Constructing B─N─P Bonds in Ultrathin Holey g-C3N4 for Regulating the Local Chemical Environment in Photocatalytic CO2 Reduction to CO.

The lack of intrinsic active sites for photocatalytic CO2 reduction reaction (CO2RR) and fast recombination rate of charge carriers are the main obstacles to achieving high photocatalytic activity. In this work, a novel phosphorus and boron binary-doped graphitic carbon nitride, highly porous material that exhibits powerful photocatalytic CO2 reduction activity, specifically toward selective CO generation, is disclosed. The coexistence of Lewis-acidic and Lewis-basic sites plays a key role in tuning the electronic structure, promoting charge distribution, extending light-harvesting ability, and promoting dissociation of excitons into active carriers. Porosity and dual dopants create local chemical environments that activate the pyridinic nitrogen atom between the phosphorus and boron atoms on the exposed surface, enabling it to function as an active site for CO2RR. The P-N-B triad is found to lower the activation barrier for reduction of CO2 by stabilizing the COOH reaction intermediate and altering the rate-determining step. As a result, CO yield increased to 22.45 µmol g-1 h-1 under visible light irradiation, which is ≈12 times larger than that of pristine graphitic carbon nitride. This study provides insights into the mechanism of charge carrier dynamics and active site determination, contributing to the understanding of the photocatalytic CO2RR mechanism.

A multivalent mRNA monkeypox virus vaccine (BNT166) protects mice and macaques from orthopoxvirus disease.

In response to the 2022 outbreak of mpox driven by unprecedented human-to-human monkeypox virus (MPXV) transmission, we designed BNT166, aiming to create a highly immunogenic, safe, accessible, and scalable next-generation vaccine against MPXV and related orthopoxviruses. To address the multiple viral forms and increase the breadth of immune response, two candidate multivalent mRNA vaccines were evaluated pre-clinically: a quadrivalent vaccine (BNT166a; encoding the MPXV antigens A35, B6, M1, H3) and a trivalent vaccine (BNT166c; without H3). Both candidates induced robust T cell responses and IgG antibodies in mice, including neutralizing antibodies to both MPXV and vaccinia virus. In challenge studies, BNT166a and BNT166c provided complete protection from vaccinia, clade I, and clade IIb MPXV. Furthermore, immunization with BNT166a was 100% effective at preventing death and at suppressing lesions in a lethal clade I MPXV challenge in cynomolgus macaques. These findings support the clinical evaluation of BNT166, now underway (NCT05988203).

Enhanced Photogating Gain in Scalable MoS2 Plasmonic Photodetectors via Resonant Plasmonic Metasurfaces.

Absorption of photons in atomically thin materials has become a challenge in the realization of ultrathin, high-performance optoelectronics. While numerous schemes have been used to enhance absorption in 2D semiconductors, such enhanced device performance in scalable monolayer photodetectors remains unattained. Here, we demonstrate wafer-scale integration of monolayer single-crystal MoS2 photodetectors with a nitride-based resonant plasmonic metasurface to achieve a high detectivity of 2.58 × 1012 Jones with a record-low dark current of 8 pA and long-term stability over 40 days. Upon comparison with control devices, we observe an overall enhancement factor of >100; this can be attributed to the local strong EM field enhanced photogating effect by the resonant plasmonic metasurface. Considering the compatibility of 2D semiconductors and hafnium nitride with the Si CMOS process and their scalability across wafer sizes, our results facilitate the smooth incorporation of 2D semiconductor-based photodetectors into the fields of imaging, sensing, and optical communication applications.

Enhancing the Performance of 2D Tin-Based Pure Red Perovskite Light-Emitting Diodes through the Synergistic Effect of Natural Antioxidants and Cyclic Molecular Additives.

Tin (Sn)-based perovskites are being investigated in many optoelectronic applications given their similar valence electron configuration to that of lead-based perovskites and the potential environmental hazards of lead-based perovskites. However, the formation of high-quality Sn-based perovskite films faces several challenges, mainly due to the easy oxidation of Sn2+ to Sn4+ and the fast crystallization rate. Here, to develop an environmentally friendly process for Sn-based perovskite fabrication, a series of natural antioxidants are studied as additives and ascorbic acid (VitC) is found to have a superior ability to inhibit the oxidation problem. A common cyclic molecule, 18-Crown-6, is further added as a second additive, which synergizes with VitC to significantly reduce the nonradiative recombination pathways in the PEA2 SnI4 film. This synergistic effect greatly improves the performance of 2D red Sn-based PeLED, with a maximum external quantum efficiency of 1.87% (≈9 times that of the pristine device), a purer color, and better bias stability. This work demonstrates the potential of the dual-additive approach in enhancing the performance of 2D Sn-based PeLEDs, while the use of these environmentally friendly additives contributes to their future sustainability.

Nanoscale Gap-Plasmon-Enhanced Superconducting Photon Detectors at Single-Photon Level.

With a growing demand for detecting light at the single-photon level in various fields, researchers are focused on optimizing the performance of superconducting single-photon detectors (SSPDs) by using multiple approaches. However, input light coupling for visible light has remained a challenge in the development of efficient SSPDs. To overcome these limitations, we developed a novel system that integrates NbN superconducting microwire photon detectors (SMPDs) with gap-plasmon resonators to improve the photon detection efficiency to 98% while preserving all detector performance features, such as polarization insensitivity. The plasmonic SMPDs exhibit a hot-belt effect that generates a nonlinear photoresponse in the visible range operated at 9 K (∼0.64Tc), resulting in a 233-fold increase in phonon-electron interaction factor (γ) compared to pristine SMPDs at resonance under CW illumination. These findings open up new opportunities for ultrasensitive single-photon detection in areas like quantum information processing, quantum optics, imaging, and sensing at visible wavelengths.

Realizing High Brightness Quasi-2D Perovskite Light-Emitting Diodes with Reduced Efficiency Roll-Off via Multifunctional Interface Engineering.

Quasi-2D perovskites have recently flourished in the field of luminescence due to the quantum-confinement effect and the efficient energy transfer between different n phases resulting in exceptional optical properties. However, owing to the lower conductivity and poor charge injection, quasi-2D perovskite light-emitting diodes (PeLEDs) typically suffer from low brightness and high-efficiency roll-off at high current densities compared to 3D perovskite-based PeLEDs, which is undoubtedly one of the most critical issues in this field. In this work, quasi-2D PeLEDs with high brightness, reduced trap density, and low-efficiency roll-off are successfully demonstrated by introducing a thin layer of conductive phosphine oxide at the perovskite/electron transport layer interface. The results surprisingly show that this additional layer does not improve the energy transfer between multiple quasi-2D phases in the perovskite film, but purely improves the electronic properties of the perovskite interface. On the one hand, it passivates the surface defects of the perovskite film; on the other hand, it promotes electron injection and prevents hole leakage across this interface. As a result, the modified quasi-2D pure Cs-based device shows a maximum brightness of > 70,000 cd m-2 (twice that of the control device), a maximum external quantum efficiency (EQE) of > 10% and a much lower efficiency roll-off at high bias voltages.

Oriented lateral growth of two-dimensional materials on c-plane sapphire.

Two-dimensional (2D) semiconducting transition metal dichalcogenides (TMDs) represent the ultimate thickness for scaling down channel materials. They provide a tantalizing solution to push the limit of semiconductor technology nodes in the sub-1 nm range. One key challenge with 2D semiconducting TMD channel materials is to achieve large-scale batch growth on insulating substrates of single crystals with spatial homogeneity and compelling electrical properties. Recent studies have claimed the epitaxy growth of wafer-scale, single-crystal 2D TMDs on a c-plane sapphire substrate with deliberately engineered off-cut angles. It has been postulated that exposed step edges break the energy degeneracy of nucleation and thus drive the seamless stitching of mono-oriented flakes. Here we show that a more dominant factor should be considered: in particular, the interaction of 2D TMD grains with the exposed oxygen-aluminium atomic plane establishes an energy-minimized 2D TMD-sapphire configuration. Reconstructing the surfaces of c-plane sapphire substrates to only a single type of atomic plane (plane symmetry) already guarantees the single-crystal epitaxy of monolayer TMDs without the aid of step edges. Electrical results evidence the structural uniformity of the monolayers. Our findings elucidate a long-standing question that curbs the wafer-scale batch epitaxy of 2D TMD single crystals-an important step towards using 2D materials for future electronics. Experiments extended to perovskite materials also support the argument that the interaction with sapphire atomic surfaces is more dominant than step-edge docking.

Type-III Superconductivity.

Superconductivity remains one of most fascinating quantum phenomena existing on a macroscopic scale. Its rich phenomenology is usually described by the Ginzburg-Landau (GL) theory in terms of the order parameter, representing the macroscopic wave function of the superconducting condensate. The GL theory addresses one of the prime superconducting properties, screening of the electromagnetic field because it becomes massive within a superconductor, the famous Anderson-Higgs mechanism. Here the authors describe another widely-spread type of superconductivity where the Anderson-Higgs mechanism does not work and must be replaced by the Deser-Jackiw-Templeton topological mass generation and, correspondingly, the GL effective field theory must be replaced by an effective topological gauge theory. These superconductors are inherently inhomogeneous granular superconductors, where electronic granularity is either fundamental or emerging. It is shown that the corresponding superconducting transition is a 3D generalization of the 2D Berezinskii-Kosterlitz-Thouless vortex binding-unbinding transition. The binding-unbinding of the line-like vortices in 3D results in the Vogel-Fulcher-Tamman scaling of the resistance near the superconducting transition. The authors report experimental data fully confirming the VFT behavior of the resistance.

Use of the Human Granulysin Transgenic Mice To Evaluate the Role of Granulysin Expression by CD8 T Cells in Immunity To Mycobacterium tuberculosis.

The cytotoxic granules of human NK and CD8 T cells contain the effector molecule granulysin. Although in vitro studies indicate that granulysin is bactericidal to Mycobacterium tuberculosis and human CD8 T cells restrict intracellular M. tuberculosis by granule exocytosis, the role of granulysin in cell-mediated immunity against infection is incompletely understood, in part because a granulysin gene ortholog is absent in mice. Transgenic mice that express human granulysin (GNLY-Tg) under the control of human regulatory DNA sequences permit the study of granulysin in vivo. We assessed whether granulysin expression by murine CD8 T cells enhances their control of M. tuberculosis infection. GNLY-Tg mice did not control pulmonary M. tuberculosis infection better than non-Tg control mice, and purified GNLY-Tg and non-Tg CD8 T cells had a similar ability to transfer protection to T cell deficient mice. Lung CD8 T cells from infected control and GNLY-transgenic mice similarly controlled intracellular M. tuberculosis growth in macrophages in vitro. Importantly, after M. tuberculosis infection of GNLY-Tg mice, granulysin was detected in NK cells but not in CD8 T cells. Only after prolonged in vitro stimulation could granulysin expression be detected in antigen-specific CD8 T cells. GNLY-Tg mice are an imperfect model to determine whether granulysin expression by CD8 T cells enhances immunity against M. tuberculosis. Better models expressing granulysin are needed to explore the role of this antimicrobial effector molecule in vivo. IMPORTANCE Human CD8 T cells express the antimicrobial peptide granulysin in their cytotoxic granules, and in vitro analysis suggest that it restricts growth of Mycobacterium tuberculosis and other intracellular pathogens. The murine model of tuberculosis cannot assess granulysin's role in vivo, as rodents lack the granulysin gene. A long-held hypothesis is that murine CD8 T cells inefficiently control M. tuberculosis infection because they lack granulysin. We used human granulysin transgenic (GNLY-Tg) mice to test this hypothesis. GNLY-Tg mice did not differ in their susceptibility to tuberculosis. However, granulysin expression by pulmonary CD8 T cells could not be detected after M. tuberculosis infection. As the pattern of granulysin expression in human CD8 T cells and GNLY-Tg mice seem to differ, GNLY-Tg mice are an imperfect model to study the role of granulysin. An improved model is needed to answer the importance of granulysin expression by CD8 T cells in different diseases.

Main-chain engineering of polymer photocatalysts with hydrophilic non-conjugated segments for visible-light-driven hydrogen evolution.

Photocatalytic water splitting is attracting considerable interest because it enables the conversion of solar energy into hydrogen for use as a zero-emission fuel or chemical feedstock. Herein, we present a universal approach for inserting hydrophilic non-conjugated segments into the main-chain of conjugated polymers to produce a series of discontinuously conjugated polymer photocatalysts. Water can effectively be brought into the interior through these hydrophilic non-conjugated segments, resulting in effective water/polymer interfaces inside the bulk discontinuously conjugated polymers in both thin-film and solution. Discontinuously conjugated polymer with 10 mol% hexaethylene glycol-based hydrophilic segments achieves an apparent quantum yield of 17.82% under 460 nm monochromatic light irradiation in solution and a hydrogen evolution rate of 16.8 mmol m-2 h-1 in thin-film. Molecular dynamics simulations show a trend similar to that in experiments, corroborating that main-chain engineering increases the possibility of a water/polymer interaction. By introducing non-conjugated hydrophilic segments, the effective conjugation length is not altered, allowing discontinuously conjugated polymers to remain efficient photocatalysis.

A Keratinocyte-Tethered Biologic Enables Location-Precise Treatment in Mouse Vitiligo.

Despite the central role of IFN-γ in vitiligo pathogenesis, systemic IFN-γ neutralization is an impractical treatment option owing to strong immunosuppression. However, most patients with vitiligo present with <20% affected body surface area, which provides an opportunity for localized treatments that avoid systemic side effects. After identifying keratinocytes as key cells that amplify IFN-γ signaling during vitiligo, we hypothesized that tethering an IFN-γ‒neutralizing antibody to keratinocytes would limit anti‒IFN-γ effects on the treated skin for the localized treatment. To that end, we developed a bispecific antibody capable of blocking IFN-γ signaling while binding to desmoglein expressed by keratinocytes. We characterized the effect of the bispecific antibody in vitro, ex vivo, and in a mouse model of vitiligo. Single-photon emission computed tomography/computed tomography biodistribution and serum assays after local footpad injection revealed that the bispecific antibody had improved skin retention, faster elimination from the blood, and less systemic IFN-γ inhibition than the nontethered version. Furthermore, the bispecific antibody conferred localized protection almost exclusively to the treated footpad during vitiligo, which was not possible by local injection of the nontethered anti‒IFN-γ antibody. Thus, keratinocyte tethering proved effective while significantly diminishing the off-tissue effects of IFN-γ blockade, offering a safer treatment strategy for localized skin diseases, including vitiligo.

Ultrathin TiN Epitaxial Films as Transparent Conductive Electrodes.

Titanium nitride (TiN), a transition-metal compound with tight covalent Ti-N bonding, has a high melting temperature and superior mechanical and chemical stabilities compared to noble metals. With a reduction in thickness, the optical transmittance of TiN films can be drastically increased, and in combination with its excellent electrical conductivity, the ultrathin and continuous TiN film can be considered as an ideal alternative of the metal oxide electrodes. However, the deposition of ultrathin and continuous metallic layer with a smooth surface morphology is a major challenge for typical deposition methods such as thermal evaporation or reactive sputtering. In particular, defects mainly related with oxygen contents and surface scattering can significantly limit the performance of ultrathin TiN films. In this work, ultrathin TiN films with 2-10 nm in thickness are grown by using the nitrogen plasma-assisted molecular-beam epitaxy (MBE) method in an ultrahigh vacuum environment. Excellent surface morphology with a root-mean-square roughness of ≤0.12 nm and a high optical transparency of 75% over the whole visible regime are achieved for ultrathin TiN epitaxial films. The dielectric properties determined by the spectroscopic ellipsometry and the electrical properties measured by the terahertz spectroscopy and the Hall effect method reveal that the percolation thickness of the TiN epitaxial film is less than 2.4 nm and its electrical conductivity is higher than 1.1 × 104 Ω-1 cm-1. These features make MBE-grown ultrathin TiN epitaxial films a good candidate for robust, low cost, and large-area transparent conductive electrodes.

Flexible Plasmonics Using Aluminum and Copper Epitaxial Films on Mica.

We demonstrate here the growth of aluminum (Al), copper (Cu), gold (Au), and silver (Ag) epitaxial films on two-dimensional, layered muscovite mica (Mica) substrates via van der Waals (vdW) heteroepitaxy with controllable film thicknesses from a few to hundreds of nanometers. In this approach, the mica thin sheet acts as a flexible and transparent substrate for vdW heteroepitaxy, which allows for large-area formation of atomically smooth, single-crystalline, and ultrathin plasmonic metals without the issue of film dewetting. The high-quality plasmonic metal films grown on mica enable us to design and fabricate well-controlled Al and Cu plasmonic nanostructures with tunable surface plasmon resonances ranging from visible to the near-infrared spectral region. Using these films, two kinds of plasmonic device applications are reported, including (1) plasmonic sensors with high effective index sensitivities based on surface plasmon interferometers fabricated on the Al/Mica film and (2) Cu/Mica nanoslit arrays for plasmonic color filters in the visible and near-infrared regions. Furthermore, we show that the responses of plasmonic nanostructures fabricated on the Mica substrates remain unaltered under large substrate bending conditions. Therefore, the metal-on-mica vdW heteroepitaxy platform is suitable for flexible plasmonics based on their bendable properties.

CD4 T cell help prevents CD8 T cell exhaustion and promotes control of Mycobacterium tuberculosis infection.

CD4 T cells are essential for immunity to tuberculosis because they produce cytokines, including interferon-γ. Whether CD4 T cells act as "helper" cells to promote optimal CD8 T cell responses during Mycobacterium tuberculosis is unknown. Using two independent models, we show that CD4 T cell help enhances CD8 effector functions and prevents CD8 T cell exhaustion. We demonstrate synergy between CD4 and CD8 T cells in promoting the survival of infected mice. Purified helped, but not helpless, CD8 T cells efficiently restrict intracellular bacterial growth in vitro. Thus, CD4 T cell help plays an essential role in generating protective CD8 T cell responses against M. tuberculosis infection in vitro and in vivo. We infer vaccines that elicit both CD4 and CD8 T cells are more likely to be successful than vaccines that elicit only CD4 or CD8 T cells.

Cubic-Phase Metasurface for Three-Dimensional Optical Manipulation.

The optical tweezer is one of the important techniques for contactless manipulation in biological research to control the motion of tiny objects. For three-dimensional (3D) optical manipulation, shaped light beams have been widely used. Typically, spatial light modulators are used for shaping light fields. However, they suffer from bulky size, narrow operational bandwidth, and limitations of incident polarization states. Here, a cubic-phase dielectric metasurface, composed of GaN circular nanopillars, is designed and fabricated to generate a polarization-independent vertically accelerated two-dimensional (2D) Airy beam in the visible region. The distinctive propagation characteristics of a vertically accelerated 2D Airy beam, including non-diffraction, self-acceleration, and self-healing, are experimentally demonstrated. An optical manipulation system equipped with a cubic-phase metasurface is designed to perform 3D manipulation of microscale particles. Due to the high-intensity gradients and the reciprocal propagation trajectory of Airy beams, particles can be laterally shifted and guided along the axial direction. In addition, the performance of optical trapping is quantitatively evaluated by experimentally measured trapping stiffness. Our metasurface has great potential to shape light for compact systems in the field of physics and biological applications.

Enhanced Spontaneous Emission of Monolayer MoS2 on Epitaxially Grown Titanium Nitride Epsilon-Near-Zero Thin Films.

Room-temperature photoluminescence enhancement of molybdenum disulfide (MoS2) monolayers on epitaxial titanium nitride (TiN) thin films grown by molecular-beam-epitaxy as well as magnetron-sputtered TiN films is observed by a confocal laser scanning microscope with excitation wavelengths covering the transition of TiN's macroscopic optical properties from dielectric to plasmonic. The photoluminescence enhancement increases as TiN becomes more metallic, and strong enhancement is obtained at the excitation wavelengths equal to or longer than the epsilon-near-zero (ENZ) wavelength of TiN films. A good agreement is observed between measured and calculated enhancements. The enhancement is attributed to the increased excitation field in MoS2 at TiN's ENZ wavelength and interference effects for thick spacers that separate the MoS2 flakes from TiN films in the metallic regime. This study enriches the fundamental understanding of emission properties on ENZ substrates that could be important for the development of advanced nanoscale lasers/light sources, optical/biosensors, and nano-optoelectronic devices.

Niobium nitride plasmonic perfect absorbers for tunable infrared superconducting nanowire photodetection.

Quantum technologies such as quantum computing and quantum cryptography exhibit rapid progress. This requires the provision of high-quality photodetectors and the ability to efficiently detect single photons. Hence, conventional avalanche photodiodes for single photon detection are not the first choice anymore. A better alternative are superconducting nanowire single photon detectors, which use the superconducting to normal conductance phase transition. One big challenge is to reduce the product between recovery time and detection efficiency. To address this problem, we enhance the absorption using resonant plasmonic perfect absorber effects, to reach near-100% absorption over small areas. This is aided by the high resonant absorption cross section and the angle insensitivity of plasmonic resonances. In this work we present a superconducting niobium nitride plasmonic perfect absorber structure and use its tunable plasmonic resonance to create a polarization dependent photodetector with near-100% absorption efficiency in the infrared spectral range. Further we fabricated a detector and investigated its response to an external light source. We also demonstrate the resonant plasmonic behavior which manifests itself through a polarization dependence detector response.

Flexible BiVO4/WO3/ITO/Muscovite Heterostructure for Visible-Light Photoelectrochemical Photoelectrode.

Flexible electronics has recently captured extensive attention due to its intriguing functionalities and great potential for influencing our daily life. In addition, with the increasing demand for green energy, photoelectrochemical (PEC) water splitting is a clean process that directly converts solar energy to chemical energy in the form of hydrogen. Thus the development of flexible green energy electronics represents a new domain in the research field of energy harvesting. In this work, we demonstrate the BiVO4 (BVO)/WO3/ITO/muscovite heterostructure photoelectrode for water splitting with flexible characteristics. The performance of BVO was modified by specific crystal facets, and the BVO/WO3 bilayer exhibited superior performance of 33% enhanced PEC activity at 1 V vs Ag/AgCl compared with pure BVO due to the proper staggered band alignment. Moreover, excellent mechanical stability was verified by a series of bending modes. This study demonstrates a pathway to a flexible photoelectrode for developing innovative devices for solar fuel generation.

Gate-Tunable Plasmon-Enhanced Photodetection in a Monolayer MoS2 Phototransistor with Ultrahigh Photoresponsivity.

Monolayer transition metal dichalcogenides (TMDs), direct bandgap materials with an atomically thin nature, are promising materials for electronics and photonics, especially at highly scaled lateral dimensions. However, the characteristically low total absorption of photons in the monolayer TMD has become a challenge in the access to and realization of monolayer TMD-based high-performance optoelectronic functionalities and devices. Here, we demonstrate gate-tunable plasmonic phototransistors (photoFETs) that consist of monolayer molybdenum disulfide (MoS2) photoFETs integrated with the two-dimensional plasmonic crystals. The plasmonic photoFET has an ultrahigh photoresponsivity of 2.7 × 104 AW-1, achieving a 7.2-fold enhancement in the photocurrent compared to pristine photoFETs. This benefits predominately from the combination of the enhancement of the photon-absorption-rate via the strongly localized-electromagnetic-field and the gate-tunable plasmon-induced photocarrier-generation-rate in the monolayer MoS2. These results demonstrate a systematic methodology for designing ultrathin plasmon-enhanced photodetectors based on monolayer TMDs for next-generation ultracompact optoelectronic devices in the trans-Moore era.

Ultra-broadband, lithography-free, omnidirectional, and polarization-insensitive perfect absorber.

Perfect absorbers (PAs) at near infrared allow various applications such as biosensors, nonlinear optics, color filters, thermal emitters and so on. These PAs, enabled by plasmonic resonance, are typically powerful and compact, but confront inherent challenges of narrow bandwidth, polarization dependence, and limited incident angles as well as requires using expensive lithographic process, which limit their practical applications and mass production. In this work, we demonstrate a non-resonant PA that is comprised of six continuous layers of magnesium fluoride (MgF2) and chromium (Cr) in turns. Our device absorbs more than 90% of light in a broad range of 900-1900 nm. In addition, such a planar design is lithography-free, certainly independent with polarization, and presents a further advantage of wide incidence up to 70°. The measured performance of our optimized PA agrees well with analytical calculations of transfer matrix method (TMM) and numerical simulations of finite element method, and can be readily implemented for practical applications.