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At least 253 records · Page 14
All sourcesNASA NTRSDOE OSTI
DOE OSTI2024

Synthesis of Samarium Nitride Thin Films on Magnesium Oxide (001) Substrates Using Molecular Beam Epitaxy

Rare-earth nitrides are an exciting family of materials with a wide variety of properties desirable for new physics and applications in spintronics and superconducting devices. Among them, samarium nitride is an interesting compound reported to have ferromagnetic behavior coupled with the potential existence of p-wave superconductivity. Synthesis of high-quality thin films is essential in order to manifest these behaviors and understand the impact that vacancies, structural distortions, and doping can have on these properties. In this study, we report the synthesis of samarium nitride monocrystalline thin films on magnesium oxide (001) substrates with a chromium nitride capping layer using molecular beam epitaxy (MBE). We observed a high-quality monocrystalline SmN film with matching orientation to the substrate, then optimized the growth temperature. Despite the initial 2 nm of growth showing formation of a potential samarium oxide layer, the subsequent layers showed high-quality SmN, with semiconducting behavior revealed by an increase in resistivity with decreasing temperature. These promising results highlight the importance of studying diverse heteroepitaxial schemes and open the door for integration of rare-earth nitrides and transition metal nitrides for future spintronic devices.

36 MATERIALS SCIENCE↗
DOE OSTI2012

Crystal structure and magnetic properties of '{alpha} Prime Prime -Fe{sub 16}N{sub 2}' containing residual {alpha}-Fe prepared by low-temperature ammonia nitridation

Slight enhancement of saturation magnetization to 219 A m{sup 2} kg{sup -1} was observed from 199 A m{sup 2} kg{sup -1} for the original {alpha}-Fe on the intermediate nitrided mixture of '{alpha} Prime Prime -Fe{sub 16}N{sub 2}' with residual {alpha}-Fe among the low temperature ammonia nitridation products under 5 T magnetic field at room temperature. The value changed not linearly against the yield as had been expected. Crystal structure refinement indicated that the phase similar to {alpha} Prime Prime -Fe{sub 16}N{sub 2} had deviations on its lattice constants and positional parameters, compared to previously reported values for {alpha} Prime Prime -Fe{sub 16}N{sub 2}. Spin-polarized total energy calculations were performed using the projector-augmented wave method as implemented in the Vienna ab-initio simulation package (VASP) to calculate magnetic moment on the refined crystal structure of the intermediate '{alpha} Prime Prime -Fe{sub 16}N{sub 2}'. The calculations supported the observed magnetization enhancement in the intermediate nitridation product. - Graphical abstract: Crystal structural parameters slightly change in the intermediate nitrided '{alpha} Prime Prime -Fe{sub 16}N{sub 2}' from those in {alpha} Prime Prime -Fe{sub 16}N{sub 2} to show the magnetization maxima in the mixture of '{alpha} Prime Prime -Fe{sub 16}N{sub 2}' and the residual {alpha}-F. Highlights: Black-Right-Pointing-Pointer Larger magnetization was observed than the value of Fe{sub 16}N{sub 2} on its intermediate nitrided mixture with residual {alpha}-Fe. Black-Right-Pointing-Pointer The enhancement was related to the crystal structural deviation from Fe{sub 16}N{sub 2} on the intermediate nitride. Black-Right-Pointing-Pointer It was supported by spin-polarized total energy calculation using the deviated structure.

36 MATERIALS SCIENCE↗
DOE OSTI2013

Synthesis of crumpled nanosheets of polymeric carbon nitride from melamine cyanurate

Polymeric carbon nitride was synthesized by pyrolysis in nitrogen flux at different temperatures between 450 and 700 °C using melamine cyanurate as a reagent and sulfuric acid as a catalyst. The obtained carbon nitride consisted of curled nanosheets (650 °C), and globular particles (700 °C) with formula C₆N₇NHNH₂. The reaction yield of the catalyzed reaction was around the 15% for the sample treated at 700 °C, in a tapped crucible. The optical band gap of the polymer obtained at 700 °C is around 2.9 eV. The gap to the Fermi level is around 2 eV, considerably above the half of the band gap (due to electrons trapped in the gap), indicating that the polymer is probably a n-type semiconductor. - Graphical abstract: Transition from amorphous to crystalline carbon nitride, which is composed of globular particles and is a n-type wide band semiconductor. Highlights: • We synthetized carbon nitride using melamine cyanurate. • The reaction of carbon nitride formation is catalyzed by sulfuric acid. • The carbon nitride obtained at 700 °C is composed of globular particles. • The material obtained at 700 °C is a n-type semiconductor.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2013

Corrosion behavior of mesoporous transition metal nitrides

Transition metal nitrides (TMN) have many desirable characteristics such as high hardness and good thermal stability under reducing conditions. This work reports an initial survey of the chemical stability of mesoporous TMNs (TM=Nb, V, Cr and Ti) in water at 80 °C at neutral, acidic and alkaline pH. The mesoporous TMNs had specific surface areas of 25–60 m{sup 2}/g with average pore sizes ranging from 10 to 50 nm. The high surface areas of these materials enhance the rate of corrosion per unit mass over that of a bulk material, making detection of corrosion much easier. The products were characterized by Rietveld refinement of powder X-ray diffraction (PXRD) patterns and by scanning electron microscopy (SEM). Several nitrides have corrosion rates that are, within error, not distinguishable from zero (±1 Å/day). Of the nitrides examined, CrN appears to be the most corrosion resistant under acidic conditions. None of the nitrides studied are corrosion resistant under alkaline conditions. - Graphical abstract: Corrosion behavior of mesoporous transition metal nitrides (TM=Nb, V, Cr and Ti) in acidic and alkaline solutions at 80 °C for 2 weeks. Display Omitted - highlights: • Corrosion rates of mesoporous transition metal nitrides in aqueous solution is reported. • The mesoporous TMNs had surface areas of 25–60 m{sup 2}/g. • CrN is the most corrosion resistant under the conditions studied.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2012

Facile synthesis of efficient photocatalytic tantalum nitride nanoparticles

Graphical abstract: Tantalum nitride nanoparticles as a visible-light-driven photocatalyst prepared by a novel homogeneously chemical reduction of tantalum pentachloride using sodium in liquid ammonia and the morphologies, visible-light photocatalytic properties and stability of tantalum nitride nanoparticles were investigated. Highlights: ► Tantalum nitride nanoparticles have been prepared by a homogeneously chemical reduction. ► The crystal structure of tantalum nitride was determined by Rietveld refinement and XRD patterns. ► The Tantalum nitride nanoparticle size was in the range of 20–50 nm. ► Much high photocatalytic activities of Ta{sub 3}N{sub 5} nanoparticles were obtained under visible-light irradiation. -- Abstract: Tantalum nitride nanoparticles, as visible-light photocatalysts were synthesized by a two-step homogeneously chemical reduction without any polymers and templates. The well-crystallized Ta{sub 3}N{sub 5} nanoparticles with a range of 20–50 nm in size have been characterized by a number of techniques, such as XRD, XPS, SEM, TEM, BET and UV–Vis spectrum. Most importantly, the Ta{sub 3}N{sub 5} nanoparticles with good stability exhibited higher photooxidation activities in the water splitting and degradation of methylene blue under visible light irradiation than bulk Ta{sub 3}N{sub 5} particles and commercial P25 TiO{sub 2}, demonstrating that Ta{sub 3}N{sub 5} nanoparticle is a promising candidate as a visible-light photocatalyst.

36 MATERIALS SCIENCE↗
DOE OSTI2015

A New Molybdenum Nitride Catalyst with Rhombohedral MoS 2 Structure for Hydrogenation Applications

Nitrogen-rich transition-metal nitrides hold great promise to be the next-generation catalysts for clean and renewable energy applications. However, incorporation of nitrogen into the crystalline lattices of transition metals is thermodynamically unfavorable at atmospheric pressure; most of the known transition metal nitrides are nitrogen-deficient with molar ratios of N:metal less than a unity. In this work, we have formulated a high-pressure route for the synthesis of a nitrogen-rich molybdenum nitride through a solid-state ion-exchange reaction. The newly discovered nitride, 3R-MoN 2 , adopts a rhombohedral R3m structure, isotypic with MoS 2 . Further, this new nitride exhibits catalytic activities that are three times more active than the traditional catalyst MoS 2 for the hydrodesulfurization of dibenzothiophene and more than twice as high in the selectivity to hydrogenation. The nitride is also catalytically active in sour methanation of syngas with >80% CO and H 2 conversion at 723 K. Lastly, our formulated route for the synthesis of 3R-MoN 2 is at a moderate pressure of 3.5 GPa and, thus, is feasible for industrial-scale catalyst production.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2014

Theoretical study of the ammonia nitridation rate on an Fe (100) surface: A combined density functional theory and kinetic Monte Carlo study

Ammonia (NH{sub 3}) nitridation on an Fe surface was studied by combining density functional theory (DFT) and kinetic Monte Carlo (kMC) calculations. A DFT calculation was performed to obtain the energy barriers (E{sub b}) of the relevant elementary processes. The full mechanism of the exact reaction path was divided into five steps (adsorption, dissociation, surface migration, penetration, and diffusion) on an Fe (100) surface pre-covered with nitrogen. The energy barrier (E{sub b}) depended on the N surface coverage. The DFT results were subsequently employed as a database for the kMC simulations. We then evaluated the NH{sub 3} nitridation rate on the N pre-covered Fe surface. To determine the conditions necessary for a rapid NH{sub 3} nitridation rate, the eight reaction events were considered in the kMC simulations: adsorption, desorption, dissociation, reverse dissociation, surface migration, penetration, reverse penetration, and diffusion. This study provides a real-time-scale simulation of NH{sub 3} nitridation influenced by nitrogen surface coverage that allowed us to theoretically determine a nitrogen coverage (0.56 ML) suitable for rapid NH{sub 3} nitridation. In this way, we were able to reveal the coverage dependence of the nitridation reaction using the combined DFT and kMC simulations.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

Ternary nitride semiconductors in the rocksalt crystal structure

Inorganic nitrides with wurtzite crystal structures are well-known semiconductors used in optical and electronic devices. In contrast, rocksalt-structured nitrides are known for their superconducting and refractory properties. Breaking this dichotomy, here we report ternary nitride semiconductors with rocksalt crystal structures, remarkable electronic properties, and the general chemical formula Mg x TM 1−x N ( TM = Ti, Zr, Hf, Nb). Our experiments show that these materials form over a broad metal composition range, and that Mg-rich compositions are nondegenerate semiconductors with visible-range optical absorption onsets (1.8 to 2.1 eV) and up to 100 cm 2 V −1 ⋅s −1 electron mobility for MgZrN 2 grown on MgO substrates. Complementary ab initio calculations reveal that these materials have disorder-tunable optical absorption, large dielectric constants, and electronic bandgaps that are relatively insensitive to disorder. These ternary Mg x TM 1−x N semiconductors are also structurally compatible both with binary TM N superconductors and main-group nitride semiconductors along certain crystallographic orientations. Overall, these results highlight Mg x TM 1−x N as a class of materials combining the semiconducting properties of main-group wurtzite nitrides and rocksalt structure of superconducting transition-metal nitrides.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Transformation of 2D group-III selenides to ultra-thin nitrides: enabling epitaxy on amorphous substrates

Here, the experimental realization of two-dimensional (2D) gallium nitride (GaN) has enabled the exploration of 2D nitride materials beyond boron nitride. Here we demonstrate one possible pathway to realizing ultra-thin nitride layers through a two-step process involving the synthesis of naturally layered, group-III chalcogenides (GIIIC) and subsequent annealing in ammonia (ammonolysis) that leads to an atomic-exchange of the chalcogen and nitrogen species in the 2D-GIIICs. The effect of nitridation differs for gallium and indium selenide, where gallium selenide undergoes structural changes and eventual formation of ultra-thin GaN, while indium selenide layers are primarily etched rather than transformed by nitridation. Further investigation of the resulting GaN films indicates that ultra-thin GaN layers grown on silicon dioxide act as effective 'seed layers' for the growth of 3D GaN on amorphous substrates.

2D materials↗
DOE OSTI2014

Low-temperature CVD of iron, cobalt, and nickel nitride thin films from bis[di(tert-butyl)amido]metal(II) precursors and ammonia

Thin films of late transition metal nitrides (where the metal is iron, cobalt, or nickel) are grown by low-pressure metalorganic chemical vapor deposition from bis[di(tert-butyl)amido]metal(II) precursors and ammonia. These metal nitrides are known to have useful mechanical and magnetic properties, but there are few thin film growth techniques to produce them based on a single precursor family. The authors report the deposition of metal nitride thin films below 300 °C from three recently synthesized M[N(t-Bu){sub 2}]{sub 2} precursors, where M = Fe, Co, and Ni, with growth onset as low as room temperature. Metal-rich phases are obtained with constant nitrogen content from growth onset to 200 °C over a range of feedstock partial pressures. Carbon contamination in the films is minimal for iron and cobalt nitride, but similar to the nitrogen concentration for nickel nitride. X-ray photoelectron spectroscopy indicates that the incorporated nitrogen is present as metal nitride, even for films grown at the reaction onset temperature. Deposition rates of up to 18 nm/min are observed. The film morphologies, growth rates, and compositions are consistent with a gas-phase transamination reaction that produces precursor species with high sticking coefficients and low surface mobilities.

75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
DOE OSTI2018

Improving the Properties of Low-Alloy and Carbon Steel Tools by Cyclic Nitriding

Cyclic nitriding characterized by uniform alternation of cycles with high and low nitrogen potential is considered. In the active stage of the process, the surface layer of the steel is saturated with nitrogen, forming a nitride zone. In the passive stage, the nitrides are resorbed and the internal nitriding zone expands. The phase composition of the nitrided layer in У8 and ХВГ tool steels may be regulated so as to increase the wear resistance of the steel and form a smooth hardness gradient over the surface layer. The length of the active and passive stages such that the wear resistance of the steel is 2.5 times greater than in traditional nitriding by ammonia is determined.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Influences of elevated thermal decomposition of ammonia gas on indium nitride grown by sol–gel spin coating method

Highlights: • A study on indium nitride growth via sol-gel spin coating and nitridation. • Thermal decomposition effects of ammonia gas on films properties are investigated. • Chemical processes describing InN crystal growth are revealed. • Thermal etching effect and metallic indium are observed at increasing temperature. • New insights in synthesizing InN thin films with a simple and low cost method. - Abstract: Indium nitride (InN) thin films grown on aluminum nitride on p-type silicon (111) [AlN/p-Si(111)] substrates are prepared via sol–gel spin coating method followed by nitridation. The thermal decomposition effects of ammonia (NH{sub 3}) gas on the structural properties and surface morphologies of the deposited films are investigated. X-ray diffraction results reveal that the crystalline quality of InN degrades markedly as thermal decomposition of NH{sub 3} gas increases from 700 to 850 °C, at which indium oxide (In{sub 2}O{sub 3}) forms in the deposited films. The thermal etching effect and formation of indium droplet on the film are observed at 850 °C. These findings are consistent with those of elementary and cross-sectional analysis obtained through energy dispersive spectroscopy and field-emission scanning electron microscopy. The findings deduced that InN thin films with densely packed grains can be grown at NH{sub 3} decomposition temperature of 700 °C.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Plasma Nitriding of AISI 304 Stainless Steel in Cathodic and Floating Electric Potential: Influence on Morphology, Chemical Characteristics and Tribological Behavior

In direct current plasma nitriding (DCPN), the treated components are subjected to a high cathodic potential, which brings several inherent shortcomings, e.g., damage by arcing and the edging effect. In active screen plasma nitriding (ASPN) processes, the cathodic potential is applied to a metal screen that surrounds the workload, and the component to be treated is placed in a floating potential. Such an electrical configuration allows plasma to be formed on the metal screen surface rather than on the component surface; thus, the shortcomings of the DCPN are eliminated. In this work, the nitrided experiments were performed using a plasma nitriding unit. Two groups of samples were placed on the table in the cathodic and the floating potential, corresponding to the DCPN and ASPN, respectively. The floating samples and table were surrounded by a steel screen. The DCPN and ASPN of the AISI 304 stainless steels are investigated as a function of the electric potential. The samples were characterized using scanning electron microscopy with energy-dispersive x-ray spectroscopy, x-ray diffraction, atomic force microscopy and transmission electron microscope. Dry sliding ball-on-disk wear tests were conducted on the untreated substrate, DCPN and ASPN samples. The results reveal that all nitrided samples successfully produced similar nitrogen-supersaturated S phase layers on their surfaces. This finding also shows the strong impact of the electric potential of the nitriding process on the morphology, chemical characteristics, hardness and tribological behavior of the DCPN and ASPN samples.

36 MATERIALS SCIENCE↗
DOE OSTI2018

Ultrathin Cobalt Oxide Overlayer Promotes Catalytic Activity of Cobalt Nitride for the Oxygen Reduction Reaction

Here, the oxygen reduction reaction (ORR) plays a crucial role in various energy devices such as proton-exchange membrane fuel cells (PEMFCs) and metal–air batteries. Owing to the scarcity of the current state-of-the-art Pt-based catalysts, cost-effective Pt-free materials such as transition metal nitrides and their derivatives have gained overwhelming interest as alternatives. In particular, cobalt nitride (CoN) has demonstrated a reasonably high ORR activity. However, the nature of its active phase still remains elusive. Here, we employ density functional theory calculations to study the surface reactivity of rocksalt (RS) and zincblend (ZB) cobalt nitride. The performances of the catalysts terminated by the facets of (100), (110), and (111) are studied for the ORR. We demonstrate that the cobalt nitride surface is highly susceptible to oxidation under ORR conditions. The as-formed oxide overlayer on the facets of CoN RS (100) and CoN ZB (110) presents a significant promotional effect in reducing the ORR overpotential, thereby increasing the activity in comparison with those of the pure CoNs. The results of this work rationalize a number of experimental reports in the literature and disclose the nature of the active phase of cobalt nitrides for the ORR. Moreover, they offer guidelines for understanding the activity of other transition metal nitrides and designing efficient catalysts for future generation of PEMFCs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2019

A map of the inorganic ternary metal nitrides

Exploratory synthesis in new chemical spaces is the essence of solid-state chemistry. However, uncharted chemical spaces can be difficult to navigate, especially when materials synthesis is challenging. Nitrides represent one such space, where stringent synthesis constraints have limited the exploration of this important class of functional materials. Here, we employ a suite of computational materials discovery and informatics tools to construct a large stability map of the inorganic ternary metal nitrides. Our map clusters the ternary nitrides into chemical families with distinct stability and metastability, and highlights hundreds of promising new ternary nitride spaces for experimental investigation - from which we experimentally realized seven new Zn- and Mg-based ternary nitrides. As a result, by extracting the mixed metallicity, ionicity and covalency of solid-state bonding from the density functional theory (DFT)-computed electron density, we reveal the complex interplay between chemistry, composition and electronic structure in governing large-scale stability trends in ternary nitride materials.

36 MATERIALS SCIENCE↗
DOE OSTI2025

Investigating the effects of local environment on nitrogen vacancies in high-entropy metal nitrides

High-entropy metal nitrides are an important material class in a variety of applications, and the role of nitrogen vacancies is of great importance for understanding their stability and mechanical properties. Here, we study six different high-entropy nitrides with eight different metal species to build a predictive model of the nitrogen-vacancy formation energy. We construct sets of supercells that maximize the number of unique nitrogen environments for a given chemistry, and then use density-functional theory to calculate the energy density for all nitrogen sites, and the vacancy formation energies for the highest, lowest, and a median subset based on the energy densities. The energy density of nitrogen sites correlates with the vacancy formation energies, for binary, ternary, and high-entropy nitrides. A linear regression model predicts the vacancy formation energies using only the nearest-neighbor composition; across our eight metals, we find the largest vacancy formation energies next to Hf, then Zr, Ti, V, Cr, Ta, Nb, and the lowest near Mo. Additionally, we see that binary nitride data show qualitatively similar vacancy formation energy trends for high-entropy nitrides; however, the binary data alone are insufficient to predict the complex nitride behavior. Our model is both predictive and easily interpretable, and correlates with experimental data.

DeSilva, Charith R. [Univ. of Illinois at Urbana-C↗
DOE OSTI2017

Investigation of Nitrogen Absorption Rate and Nitride Growth on SRF Cavity Grade RRR Niobium as a Function of Furnace Temperature

The current state of the art processing of niobium superconducting radio frequency cavities with nitrogen diffusion is performed at 800 C in a furnace with a partial pressure of approximately ~20 mTorr of nitrogen. Multiple studies have shown the bulk of the nitrogen absorbed by the niobium forms a thick (1-3 microns) non-superconducting nitride layer which must be removed to produce optimal RF results. The depth profiling of interstitial nitrogen and surface nitrides has already been probed using SIMS measurements for this recipe. These measurements have been successfully modelled by extrapolating data from nitride growth studies performed at atmospheric pressure and temperatures above 1000 C.1 One open question is whether there is a diffusion-only zone at lower temperature in the ~20 mTorr range in which the niobium will absorb nitrogen but not create a non-superconducting nitride layer; or is the absorption of nitrogen only possible by first forming a nitride buffer layer which then frees up nitrogen for absorption which is what has been shown down to 600 C at atmospheric pressures on long time scales. A systematic study of absorption vs. temperature and correlated SIMS measurements is required to answer this question. We report on measurements of the parabolic rate constant vs. temperature from 400 C to 900 C of cavity grade niobium with metallurgically flat witness samples. Depth profiles of witness samples using SIMS are presented together with SEM imaging for nitride crystals and correlated with N absorption.

Reece, Charles↗
DOE OSTI2014

Electrochemical Solution Growth of Magnetic Nitrides

Magnetic nitrides, if manufactured in bulk form, would provide designers of transformers and inductors with a new class of better performing and affordable soft magnetic materials. According to experimental results from thin films and/or theoretical calculations, magnetic nitrides would have magnetic moments well in excess of current state of the art soft magnets. Furthermore, magnetic nitrides would have higher resistivities than current transformer core materials and therefore not require the use of laminates of inactive material to limit eddy current losses. However, almost all of the magnetic nitrides have been elusive except in difficult to reproduce thin films or as inclusions in another material. Now, through its ability to reduce atmospheric nitrogen, the electrochemical solution growth (ESG) technique can bring highly sought after (and previously inaccessible) new magnetic nitrides into existence in bulk form. This method utilizes a molten salt as a solvent to solubilize metal cations and nitrogen ions produced electrochemically and form nitrogen compounds. Unlike other growth methods, the scalable ESG process can sustain high growth rates (~mm/hr) even under reasonable operating conditions (atmospheric pressure and 500 °C). Ultimately, this translates into a high throughput, low cost, manufacturing process. The ESG process has already been used successfully to grow high quality GaN. Below, the experimental results of an exploratory express LDRD project to access the viability of the ESG technique to grow magnetic nitrides will be presented.

36 MATERIALS SCIENCE↗