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At least 19 records
All sourcesNASA NTRSDOE OSTI
DOE OSTI2022

Properties and microstructure evolution of silicon nitride and zirconium nitride following Ni ion irradiation

We report that silicon nitride and zirconium nitride have been proposed as potential materials for multiple nuclear applications (inert matrix fuels, accident tolerant fuels, space nuclear power, fusion reactor design), yet knowledge on their behavior under irradiation remains limited. Ion irradiations were performed using 15 MeV Ni 5+ ions on Si 3 N 4 and ZrN samples, with midrange doses (around 3 µm) from 1 to 50 dpa and temperatures from 300 to 700°C. Volumetric lattice swelling was determined by grazing incidence X-ray diffraction, defect production and evolution were tracked using Transmission Electron Microscopy, and nanoindentation was performed to quantify the ceramics’ mechanical properties evolution. The results from these irradiation studies on nitride ceramics help fill the current gap present in the literature. Behavior consistent with past work on irradiated Si 3 N 4 was observed with respect to mechanical properties and defect formation up to 15 dpa and 500°C. Failure of the grain boundary sintering aid in Si 3 N 4 was observed above these conditions. Different behavior was observed in both nitrides at 50 dpa and 700°C, where lattice swelling increased past potential saturation values. Unreported cavity formation was witnessed in both materials under all irradiation conditions, with stable number density and slight size increase above 15 dpa. The mechanism for the cavity formation remains to be determined.

36 MATERIALS SCIENCE↗
DOE OSTI2015

On the mechanism of zirconium nitride formation by zirconium, zirconia and yttria burning in air

The combustion of Zr and (Zr+ZrO{sub 2}) powdery mixtures in air was accompanied by major ZrN stabilization. The synthesis of cheap ZrN with the high yield in air was facile and utile. The influence of Y{sub 2}O{sub 3} additive on the content of ZrN the solid combustion products (SCP) was investigated. The reagents and SCP were analyzed by BET, DTA–TGA, XRD, SEM and EDS. Burning temperature was measured by thermal imager. The yield of ZrN in the SCP has been varied by the time regulation of the combustion process. The burning samples were quenched at a certain time to avoid the re-oxidation of the obtained ZrN by oxygen. The quenching of the burned (Zr+ZrO{sub 2}) samples with the Y{sub 2}O{sub 3} additive was allowed increasing the ZrN yield in SCP up to 66 wt%. The chemical mechanism of ZrN formation in air was discussed and the probable source of ZrN massive formation is suggested. - Highlights: • Combustion of Zr, (Zr+ZrO{sub 2}) and (Zr+ZrO{sub 2}+Y{sub 2}O{sub 3}) powdery mixtures in air was studied. • The new combustion phenomenon has been found: metal (Zr) chemically reacts with its oxide (ZrO{sub 2}) in the burning wave. • The effective influence of Y{sub 2}O{sub 3} additive (2–3 wt%) on ZrN yield in combustion products is shown. • The yield of ZrN in the combustion products can be varied by the burning time regulation (quenching)

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2018

Molecular Zirconium Nitride Super Base from a Mononuclear Parent Imide

In this work, we prepared, isolated, and structurally characterized a zirconium complex having a terminally bound imide motif, (PN) 2 Zr≡NH (PN – = (N-(2- i Pr 2 P-4-methylphenyl)-2,4,6-trimethylanilide)), along with the zirconium nitride complex {(PN) 2 Zr≡N[μ 2 -Li(THF)]} 2 . (PN) 2 Zr≡NH was prepared by reduction of trans-(PN) 2 Zr(N 3 ) 2 with KC 8 . Isotopic labeling and spectroscopic studies were conducted using the respective 15 N enriched isotopologues, whereas solid-state structural studies confirmed some of the shortest Zr≡N distances known to date (Zr≡NH, 1.830(3) Å; Zr≡N – , 1.822(2) Å). It was found that the nitride in {(PN) 2 Zr≡N[μ 2 -Li(THF)]} 2 is super basic and in the range of –36 to –43 pK b units. Furthermore, computational studies have been applied to probe the bonding and structure for this new class of zirconium–nitrogen multiple bonds.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
DOE OSTI2015

Low temperature plasma enhanced atomic layer deposition of conducting zirconium nitride films using tetrakis (dimethylamido) zirconium and forming gas (5% H{sub 2} + 95% N{sub 2}) plasma

Zirconium nitride (ZrN) has the lowest bulk electrical resistivity and high thermal stability among group IV and V transition metal nitrides, which makes it a promising material for ULSI applications such as a diffusion barrier for Cu interconnects, contact metal in III-V semiconductor devices, and in high density memory structures. Plasma enhanced atomic layer deposition (PEALD) of conducting ZrN thin films using Zr[N(CH{sub 3}){sub 2}]{sub 4} and forming gas (5% H{sub 2} + 95% N{sub 2}) plasma is reported in this article. The growth per cycle (GPC) for every deposition was determined from analysis of dynamic in-situ spectroscopic ellipsometry (d-iSE) measurements. An experimental design is proposed for faster determination of ALD growth saturation curves. At substrate temperature of 150 °C, a GPC of 0.10 nm/cycle was observed for self-limiting ZrN PEALD growth. The electrical resistivity of ZrN films deposited on SiO{sub 2} substrate was found to be 559.5 ± 18.5 μΩ cm with negligible change in resistivity even after ∼1000 h exposure to air. The metallic behavior of our ZrN films was evident from the free electron dispersion component in dielectric response, the broad band of photoelectron emission across Fermi level and the positive temperature coefficient for resistivity of 0.0088/ °C.

36 MATERIALS SCIENCE↗
DOE OSTI2016

Development of a Modified Embedded Atom Force Field for Zirconium Nitride Using Multi-Objective Evolutionary Optimization

Zirconium nitride (ZrN) exhibits exceptional mechanical, chemical, and electrical properties, which make it attractive for a wide range of technological applications, including wear-resistant coatings, protection from corrosion, cutting/shaping tools, and nuclear breeder reactors. Despite its broad usability, an atomic scale understanding of the superior performance of ZrN, and its response to external stimuli, for example, temperature, applied strain, and so on, is not well understood. This is mainly due to the lack of interatomic potential models that accurately describe the interactions between Zr and N atoms. To address this challenge, we develop a modified embedded atom method (MEAM) interatomic potential for the Zr–N binary system by training against formation enthalpies, lattice parameters, elastic properties, and surface energies of ZrN (and, in some cases, also Zr3N4) obtained from density functional theory (DFT) calculations. The best set of MEAM parameters are determined by employing a multiobjective global optimization scheme driven by genetic algorithms. Our newly developed MEAM potential accurately reproduces structure, thermodynamics, energetic ordering of polymorphs, as well as elastic and surface properties of Zr–N compounds, in excellent agreement with DFT calculations and experiments. As a representative application, we employed molecular dynamics simulations based on this MEAM potential to investigate the atomic scale mechanisms underlying fracture of bulk and nanopillar ZrN under applied uniaxial strains, as well as the impact of strain rate on their mechanical behavior. These simulations indicate that bulk ZrN undergoes brittle fracture irrespective of the strain rate, while ZrN nanopillars show quasi-plasticity owing to amorphization at the crack front. The MEAM potential for Zr–N developed in this work is an invaluable tool to investigate atomic-scale mechanisms underlying the response of ZrN to external stimuli (e.g, temperature, pressure etc.), as well as other interesting phenomena such as precipitation.

36 MATERIALS SCIENCE↗
DOE OSTI2020

Stabilization of Low Valent Zirconium Nitrides in Titanium Nitride via Plasma-Enhanced Atomic Layer Deposition and Assessment of Electrochemical Properties

The increasing awareness of metal nitrides as feasible electrocatalysts in numerous energy-relevant transformations motivates greater synthetic control of mixed metal nitride compositions and their valence states. We report plasma-enhanced atomic layer deposition of titanium zirconium nitride, with an emphasis on the experimental parameters that influence the valence states of the two metal ions. We further examined the consequence of various ratios of Ti and Zr on the electrochemically active surface areas (ECSAs). Films with a Zr-to-Ti ratio of 1:2 or 1:1 yielded the highest ECSA; deviation from these values led to a large fraction of electrically insulating or semiconducting titanium or zirconium oxynitrides/oxides. The systematic examination establishes a fundamental structure-property relationship critical to assessing the electrochemical/electrocatalytic properties of metal nitrides.

36 MATERIALS SCIENCE↗
DOE OSTI2014

Deposition and characterization of zirconium nitride (ZrN) thin films by reactive magnetron sputtering with linear gas ion source and bias voltage

Zirconium nitride thin films have been prepared on stainless steel substrate (304L grade) by reactive cylindrical magnetron sputtering method with Gas Ion Source (GIS) and bias voltage using optimized coating parameters. The structure and surface morphologies of the ZrN films were characterized using X-ray diffraction, atomic microscopy and scanning electron microscopy. The adhesion property of ZrN thin film has been increased due to the GIS. The coating exhibits better adhesion strength up to 10 N whereas the ZrN thin film with bias voltage exhibits adhesion up to 500 mN.

36 MATERIALS SCIENCE↗
DOE OSTI2014

FP-LAPW investigation of electronic, magnetic, elastic and thermal properties of Fe-doped zirconium nitride

Full Potential- Linear Augmented Plane Wave (FP-LAPW) method has been employed to study the electronic, magnetic, elastic and thermal properties of Fe-doped Zirconium nitride. In this work, Fe-atoms were doped into the super cell of ZrN in doping concentrations of 12.5%, 25% and 37.5% to replace Zr atoms. Electronic properties such as band structure and DOS were plotted and compared for the doped compounds. Charge density contours were plotted for all the doped compounds. The non-magnetic ZrN doped in different Fe concentrations were found to be ferromagnetic. Magnetic moments have been calculated and compared. Elastic properties have been studied and compared with electronic properties. Appearance of magnetic ordering and its influence with the elastic properties have been reported. Impact of 3d states of Fe in DOS plot on the elastic nature of the compounds has been highlighted. Thermal properties such as Debye temperature and molar heat capacities at low temperature have been determined. Debye temperature is found to decrease with higher doping concentrations. Molar heat capacities are found to increase with higher concentrations of Fe atoms.

36 MATERIALS SCIENCE↗
DOE OSTI2017

Fluidized Bed Chemical Vapor Deposition of Zirconium Nitride Films

A fluidized bed-chemical vapor deposition (FB-CVD) process was designed and established in a two-part experiment to produce zirconium nitride barrier coatings on uranium-molybdenum particles for a reduced enrichment dispersion fuel concept. A hot-wall, inverted fluidized bed reaction vessel was developed for this process, and coatings were produced from thermal decomposition of the metallo-organic precursor tetrakis(dimethylamino)zirconium (TDMAZ) in high purity argon gas. Experiments were executed at atmospheric pressure and low substrate temperatures (i.e., 500 to 550 K). Deposited coatings were characterized using scanning electron microscopy, energy dispersive spectroscopy, and wavelength dispersive spectroscopy. Successful depositions were produced on 1 mm diameter tungsten wires and fluidized ZrO 2 -SiO 2 microspheres (185 to 250 µm diameter) with coating thicknesses ranging from 0.5 to 30 µm. The coating deposition rate was nominally estimated to be 0.04 ± 0.02 µm/h. The ZrN coating adhered to the microspheres but there was a significant oxygen and possible carbon contamination.

11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS↗
DOE OSTI2024

Molecular beam epitaxy of superconducting zirconium nitride on GaN substrates

Epitaxial integration of metals and semiconductors can enable enhanced performance and novel functionality. Achieving such pristine interfaces with superconducting materials is of increasing interest for quantum devices and detectors, but the experimental demonstration remains challenging, given the very limited studies on single crystalline systems. To expand the potential materials for these systems, this work explores the deposition of zirconium nitride superconducting thin films on GaN substrates at various temperatures using molecular beam epitaxy. A general trend of decreasing superconducting critical temperature is observed as the deposition temperature is reduced. The optical properties reveal a transition from metallic to dielectric behavior with colder deposition. The plasma frequency of the metallic films is also observed to be a function of growth temperature. These results pave the way for the integration of a highly tunable metal nitride with a well-established semiconductor system.

36 MATERIALS SCIENCE↗
DOE OSTI2017

First-principles study of fission gas incorporation and migration in zirconium nitride

To evaluate the effectiveness of ZrN as a diffusion barrier against fission gases, we investigate in this paper the incorporation and migration of fission gas atoms, with a focus on Xe, in ZrN by first-principles calculations. The formations of point defects in ZrN, including vacancies, interstitials, divacancies, Frenkel pairs, and Schottky defects, are first studied. Among all the defects, the Schottky defect with two vacancies as first nearest neighbor is predicted to be the most favorable incorporation site for fission gas Xe in ZrN. The migration of Xe gas atom in ZrN is investigated through two diffusion mechanisms, i.e., interstitial and vacancy-assisted diffusions. The migration barrier of Xe gas atom through the intrinsic interstitials in ZrN is considerably lower than that through vacancies. Finally, therefore, at low temperatures fission gas Xe atoms diffuse mainly through interstitials in single crystal ZrN, whereas at high temperatures Xe may diffuse in ZrN assisted by vacancies.

36 MATERIALS SCIENCE↗
DOE OSTI2011

Zirconium nitride films deposited in (Ar + N{sub 2} + H{sub 2}) sputtering atmosphere: Optical, structural, and electrical properties

Zr-N films were grown on glass substrates via radio-frequency magnetron sputtering using an Ar + N{sub 2} + H{sub 2} mixture. Hydrogen was employed in order to reduce oxygen contamination coming from background pressure, as confirmed by secondary ion mass spectroscopy analysis. The tuned process parameter was the nitrogen flux percentage (R{sub N2}) in the mixture. The crystallographic structure of the films was studied using x-ray diffraction. The measurements show that the films deposited at low R{sub N2} (lower than or equal to 50%) crystallize in the rocksalt ZrN structure. As R{sub N2} exceeds 50%, the film exhibits the co-presence of ZrN and Zr{sub 3}N{sub 4} (denoted as o-Zr{sub 3}N{sub 4}) phases. When the deposition is performed in only nitrogen atmosphere (R{sub N2} = 100%), a broad peak located at 2{theta}{approx_equal} 32.2 deg. is mainly attributed to the contribution coming from (320) planes of the o-Zr{sub 3}N{sub 4}. An envelope method, based on the optical reflection and transmission spectra taken at normal incidence, has been applied for the optical characterization of the nitride films. Such a method allows the determination of the samples' average thickness and optical constants (refractive index n and extinction coefficient k) in the ultraviolet-visible-near infrared regions. The evaluated thickness was about 2500 nm, which is in good agreement with the value obtained from profilometry. The absorption coefficient {alpha} was calculated from reflectance and transmittance spectra. The energy bandgap ranges from 2.3 eV to 2.4 eV. Electrical characterization was performed using capacitance-voltage measurements, which showed that the films evolve from insulating to semiconductor behavior when the nitrogen content in the sputtering atmosphere is decreased, confirming structural and optical results.

36 MATERIALS SCIENCE↗
DOE OSTI2016

First-principles study of inert gas incorporation and migration in zirconium nitride

Uranium-Molybdenum alloy based fuels are the most promising fuel for the future high performance research reactors using low enriched uranium (LEU). However, when used in dispersion with aluminum, significant amount of interaction products form at the interface between the UMo fuel particle and the surrounding Al during in-pile tests which leads to non-acceptable swelling. To reduce the swelling in U-Mo/Al dispersion fuel at high burnups, different diffusion barrier coatings, e.g., ZrN, were deposited on the U-Mo particles to avoid the interaction between fuel particles and the Al matrix. These diffusion barrier coatings are very effective in reducing the formation of interaction layer and therefore the fuel swelling. So far, ZrN is selected as the candidate coating material for the European Dispersion Fuel program due to the superior thermophysical properties of ZrN. The thermodynamic and kinetic stability of ZrN coating with respect to Al and U-Mo has been studied by the current authors using density functional theory calculations. So far there are very few studies of the diffusion behaviors of inert gases in ZrN. A recent publication on irradiated (Pu,Zr)N reveals that the majority of fission-induced Xe is retained in the material, while He is release to the fuel pin to a large extent. This raises the questions on the underlying differences of inert gas behavior in nitride fuel. Therefore, the purpose of this study is to understand the incorporation and migration behavior of inert gases He, Kr and Xe in ZrN using density functional theory (DFT) based first-principles calculations. Using density-functional theory calculations we provided a systematic study of the incorporation and migration of fission gases in ZrN. We investigated the formation energies of several defects (vacancies, interstitials, divacancies, Frenkel pairs, and Schottky defects) and the incorporation energies of inert gases in these defects. Results show that the formation energies of point defects are strongly affected by the chemical potentials of N and Zr species. The energetically most favorable incorporation site for fission gases is found to be the first nearest neighbor Schottky defect, in which the fission gas atom sits at somewhere between the Zr and N vacancies. The predicted solution energies of rare gases, i.e, He, Kr and Xe, in ZrN, is almost linearly dependent on the atom size of inert gases. We compared the solution energy Xe in ZrN with several other nuclear materials with the same B1 structure (MX), e.g., TiN, UN and UC. The solution energies of Xe in MX are closely related to the size of vacancy sites. The potential migration mechanisms of Xe in ZrN include interstitial and vacancy-assisted diffusion. The calculations show that vacancies essentially act as Xe trapping sites. The migration behavior of Xe in N and Zr divacancy and Schottky defects were compared with that through tetrahedral interstitials. It is found that the migration barrier is much lower with the interstitial mechanism than those with the vacancy mechanism. Therefore, at low temperatures Xe diffusion in ZrN is mostly through the interstitial mechanism or existing grain boundaries while at high temperature volume diffusion could be preferred, i.e., diffusion with Zr and N vacancies. (authors)

36 MATERIALS SCIENCE↗