Synthesis and Comprehensive Studies of Be-IV-N2 (IV = Si, Ge): Solving the Mystery of Wurtzite-Type Pmc21 Structures.

The research for wurtzite-type ternary nitride semiconductors containing earth abundant elements with a stoichiometry of 1:1:2 was focused on metals like Mg or Zn, so far. The vast majority of these Grimm-Sommerfeld analogous compounds crystallize in the ß-NaFeO2 structure, although a second arrangement in space group Pmc21 is predicted to be a viable alternative. Despite extensive theoretical and experimental studies, this structure has so far remained undiscovered. Herein, we report on BeGeN2 in a Pmc21 structure, synthesized from Be3N2 and Ge3N4 using a high-pressure high-temperature approach at 6 GPa and 800 °C. The compound was characterized by powder X-ray diffraction (PXRD), solid state nuclear magnetic resonance (NMR), Raman and energy dispersive X-ray (EDX) spectroscopy, temperature-dependent PXRD, second harmonic generation (SHG) and UV/VIS measurements and in addition also compared to its lighter homologue BeSiN2 in all mentioned analytic techniques. The synthesis and investigation of both the first beryllium germanium nitride and the first ternary wurtzite-type nitride crystallizing in space group Pmc21 open the door to a new field of research on wurtzite-type related structures.

Patterning optimization for device realization of patterned GaAsSbN nanowire photodetectors.

Vertically grown nanowires are a research interest in optoelectronics and photovoltaic applications due to their high surface to volume ratio and good light trapping capabilities. This study presents the effects of process and design parameters on self-catalyzed GaAsSbN nanowires (NWs) grown by plasma-assisted molecular beam epitaxy on patterned silicon substrates using electron beam lithography. Vertical alignment of the patterned NWs examined via scanning electron microscopy show the sensitivity of patterned nanowire growth to the parameters of nanowire diameter, pitch, dose time, etching techniques and growth plan. Diameters range from 90 nm to 250 nm. Pitch lengths of 200 nm, 400 nm, 600 nm, 800 nm, 1000 nm, and 1200 nm were examined. Dry etching of the oxide layer of the silicon substrate and PMMA coating is performed using reactive ion etching for 20 s and 120 s respectively. Comparisons of different HF etch durations performed pre and post PMMA removal are presented. Additionally, the report of an observed surfactant effect in dilute nitride GaAsSbN nanowires in comparison to non-nitride GaAsSb is presented. Optimizations to patterning, reactive ion etching, and HF etching are presented to obtain higher vertical yield of patterned GaAsSbN nanowires, achieving ~80% of the expected NW/µm2. Room temperature and 4K photoluminescence results show the effect of nitride incorporation for further bandgap tuning, and patterned pitch on the optical characteristics of the nanowires which gives insights to the compositional homogeneity for nanowires grown at each pitch length.

Nonvolatile Control of Valley Polarized Emission in 2D WSe2-AlScN Heterostructures.

Achieving robust and electrically controlled valley polarization in monolayer transition metal dichalcogenides (ML-TMDs) is a frontier challenge for realistic valleytronic applications. Theoretical investigations show that the integration of 2D materials with ferroelectrics is a promising strategy; however, an experimental demonstration has remained elusive. Here, we fabricate ferroelectric field-effect transistors using a ML-WSe2 channel and an Al0.68Sc0.32N (AlScN) ferroelectric dielectric and experimentally demonstrate efficient tuning as well as non-volatile control of valley polarization. We measure a large array of transistors and obtain a maximum valley polarization of ∼27% at 80 K with stable retention up to 5400 s. The enhancement in the valley polarization is ascribed to the efficient exciton-to-trion (X-T) conversion and its coupling with an out-of-plane electric field, viz., the quantum-confined Stark effect. This changes the valley depolarization pathway from strong exchange interactions to slow spin-flip intervalley scattering. Our research demonstrates a promising approach for achieving non-volatile control over valley polarization for practical valleytronic device applications.

A polyfunctionalized carbon framework composite for efficient decontamination of Cr(VI) and polycyclic aromatic nitrides from acidic wastewater.

Developing multifunctional engineered adsorbents is an effective strategy for decontaminating the environment from various pollutants. In this study, a polyfunctionalized carbon-framework composite, MSC-CFM, was synthesized. The composite comprises an aromatic carbon framework enriched with various functional groups, including magnetic nanoparticles, hydroxyl, and amino groups. MSC-CFM was used to decontaminate Cr(VI) and polycyclic aromatic nitrides (p-dimethylaminoazobenzene sulfonate (DAS) and diphenyl-4, 4 '-di [sodium (azo-2 -) -1-amino-naphthalene-4-sulfonate] (DANS)) from acidic wastewater. The adsorption capacities of MSC-CFM for Cr(VI), DAS and DANS, quantified using the Langmuir isotherm model, were 161.28, 310.83, and 1566.09 mg/g, respectively. Cr(VI) and PAHs (DAS and DANS) were monolayer adsorbed controlled by chemisorption. MSC-CFM could maintain good adsorption efficiency after up to 6 adsorption and desorption cycles. The presence of polycyclic aromatic nitrides promoted the adsorption of Cr(VI) in the Cr(VI)-DAS/DANS binary systems. Removal of pollutants by MSC-CFM involved a variety of unreported reaction mechanisms, such as electrostatic attraction, redox reaction, anion exchange, intermolecular hydrogen bonding, complexation reaction, π-π interaction, and anion-π interaction. MSC-CFM, enriched with a variety of functional groups, is a promising new material for environmental protection. It has good potential for practical application in treating polluted wastewater.

Nanozyme Metabolism Controls Air Pollution over an Atomic Potassium Cyano Site.

Increasing threats of air pollution prompt the design of air purification systems. As a promising initiative defense strategy, nanocatalysts are integrated to catalyze the detoxification of specific pollutants. However, it remains a grand challenge to tailor versatile nanocatalysts to cope with diverse pollutants in practice. Here, we report a nanozyme metabolism system to realize broad-spectrum protection from air pollution. Atomic K-modified carbon nitride featuring flavin oxidase-like and peroxidase-like activities was synthesized to initiate nanozyme metabolism. In situ experiments and theoretical investigations collectively show that K sites optimize the geometric and electronic structure of cyano sites for both enzyme-like activities. As a proof of concept, the nanozyme metabolism was applied to the mask against volatile organic compounds, persistent organic pollutants, reactive oxygen species, bacteria, and so on. Our finding provides a thought to tackle global air pollution and deepens the understanding of nanozyme metabolism.

Molten Salt-Assisted Synthesis of Titanium Nitride.

Titanium nitride is an exciting plasmonic material, with optical properties similar to gold. However, synthesizing TiN nanocrystals is highly challenging and typically requires solid-state reactions at very high temperatures (800-1000°C). Here, the synthesis of TiN nanocrystals is achieved at temperatures as low as 350°C, in just 1 h. The strategy comprises molten salt, Mg as reductant and Ca3N2 as nitride source. This brings TiN from the realm of solid-state chemistry into the field of solution-based synthesis in regular, borosilicate glassware.

Mixed Tin Valence in the Tin(II/IV)-Nitridophosphate Sn3P8N16.

Sn3P8N16 combines the structural versatility of nitridophosphates and Sn within one compound. It was synthesized as dark gray powder in a high-pressure high-temperature reaction at 800 °C and 6 GPa from Sn3N4 and P3N5. The crystal structure was elucidated from single-crystal diffraction data (space group C2/m (no. 12), a=12.9664(4), b=10.7886(4), c=4.8238(2) Å, ß=109.624(1)°) and shows a 3D-network of PN4 tetrahedra, incorporating Sn in oxidation states +II and +IV. The Sn cations are located within eight-membered rings of vertex-sharing PN4 tetrahedra, stacked along the [001] direction. A combination of solid-state nuclear magnetic resonance spectroscopy, 119Sn Mössbauer spectroscopy and density functional theory calculations was used to confirm the mixed oxidation of Sn. Temperature-dependent powder X-ray diffraction measurements reveal a low thermal expansion of 3.6 ppm/K up to 750 °C, beyond which Sn3P8N16 starts to decompose.

ScN/GaN(11Ì 00): A New Platform for the Epitaxy of Twin-Free Metal-Semiconductor Heterostructures.

We study the molecular beam epitaxy of rock-salt ScN on the wurtzite GaN(11̅00) surface. To this end, ScN is grown on freestanding GaN(11̅00) substrates and self-assembled GaN nanowires exhibiting (11̅00) sidewalls. On both substrates, ScN crystallizes twin-free thanks to a specific epitaxial relationship, namely ScN(110)[001]∥GaN(11̅00)[0001], providing a congruent, low-symmetry interface. The 13.1% uniaxial lattice mismatch occurring in this orientation mostly relaxes within the first few monolayers of growth by forming a near-coincidence site lattice, where 7 GaN planes coincide with 8 ScN planes, leaving the ScN surface nearly free of extended defects. Overgrowth of the ScN with GaN leads to a kinetic stabilization of the zinc blende phase, that rapidly develops wurtzite inclusions nucleating on {111} nanofacets, commonly observed during zinc blende GaN growth. Our ScN/GaN(11̅00) platform opens a new route for the epitaxy of twin-free metal-semiconductor heterostructures including closely lattice-matched GaN, ScN, HfN, and ZrN compounds.

Silver Nanoparticle-Embedded Carbon Nitride: Antifungal Activity on Candida albicans and Toxicity toward Animal Cells.

The development of engineered nanomaterials has been considered a promising strategy to control oral infections. In this study, silver-embedded carbon nitrides (Ag@g-CN) were synthesized and tested against Candida albicans, investigating their antifungal action and biocompatibility in animal cells. Ag@g-CN was synthesized by a simple one-pot thermal polymerization technique and characterized by various analytical techniques. X-ray diffraction (XRD) analysis revealed slight alterations in the crystal structure of g-CN upon the incorporation of Ag. Fourier transform infrared (FT-IR) spectroscopy confirmed the presence of Ag-N bonds, indicating successful silver incorporation and potential interactions with g-CN's amino groups. UV-vis spectroscopy demonstrated a red shift in the absorption edge of Ag@g-CN compared with g-CN, attributed to the surface plasmon resonance effect of silver nanoparticles. Field emission scanning electron microscopy (FE-SEM) and transmission electron microscopy (TEM) confirmed the 2D layered sheet like morphology of both materials. The Ag 3d peaks found in X-ray photoelectron spectroscopy (XPS) confirmed the presence of metallic Ag0 nanoparticles in Ag@g-CN. The Ag@g-CN materials exhibited high antifungal activity against reference and oral clinical strains of C. albicans, with minimal inhibitory concentration (MIC) ranges between 16-256 µg/mL. The mechanism of Ag@g-CN on C. albicans was attributed to the disruption of the membrane integrity and disturbance of the biofilm. In addition, the Ag@g-CN material showed good biocompatibility in the fibroblastic cell line and in Galleria mellonella, with no apparent cytotoxicity observed at a concentration up to 1000 µg/mL. These findings demonstrate the potential of the Ag@g-CN material as an effective and safe antifungal agent for the treatment of oral fungal infections.

On Decorating a Honeycomb AlN Monolayer with Hydrogen and Fluorine Atoms: Ab Initio and Experimental Aspects.

Mono- and few-layer hexagonal AlN (h-AlN) has emerged as an alternative "beyond graphene" and "beyond h-BN" 2D material, especially in the context of its verification in ultra-high vacuum Scanning Tunneling Microscopy and Molecular-beam Epitaxy (MBE) experiments. However, graphitic-like AlN has only been recently obtained using a scalable and semiconductor-technology-related synthesis techniques, such as metal-organic chemical vapor deposition (MOCVD), which involves a hydrogen-rich environment. Motivated by these recent experimental findings, in the present work, we carried out ab initio calculations to investigate the hydrogenation of h-AlN monolayers in a variety of functionalization configurations. We also investigated the fluorination of h-AlN monolayers in different decoration configurations. We find that a remarkable span of bandgap variation in h-AlN, from metallic properties to nar-row-bandgap semiconductor, and to wide-bandgap semiconductor can be achieved by its hy-drogenation and fluorination. Exciting application prospects may also arise from the findings that H and F decoration of h-AlN can render some such configurations magnetic. We complemented this modelling picture by disclosing a viable experimental strategy for the fluorination of h-AlN.

Ammonothermal Synthesis and Solid-State NMR Study of the Imidonitridosilicate Rb3Si6N5(NH)6.

The imidonitridosilicate Rb3Si6N5(NH)6, being only the second representative of this compound class, was synthesized ammonothermally at 870 K and 230 MPa. Its crystal structure was solved from single-crystal X-ray diffraction data. The imidonitridosilicate crystallizes isotypically with the respective potassium compound in space group P4132 with the lattice parameter a=10.9422(4) Šforming a three-dimensional imidonitridosilicate tetrahedra network with voids for the rubidium ions. The structure model and the presence of the imide groups were verified by Fourier-Transform infrared (FTIR) and magic-angle spinning (MAS) NMR spectroscopy, using cross polarization 15N{1H} and 29Si{1H} MAS NMR experiments. Rb3Si6N5(NH)6 represents a possible intermediate during the ammonothermal synthesis of nitridosilicates. The characterization of such intermediates improves the understanding of the reaction pathway from ammonothermal solutions to nitrides. Thus, the ammonothermal synthesis is an alternative approach to the well-established high-temperature synthesis leading to the compound class of nitridosilicates.

Highly Condensed and Super-Incompressible Be2PN3.

Although beryllium and its compounds show outstanding properties, owing to its toxic potential and extreme reaction conditions the chemistry of Be under high-pressure conditions has only been investigated sparsely. Herein, we report on the highly condensed wurtzite-type Be2PN3, which was synthesized from Be3N2 and P3N5 in a high-pressure high-temperature approach at 9 GPa and 1500 °C. It is the missing member in the row of formula type M2PN3 (M = Mg, Zn). The structure was elucidated by powder X-ray diffraction (PXRD), revealing that Be2PN3 is a double nitride, rather than a nitridophosphate. The structural model was further corroborated by 9Be and 31P solid-state nuclear magnetic resonance (NMR) spectroscopy. We present 9Be NMR data for tetrahedral nitride coordination for the first time. Infrared and energy-dispersive X-ray spectroscopy (FTIR and EDX), as well as temperature dependent PXRD complement the analytical characterization. Density functional theory (DFT) calculations reveal super-incompressible behavior and the remarkable hardness of this low-density material. The formation of Be2PN3 through a high-pressure high-temperature approach expands the synthetic access to Be-containing compounds and may open access to various multinary beryllium nitrides.

Recent Advancements in Ascribing Several Platinum Free Electrocatalysts Pertinent to Hydrogen Evolution from Water Reduction.

The advancement of a sustainable and scalable catalyst for hydrogen production is crucial for the future of the hydrogen economy. Electrochemical water splitting stands out as a promising pathway for sustainable hydrogen production. However, the development of Pt-free electrocatalysts that match the energy efficiency of Pt while remaining economical poses a significant challenge. This review addresses this challenge by highlighting latest breakthroughs in Pt-free catalysts for the hydrogen evolution reaction (HER). Specifically, we delve into the catalytic performance of various transition metal phosphides, metal carbides, metal sulphides, and metal nitrides toward HER. Our discussion emphasizes strategies for enhancing catalytic performance and explores the relationship between structural composition and the performance of different electrocatalysts. Through this comprehensive review, we aim to provide insights into the ongoing efforts to overcome barriers to scalable hydrogen production and pave the way for a sustainable hydrogen economy.

Mo5N6 nanosheets for fluorescent quenching and target recognition: Highly selectively sensing of sodium hexametaphosphate.

Typical fluorescent biosensors use fluorescently labeled ssDNA for target recognition and nanomaterials for signal transduction. Herein, we propose a reverse sensing strategy that Mo5N6 nanosheets are used for target recognition while fluorescein (FAM)-labeled ssDNA only serves for signal generation. We discover that Mo5N6 nanosheets show high fluorescence quenching ability (>95%) and selective recognition for sodium hexametaphosphate (SHMP). After FAM-labeled ssDNA is adsorbed on Mo5N6 nanosheets, the fluorescence is quenched due to the photoinduced electron transfer (PET) effect between FAM and Mo5N6 nanosheets. SHMP can specifically displace the adsorbed FAM-labeled ssDNA from Mo5N6 nanosheets, resulting in more than 80% fluorescence recovery on addition of 5 µmol L-1 SHMP. This biosensor can sensitively detect SHMP down to 150 nmol L-1 and selectively recognize SHMP over glucose, lactose, common amino acids, Zn2+, Mg2+, Ca2+ and other phosphates (such as Na2HPO4, sodium pyrophosphate, sodium tripolyphosphate). This biosensor also shows great potential for the detection of SHMP in bacon sample. This work not only provides a facile sensitive and selective biosensor for SHMP but also exploits the application of transition metal nitrides in the field of sensing and biosensing.

Intrinsic Self-Trapped Excitons in Graphitic Carbon Nitride.

Graphitic carbon nitrides (g-C3N4) as low-cost, chemically stable, and ecofriendly layered semiconductors have attracted rapidly growing interest in optoelectronics and photocatalysis. However, the nature of photoexcited carriers in g-C3N4 is still controversial, and an independent charge-carrier picture based on the band theory is commonly adopted. Here, by performing transient spectroscopy studies, we show characteristics of self-trapped excitons (STEs) in g-C3N4 nanosheets including broad trapped exciton-induced absorption, picosecond exciton trapping without saturation at high photoexcitation density, and transient STE-induced stimulated emissions. These features, together with the ultrafast exciton trapping polarization memory, strongly suggest that STEs intrinsically define the nature of the photoexcited states in g-C3N4. These observations provide new insights into the fundamental photophysics of carbon nitrides, which may enlighten novel designs to boost energy conversion efficiency.

Role of Surface Chemistry of Ta Metal Foil on the Growth of GaN Nanorods by Laser Molecular Beam Epitaxy and Their Field Emission Characteristics.

This study investigates the influence of surface nitridation of Ta metal foil substrates on the growth of GaN nanorods using the laser molecular beam epitaxy (LMBE) technique and the field emission characteristics of the grown GaN nanorod ensemble. Surface morphology examinations underscore the pivotal role of Ta foil nitridation in shaping the dimensions and densities of GaN nanorods. Bare Ta foil fosters the formation of high-density, vertically self-aligned GaN nanorods at a growth temperature of 700 °C. Furthermore, the density of these nanorods is directly related to the duration of Ta foil nitridation, with increased duration leading to a reduced nanorod density. X-ray Photoelectron Spectroscopy (XPS) studies reveal that the transition of the Ta foil surface from tantalum oxide to tantalum nitride during nitridation emerges as a crucial factor influencing GaN nanorod growth. Photoluminescence (PL) spectroscopy at ambient temperature reveals a strong near-band-edge (NBE) emission peak with negligible defect-related peaks, displaying the high optical quality of the GaN nanorods. The highly dense vertically aligned GaN nanorod ensemble growth without Ta prenitridation exhibits the most favorable field emission performance, featuring a turn-on field of 2.1 V/µm, a field enhancement factor of 2480, and a stable long-term operation at the emission current density of 2.26 mA/cm2. This study advances the understanding of the role of the surface chemistry of metal foil in determining GaN nanorod growth and opens up exciting possibilities for tailoring advanced optoelectronic devices for specific application requirements.

Multicationic Tetrahedra Networks: Alkaline-Earth-Centered Polyhedra and Non-Condensed AlN6-Octahedra in the Imidonitridophosphates AE2AlP8N15(NH) (AE=Ca, Sr, Ba).

A series of isostructural imidonitridophosphates AE2AlP8N15(NH) (AE=Ca, Sr, Ba) was synthesized at high-pressure/high-temperature conditions (1400 °C and 5-9 GPa) from alkaline-earth metal nitrides or azides Ca3N2/Sr(N3)2/Ba(N3)2 and the binary nitrides AlN and P3N5. NH4F served as a hydrogen source and mineralizing agent. The crystal structures were determined by single-crystal X-ray diffraction and feature a three-dimensional network of vertex-sharing PN4-tetrahedra forming diverse-sized rings that are occupied by aluminum and alkaline earth ions. These structures represent another example of nitridophosphate-based networks that simultaneously incorporate AlN6-octahedra and alkaline-earth-centered polyhedra, with aluminum not participating in the tetrahedra network. They differ from previously reported ones by incorporating non-condensed octahedra instead of strongly condensed octahedra units and contribute to the diversity of multicationic nitridophosphate network structures. The results are supported by atomic resolution EDX mapping, solid-state NMR and FTIR measurements. Eu2+-doped samples show strong luminescence with narrow emissions in the range of green to blue under UV excitation, marking another instance of Eu2+-luminescence within imidonitridophosphates.

Cathodoluminescence investigations of dark-line defects in platelet-based InGaN nano-LED structures.

We have investigated the optical properties of heterostructured InGaN platelets aiming at red emission, intended for use as nano-scaled light-emitting diodes. The focus is on the presence of non-radiative emission in the form of dark line defects. We have performed the study using hyperspectral cathodoluminescence imaging. The platelets were grown on a template consisting of InGaN pyramids, flattened by chemical mechanical polishing. These templates are defect free, whereas the dark line defects are introduced in the lower barrier and tend to propagate through all the subsequent layers, as revealed by the imaging of different layers in the structure. We conclude that the dark line defects are caused by stacking mismatch boundaries introduced by multiple seeding and step bunching at the edges of the as-polished, dome shaped templates. To avoid these defects, we suggest that the starting material must be flat rather than dome shaped.

Cr5.7Si2.3P8N24-A Chromium(+IV) Nitridosilicate Phosphate with Amphibole-Type Structure.

The first nitridic analog of an amphibole mineral, the quaternary nitridosilicate phosphate Cr5.7Si2.3P8N24 was synthesized under high-pressure high-temperature conditions at 1400 °C and 12 GPa from the binary nitrides Cr2N, Si3N4 and P3N5, using NH4N3 and NH4F as additional nitrogen source and mineralizing agent, respectively. The crystal structure was elucidated by single-crystal X-ray diffraction with microfocused synchrotron radiation (C2/m, a=9.6002(19), b=17.107(3), c=4.8530(10) Å, ß=109.65(3)°). The elemental composition was analyzed by energy dispersive X-ray spectroscopy. The structure consists of vertex-sharing PN4-tetrahedra forming zweier double chains and edge-sharing (Si,Cr)-centered octahedra forming separated ribbons. Atomic resolution scanning transmission electron microscopy shows ordered Si and Cr sites next to a disordered Si/Cr site. Optical spectroscopy indicates a band gap of 2.1 eV. Susceptibility measurements show paramagnetic behavior and support the oxidation state Cr+IV, which is confirmed by EPR. The comprehensive analysis expands the field of Cr-N chemistry and provides access to a nitride analog of one of the most prevalent silicate structures.

Construction of Heterojunction-Rich Metal Nitrides Porous Nanosheets Electrocatalyst for Alkaline Water/Seawater Splitting at Large Current Density.

The exploiting electrocatalysts for water/seawater electrolysis with remarkable activity and outstanding durability at industrial grade current density remains a huge challenge. Herein, CoMoNx and Fe-doped CoMoNx nanosheet arrays are in-situ grown on Ni foam, which possess plentiful holes, multilevel heterostructure, and lavish Co5.47 N/MoN@NF and Fe-Co5.47 N/MoN@NF interfaces. They require low overpotentials of 213 and 296 mV for hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) under alkaline media to achieve current density of 800 mA cm-2 , respectively, and both possess low Tafel slopes (51.1 and 49.1 mV dec-1 ) and undiminished stability over 80 h. Moreover, the coupled Co5.47 N/MoN@NF and Fe-Co5.47 N/MoN@NF electrolyzer requires low voltages of 1.735 V to yield 500 mA cm-2 in alkaline water. Notably, they also exhibit exceptional electrocatalytic properties in alkaline seawater (1.833 V@500 mA cm-2 ). The experimental studies and theoretical calculations verify that Fe doping does reduce the energy barrier from OH* to O* intermediates during OER process after catalyst reconstruction, and the non-metallic N site from MoN exhibits the lowest theoretical overpotential. The splendid catalytic performance is attributed to the optimized local electron configuration and porous structure. This discovery provides a new design method toward low-cost and excellent catalysts for water/seawater splitting to produce hydrogen.