels with the NO3 triangular planar motifs in the center, and isolated OLn4 tetrahedra separated from each other by N3 triangular motifs. Each NO3 triangle is in fact a part of rather unusual (NB3O12) block consisting of 3 distorted BO4 tetrahedra around central nitrogen atom. Under near-infrared (NIR) (λex = 1064 nm) excitation, both compounds revealed a strong signal of second harmonic generation (SHG) at half the excitation wavelength (λem = 532 nm), which is in agreement with their noncentrosymmetric structure. In addition, a photon up-conversion (UC) emission at λem = 880 nm was observed for microcrystals of Nd7(BO3)3(NO3)N3O, which was assigned to the UC process occurring within the 4f electronic manifold of Nd3+ ions. The dual-emission (SHG/UC) properties of Nd7(BO3)3(NO3)N3O microcrystals, concomitant with the absence of photobleaching, makes them prospective candidates for microscopic probes in biological studies.

Quantum spin-liquid states in an organic magnetic layer and molecular rotor hybrid.

The exotic properties of quantum spin liquids (QSLs) have continually been of interest since Anderson's 1973 ground-breaking idea. Geometrical frustration, quantum fluctuations, and low dimensionality are the most often evoked material's characteristics that favor the long-range fluctuating spin state without freezing into an ordered magnet or a spin glass at low temperatures. Among the few known QSL candidates, organic crystals have the advantage of having rich chemistry capable of finely tuning their microscopic parameters. Here, we demonstrate the emergence of a QSL state in [EDT-TTF-CONH2]2 +[[Formula: see text]] (EDT-BCO), where the EDT molecules with spin-1/2 on a triangular lattice form layers which are separated by a sublattice of BCO molecular rotors. By several magnetic measurements, we show that the subtle random potential of frozen BCO Brownian rotors suppresses magnetic order down to the lowest temperatures. Our study identifies the relevance of disorder in the stabilization of QSLs.

Intermolecular Resonance Correlates Electron Pairs Down a Supermolecular Chain: Antiferromagnetism in K-Doped p-Terphenyl.

Recent interest in potassium-doped p-terphenyl has been fueled by reports of superconductivity at Tc values surprisingly high for organic compounds. Despite these interesting properties, studies of the structure-function relationships within these materials have been scarce. Here, we isolate a phase-pure crystal of potassium-doped p-terphenyl: [K(222)]2[p-terphenyl3]. Emerging antiferromagnetism in the anisotropic structure is studied in depth by magnetometry and electron spin resonance. Combining these experimental results with density functional theory calculations, we describe the antiferromagnetic coupling in this system that occurs in all 3 crystallographic directions. The strongest coupling was found along the ends of the terphenyls, where the additional electron on neighboring p-terphenyls antiferromagnetically couple. This delocalized bonding interaction is reminiscent of the doubly degenerate resonance structure depiction of polyacetylene. These findings hint toward magnetic fluctuation-induced superconductivity in potassium-doped p-terphenyl, which has a close analogy with high Tc cuprate superconductors. The new approach described here is very versatile as shown by the preparation of two additional salts through systematic changing of the building blocks.

Photocatalytic Nanowires-Based Air Filter: Towards Reusable Protective Masks.

In the last couple decades, several viral outbreaks resulting in epidemics and pandemics with thousands of human causalities have been witnessed. The current Covid-19 outbreak represents an unprecedented crisis. In stopping the virus' spread, it is fundamental to have personal protective equipment and disinfected surfaces. Here, the development of a TiO2 nanowires (TiO2NWs) based filter is reported, which it is believed will work extremely well for personal protective equipment (PPE), as well as for a new generation of air conditioners and air purifiers. Its efficiency relies on the photocatalytic generation of high levels of reactive oxygen species (ROS) upon UV illumination, and on a particularly high dielectric constant of TiO2, which is of paramount importance for enhanced wettability by the water droplets carrying the germs. The filter pore sizes can be tuned by processing TiO2NWs into filter paper. The kilogram-scale production capability of TiO2NWs gives credibility to its massive application potentials.

Patterns and driving forces of dimensionality-dependent charge density waves in 2H-type transition metal dichalcogenides.

Charge density wave (CDW) is a startling quantum phenomenon, distorting a metallic lattice into an insulating state with a periodically modulated charge distribution. Astonishingly, such modulations appear in various patterns even within the same family of materials. Moreover, this phenomenon features a puzzling diversity in its dimensional evolution. Here, we propose a general framework, unifying distinct trends of CDW ordering in an isoelectronic group of materials, 2H-MX2 (M = Nb, Ta and X = S, Se). We show that while NbSe2 exhibits a strongly enhanced CDW order in two dimensions, TaSe2 and TaS2 behave oppositely, with CDW being absent in NbS2 entirely. Such a disparity is demonstrated to arise from a competition of ionic charge transfer, electron-phonon coupling, and electron correlation. Despite its simplicity, our approach can, in principle, explain dimensional dependence of CDW in any material, thereby shedding new light on this intriguing quantum phenomenon and its underlying mechanisms.

Filamentous and step-like behavior of gelling coarse fibrin networks revealed by high-frequency microrheology.

By a micro-experimental methodology, we study the ongoing molecular process inside coarse fibrin networks by means of microrheology. We made these networks gelate around a probe microbead, allowing us to observe a temporal evolution compatible with the well-known molecular formation of fibrin networks in four steps: monomer, protofibril, fiber and network. Thanks to the access that optical-trapping interferometry provides to the short-time scale on the bead's Brownian motion, we observe a Kelvin-Voigt mechanical behavior from low to high frequencies, range not available in conventional rheometry. We exploit that mechanical model for obtaining the characteristic lengths of the filamentous structures composing these fibrin networks, whose obtained values are compatible with a non-affine behavior characterized by bending modes. At very long gelation times, a ω7/8 power-law is observed in the loss modulus, theoretically related with the longitudinal response of the molecular structures.

Tuning ferromagnetism at room temperature by visible light.

Most digital information today is encoded in the magnetization of ferromagnetic domains. The demand for ever-increasing storage space fuels continuous research for energy-efficient manipulation of magnetism at smaller and smaller length scales. Writing a bit is usually achieved by rotating the magnetization of domains of the magnetic medium, which relies on effective magnetic fields. An alternative approach is to change the magnetic state directly by acting on the interaction between magnetic moments. Correlated oxides are ideal materials for this because the effects of a small external control parameter are amplified by the electronic correlations. Here, we present a radical method for reversible, light-induced tuning of ferromagnetism at room temperature using a halide perovskite/oxide perovskite heterostructure. We demonstrate that photoinduced charge carriers from the [Formula: see text] photovoltaic perovskite efficiently dope the thin [Formula: see text] film and decrease the magnetization of the ferromagnetic state, allowing rapid rewriting of the magnetic bit. This manipulation could be accomplished at room temperature; hence this opens avenues for magnetooptical memory devices.

Mahan excitons in room-temperature methylammonium lead bromide perovskites.

In a seminal paper, Mahan predicted that excitonic bound states can still exist in a semiconductor at electron-hole densities above the insulator-to-metal Mott transition. However, no clear evidence for this exotic quasiparticle, dubbed Mahan exciton, exists to date at room temperature. In this work, we combine ultrafast broadband optical spectroscopy and advanced many-body calculations to reveal that organic-inorganic lead-bromide perovskites host Mahan excitons at room temperature. Persistence of the Wannier exciton peak and the enhancement of the above-bandgap absorption are observed at all achievable photoexcitation densities, well above the Mott density. This is supported by the solution of the semiconductor Bloch equations, which confirms that no sharp transition between the insulating and conductive phase occurs. Our results demonstrate the robustness of the bound states in a regime where exciton dissociation is otherwise expected, and offer promising perspectives in fundamental physics and in room-temperature applications involving high densities of charge carriers.

Infrared and 2-Dimensional Correlation Spectroscopy Study of the Effect of CH3NH3PbI3 and CH3NH3SnI3 Photovoltaic Perovskites on Eukaryotic Cells.

We studied the effect of the exposure of human A549 and SH-SY5Y cell lines to aqueous solutions of organic/inorganic halide perovskites CH3NH3PbI3 (MAPbI3) and CH3NH3SnI3 (MASnI3) at the molecular level by using Fourier transform infrared microspectroscopy. We monitored the infrared spectra of some cells over a few days following exposure to the metals and observed the spectroscopic changes dominated by the appearance of a strong band at 1627 cm-1. We used Infrared (IR) mapping to show that this change was associated with the cell itself or the cellular membrane. It is unclear whether the appearance of the 1627 cm-1 band and heavy metal exposure are related by a direct causal relationship. The spectroscopic response of exposure to MAPbI3 and MASnI3 was similar, indicating that it may arise from a general cellular response to stressful environmental conditions. We used 2D correlation spectroscopy (2DCOS) analysis to interpret spectroscopic changes. In a novel application of the method, we demonstrated the viability of 2DCOS for band assignment in spatially resolved spectra. We assigned the 1627 cm-1 band to the accumulation of an abundant amide or amine containing compound, while ruling out other hypotheses. We propose a few tentative assignments to specific biomolecules or classes of biomolecules, although additional biochemical characterization will be necessary to confirm such assignments.

Characterizing the maximum number of layers in chemically exfoliated graphene.

An efficient route to synthesize macroscopic amounts of graphene is highly desired and bulk characterization of such samples, in terms of the number of layers, is equally important. We present a Raman spectroscopy-based method to determine the typical upper limit of the number of graphene layers in chemically exfoliated graphene. We utilize a controlled vapour-phase potassium intercalation technique and identify a lightly doped stage, where the Raman modes of undoped and doped few-layer graphene flakes coexist. The spectra can be unambiguously distinguished from alkali doped graphite, and modeling with the typical upper limit of the layers yields an upper limit of flake thickness of five layers with a significant single-layer graphene content. Complementary statistical AFM measurements on individual few-layer graphene flakes find a consistent distribution of the layer numbers.