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Andriy Zakutayev

Publications and source records attributed to Andriy Zakutayev.

At least 19 recordsLinked to original sources

Revealing the Atomic Structure of NiO/Ga$_{2}$O$_{3}$ Interfaces

NiO/Ga$_{2}$O$_{3}$ heterojunctions have garnered significant attention for use in power electronics due to the ultrawide bandgap and wafer-scale availability of Ga$_{2}$O$_{3}$ and the controllable p-type doping of NiO. However, the structure of NiO/Ga$_{2}$O$_{3}$ interfaces remains underexplored, largely due to the complexity of the junction between their dissimilar cubic and monoclinic crystal structures. Here we investigate the atomistic structure of the NiO/Ga$_{2}$O$_{3}$ interface for (100), (-201), and (001) oriented Ga$_{2}$O$_{3}$ substrates using aberration-corrected scanning transmission electron microscopy (STEM) in combination with interface modeling and image simulations. We evaluate the abruptness and consistency of the interfaces and compare them to calculated interface models, proposing precise atomic structures and assessing potential structural variation arising from complexity of the monoclinic Ga$_{2}$O$_{3}$ crystal structure. Our interface analysis supports increased focus on (100) oriented Ga$_{2}$O$_{3}$ as a candidate for fabricating high quality, low defect density NiO/Ga$_{2}$O$_{3}$ heterojunction devices. Importantly, we consider the effects of specimen thickness and 3D-to-2D projection during the STEM imaging process to differentiate such effects from real crystal variations. This work provides insight into the effect of substrate orientation on NiO film and interface quality, creating a pathway to improving heterojunction properties. It further highlights important considerations for interpretation of stability and interlayer phase formation in these interfaces, which is crucial for their integration into reliable and robust power electronic devices.

cond-mat.mtrl-sci

Fast Homoepitaxy on (100) \b{eta}-Ga2O3 Substrates with Large Grown-In Offcut

The choice of crystalline orientation and offcut angle is non-trivial for low-symmetry $\beta\text{-Ga}_2\text{O}_3$, where anisotropy impacts bulk and thin film synthesis, material properties, and power device fabrication and performance. Scalable (100)-oriented $\beta\text{-Ga}_2\text{O}_3$ wafers are desirable for electronic devices but are not typically used due to 10-30x slower growth rates compared to other orientations. Here we report molecular beam epitaxy (MBE) growth rates equal to the fast growth direction by using (100) $Ga_2O_3$ wafers with large grown-in offcuts. The offcuts (up to 13.4{\deg}) are directly grown by Edge-defined Film-fed Growth (EFG) of 2D ribbons with rotated seed crystals, avoiding material loss from crystal boule offcut methods while maintaining high crystalline quality. Chemical-mechanical polishing produces epitaxy-ready substrates, and step flow growth is observed across all offcut angles. We measure an unintentional n-type doping density of $2{\times}10^{15} cm^{-3}$, one of the lowest values reported for MBE-grown films. Planar Schottky barrier diodes on these epilayers without edge termination have an on/off ratio ~10$^5$ and an average breakdown field of 1.56 MV/cm, comparable to or exceeding similar devices fabricated on other orientations. Overall, these results illustrate the importance of both crystal face and offcut angle and validate the use of the scalable (100)-oriented $\beta\text{-Ga}_2\text{O}_3$ wafers.

cond-mat.mtrl-sci

Composition-dependent Thin-film Synthesis of Layered Ternary Iron Nitrides FeMN2 (M = W, Mo)

Ternary transition-metal nitrides with layered crystal structures host anisotropic bonding and reduced dimensionality that may enable unconventional electronic and magnetic behavior. Yet, synthesis of such nitride thin films remains challenging because reactive sputtering often favors metastable rocksalt-derived structures. We report the composition-dependent synthesis, structure, and properties of layered FeMN2 (M = W, Mo) thin films with triangular Fe sublattices, prepared by reactive sputtering and post-deposition NH3 annealing. Using synchrotron grazing-incidence wide-angle X-ray scattering (GIWAXS) and X-ray absorption spectroscopy (XAS), we investigate the evolution of phase formation, crystallographic texture, and local Fe coordination across composition. Both layered phase form over broad composition ranges. FeWN2 maintains high phase purity across compositions, consistent with cation substitution, whereas FeMoN2 only exhibits good phase purity at Fe-poor compositions. Azimuthal GIWAXS analysis shows that Fe-rich films in both systems exhibit out-of-plane fiber texture, which progressively evolves toward predominantly in-plane orientation near stoichiometry in FeWN2, while FeMoN2 develops a more randomly oriented polycrystalline microstructure. Electrical measurements reveal relatively low and composition-insensitive resistivity in FeWN2 (~1 m{\Omega}.cm), whereas FeMoN2 exhibits a pronounced resistivity maximum near nominal stoichiometry. Preliminary room-temperature magnetization measurements on FeWN2 further reveal weak ferromagnetic-like behavior in Fe-poor films, while stoichiometric compositions remain predominantly paramagnetic. These results demonstrate fundamentally different structural accommodation mechanisms in FeWN2 and FeMoN2, and highlight the strong coupling between composition, microstructure, and electronic/magnetic properties in layered nitride thin films.

cond-mat.mtrl-sci

Synthesis and properties of bulk Mg$_3$WN$_4$ in a wurtzite-derived structure

Experimental synthesis of theoretically predicted materials with controlled elemental coordination environments can lead to realization of useful properties, such as facile ion transport or ferroelectric switching. Among such materials are new ternary nitrides in the Mg-W-N composition space, where several new stable and metastable compounds have been predicted and synthesized recently in bulk and film forms. Here, we report for the first time on the bulk synthesis of Mg$_3$WN$_4$ in a wurtzite-derived crystal structure via a solid state metathesis reaction. $In$ $situ$ synchrotron powder X-ray diffraction shows how the ion exchange proceeds from Li$_6$WN$_4$ + 3 MgCl$_2$ precursors to Mg$_3$WN$_4$ + 6 LiCl products, with the reaction starting slowly near 380 $^\circ$C and completing by 600 $^\circ$C, including the presence of a competing disordered rocksalt-derived phase (Mg,W)N above 440 $^\circ$C. The follow up $ex$ $situ$ powder synthesis at 400 $^\circ$C for 0.5 hour with 10% excess MgCl$_2$ reveals the cation-ordered nature of the wurtzite-derived Mg$_3$WN$_4$ structure with polar symmetry confirmed by second harmonic generation measurements. Optical absorption spectra, chemical composition analysis, and electron microscopy imaging suggests that bulk wurtzite Mg$_3$WN$_4$ is prone to defect formation. Overall, this study shows that selective $ex$ $situ$ synthesis of the phase pure ternary nitrides, informed by \textit{in situ} measurements, is possible by carefully controlling the thermal budget of the reaction, and paves a way towards property characterization of wurtzite Mg$_3$WN$_4$.

cond-mat.mtrl-sci

Systematic comparison of approximations and functionals in first-principle calculations of aluminum-based III-V ferroelectric nitrides

We revisit first-principles predictions of structural, ferroelectric, and electronic properties in aluminum-based III-V nitride alloys, focusing on Al1-xScxN and Al1-xBxN. Using density functional theory within a unified 48-atom supercell framework, we systematically assess the role of chemical disorder and exchange-correlation approximations by comparing the virtual crystal approximation (VCA) and special quasirandom structures (SQS), as well as PBE, PBESol, SCAN, and SCAN+rVV10 functionals. We demonstrate that, even amongst the similar PBE and PBESol functionals, big quantitative and qualitative differences emerge. In particular, the VCA or SQS PBESol (a popular functional) strongly underestimate the stability domain of the ferroelectric wurtzite phase in Al1-xScxN compared to SQS PBE or SQS SCAN. We demonstrate that the 5-fold coordinated hexagonal phase predicted in 2002 by Farrer and Bellaiche [Phys. Rev. B 66, 201203] is a low-energy metastable state between the four-fold coordinated ferroelectric wurtzite phase and the six-fold coordinated rocksalt phase near the transition point upon increasing the Sc content. In contrast, Al1-xBxN shows a much faster destabilization of the wurtzite ferroelectric phase, with bond breaking which strongly distorts the wurtzite structure (with enhanced polarization) and eventually favor a zincblende phase and a threefold coordinated hexagonal layer phase. Our analysis highlights the critical importance of both local disorder and exchange-correlation treatment in predicting the functional properties of III-V nitride ferroelectrics. Overall, SQS combined with SCAN provides the most consistent theoretical framework for understanding and optimizing emerging nitride-based ferroelectric materials.

cond-mat.mtrl-sci

Born-Qualified: An Autonomous Framework for Deploying Advanced Energy and Electronic Materials

Autonomous science is transforming how we discover materials and chemical systems for advanced energy technologies. However, many initially promising systems never reach deployment. This "valley of death" stems from optimization that prioritizes laboratory metrics over industrial viability. We propose a new strategy: "born-qualified" autonomous development, which embeds manufacturability, cost, and durability constraints from the outset. This approach is enabled by four pillars, including the development of multi-objective metrics, causal models, a modular infrastructure, and embedding manufacturing in the discovery loop. Realizing this vision will require sustained, community-wide commitment, but the potential return on that investment is commensurate with the scale of the challenge.

cond-mat.mtrl-sci

Thin film synthesis of SrZn2P2 with SrI2 post-annealing for enhanced crystallinity and optoelectronic quality

Ternary Zintl phosphides are promising light-absorbing semiconductors for thin-film optoelectronic applications, but strategies for controlling their microstructure and optoelectronic quality remain underexplored. Here, we report the synthesis of phase-pure SrZn2P2 thin films using radio-frequency co-sputtering in a PH3 + Ar atmosphere and investigate the impact of post-growth processing on their structural and optical properties. Grazing-incidence X-ray scattering and Raman spectroscopy confirm the formation of crystalline SrZn2P2 films over a finite compositional window. Optical measurements reveal strong absorption near the direct-band-gap energy (~1.8 eV) and near-band-edge photoluminescence. Further, we have studied the effects of chemically compatible halide-assisted annealing. It is found that SrI2 treatments lead to pronounced grain growth and reduced diffraction peak broadening while preserving phase purity, in contrast to rapid thermal or forming-gas annealing. Notably, annealing with SrI2 at 450 {\deg}C significantly enhances both the intensity and spatial uniformity of the photoluminescence, thus connecting the observed microstructural consolidation with improved radiative recombination. Our study demonstrates that halide-assisted annealing provides an effective pathway for microstructural control in SrZn2P2 thin films and highlights a generalizable processing strategy for advancing Zintl phosphide semiconductors toward optoelectronic applications.

cond-mat.mtrl-sci

Autonomous Reliability Qualification of Ga$_2$O$_3$-based diode sensors via Safe Active Learning

Ultra-wide bandgap (UWBG) Ga$_2$O$_3$ is a promising semiconductor for high-power and high-temperature electronics. Reliable qualification of these devices under extreme operating conditions is essential, yet conventional reliability testing is inherently time-consuming. Autonomous experimentation offers a new paradigm by enabling measurement planning and model refinement to evolve in parallel in real time. We present a Safe Active Learning (SAL) framework for autonomous reliability characterization of Ga$_2$O$_3$-based diode sensors under coupled thermal and hydrogen stress. We first evaluate SAL in simulation, where it safely expands the explored region while learning the evolving rectification surface. Second, we demonstrate SAL experimentally on an automated high-temperature probe-station platform using a Pt/Cr$_2$O$_3$:Mg/$\beta$-Ga$_2$O$_3$ diode sensor of H$_2$ and temperature, spanning 0-800 ppm H$_2$ and 350-550 {\deg}C. Finally, we use the SAL-generated dataset for offline long-horizon forecasting of the diode current at a target voltage with a structured Gaussian-process model. Its condition-dependent Kohlrausch--Williams--Watts mean and residual covariance kernel were engineered with artificial-intelligence assistance using the SAL data and an auxiliary validation dataset spanning 1,000 hours at 400 {\deg}C across multiple H$_2$ concentrations. This dataset guided kernel design and validation, and the resulting model captures its long-time, saturating degradation trends. Although demonstrated here for a rectifying Ga$_2$O$_3$-based diode, SAL is applicable to other device classes whenever a suitable safety observable can be measured in situ.

physics.app-ph

Long photoexcited carrier lifetime in a stable and earth-abundant zinc polyphosphide

Halide perovskites have revolutionized optoelectronics by demonstrating that long carrier lifetime can be achieved in materials processed in relatively uncontrolled environments, whereas conventional inorganic semiconductors typically suffer from short carrier lifetime unless very carefully prepared and postprocessed. Here, we report the discovery of exceptionally long photoexcited carrier lifetime in monoclinic ZnP2, effectively bridging the carrier lifetime gap between direct-gap inorganic semiconductors and halide perovskites. Through computational screening, ZnP2 is identified as a long carrier lifetime semiconductor characterized by an unconventional polyphosphide bonding, combining covalently bonded phosphorus chains and polar-covalent Zn-P tetrahedra. Experimentally, ZnP2 crystals synthesized from low-purity precursors exhibit bright band-to-band photoluminescence at 1.49 eV and carrier lifetimes of up to 1 $\mu$s. Further analysis reveals that the polyphosphide bonding of ZnP2 suppresses the formation of deep intrinsic defects, making it defect resistant. Combined with its remarkable environmental stability, ZnP2 presents a highly promising material for solar absorbers and light emitters. Our work illustrates that underexplored inorganic materials spaces with unusual chemical bonding hold great promise for discovering novel optoelectronic materials.

cond-mat.mtrl-sci

Thin-Film Stabilization and Magnetism of {\eta}-Carbide Type Iron Nitrides

Transition-metal nitrides in {\eta}-carbide type structures exhibit unusual bonding motifs and proximity to magnetic instabilities. Yet they remain unexplored in thin-film form due to the difficulty of stabilizing nitrogen-poor ternaries among competing phases. Here, we report the thin-film synthesis and phase-stability mapping of the {\eta}-nitride systems Fe-W-N and Fe-Mo-N. Amorphous Fe-M-N (M = W, Mo) combinatorial libraries deposited by reactive co-sputtering crystallize upon rapid thermal annealing, enabling systematic identification of synthesis windows as a function of composition and annealing temperature. Using laboratory powder X-ray diffraction and synchrotron grazing incidence wide angle X-ray scattering, we establish that Fe3Mo3N-based {\eta}-carbide phases form over a substantially broader compositional and thermal range than W-based compositions, where {\eta} structures are stabilized only when the films are Fe-rich. These trends are rationalized using mixed chemical-potential vs. composition phase diagrams that capture the narrow nitrogen chemical-potential stability of {\eta}-nitrides. Magnetic measurements reveal that ferromagnetism is induced in Fe-rich Fe3.54Mo2.46N with a small exchange-bias-like response that is absent in Fe3W3N-based compositions, highlighting the sensitivity of magnetic behavior to modest deviations from stoichiometry. This work establishes practical thin-film synthesis routes for {\eta}-nitride materials and demonstrates how composition can be tuned to access emergent magnetic phenomena in these complex nitrides.

cond-mat.mtrl-sci

Epitaxial growth and semiconductor properties of NiGa2O4 spinel for Ga2O3/NiO interfaces

Unintentionally formed interfacial layers are ubiquitous in semiconductor devices that operate at extreme conditions. However, these layers' structure and properties often remain unknown due to the thinness of these naturally formed interphases. Here, we report on the intentional epitaxial growth and semiconductor properties of NiGa2O4 spinel layers that form at Ga2O3/NiO interfaces used in high-power and high-temperature electronic devices. Cubic spinel NiGa2O4 films of 10-50 nm thicknesses and low surface roughness (~ 2 nm) were grown using pulsed laser deposition at a substrate temperatures in the 300-900 {\deg}C range on {\alpha}-Al2O3 and {\beta}-Ga2O3 substrates of different orientation. The optical absorption onset (3.6-3.9 eV) and thermal conductivity (4-9 W m-1 K-1) vary systematically with substrate temperature, consistent with theoretical predictions of varying Ni and Ga cation ordering on the spinel lattice. The valence band offset between NiGa2O4 and {\beta}-Ga2O3 is determined to be 1.8 eV. The NiGa2O4-based p-n heterojunction devices on Ga2O3 (001) substrates exhibit a rectification ratio of 10^8 (for +/-2V) and a turn-on voltage of 1.4 V, maintaining diode behavior up to 600 {\deg}C. These results highlight the potential of NiGa2O4 as a p-type interlayer in Ga2O3-based devices and shows a new approach to investigate such interfacial layers.

cond-mat.mtrl-sci

Towards a deeper fundamental understanding of (Al,Sc)N ferroelectric nitrides

Density Functional Theory (DFT) calculations, within the virtual crystal alloy approximation, are performed, along with the development of a Landau-type model employing a symmetry-allowed analytical expression of the internal energy and having parameters being determined from first principles, to investigate properties and energetics of Al1-xScxN ferroelectric nitrides in their hexagonal forms. These DFT computations and this model predict the existence of two different types of minima, namely the 4-fold-coordinated wurtzite (WZ) polar structure and a 5-times paraelectric hexagonal phase (to be denoted as H5), for any Sc composition up to 40%. The H5 minimum progressively becomes the lowest energy state within hexagonal symmetry as the Sc concentration increases from 0 to 40%. Furthermore, the model points out to several key findings. Examples include the crucial role of the coupling between polarization and strains to create the WZ minimum, in addition to polar and elastic energies, and that the origin of the H5 state overcoming the WZ phase as the global minimum within hexagonal symmetry when increasing the Sc composition mostly lies in the compositional dependency of only two parameters, one linked to the polarization and another one being purely elastic in nature. Other examples are that forcing Al1-xScxN systems to have no or a weak change in lattice parameters when heating them allows to reproduce well their finite-temperature polar properties, and that a value of the axial ratio close to that of the ideal WZ structure does imply a large polarization at low temperatures but not necessarily at high temperatures because of the ordered-disordered character of the temperature-induced formation of the WZ state. Such findings should allow for a better fundamental understanding of (Al,Sc)N ferroelectric nitrides, which may be used to design efficient devices operating at low voltages.

cond-mat.mtrl-sci

Emerging ultra-wide band gap semiconductors for future high-frequency electronics

To meet the growing demands of advanced electronic systems, next-generation power and RF semiconductor devices must operate efficiently at higher power levels and switching frequencies while remaining compact. Current state-of-the-art GaN semiconductor devices alone cannot meet all these demands. Emerging ultra-wide band gap (UWBG) alternatives like diamond, BN, AlN, and Ga2O3, face significant challenges including limited wafer availability, doping difficulties, and thermal management constraints. Herein we conduct a high-throughput computational screening for new semiconductors for high-frequency electronics. In our analysis we compute the modeled Johnson and Baliga high-frequency figures of merit in combination with thermal conductivity to assess their potential for RF and power devices. We show that there are plenty of alternative materials to explore and conclude by discussing dopability and synthesis of select candidate materials. This study lays the foundation for discovering new semiconductors that can push the boundaries of performance in applications ranging from EV chargers and solid-state transformers to sub-THz communications and advanced radar technologies.

cond-mat.mtrl-sci

Structural stability, elemental ordering, and transport properties of layered ScTaN2

Some ternary TM nitrides are predicted to adopt layered structures that make them interesting for thermoelectric conversion and quantum materials applications. Synthesis of TM ternary nitride films by physical vapor deposition often favors disordered 3D structures rather than the predicted 2D-like layered structure. In this study, we investigate the structural interplay in the Sc-Ta-N material system, focusing on ScTaN2. We use a two-step combinatorial approach to deposit Sc-Ta-N films by RF co-sputtering and then process the resulting 3D-structured precursor with RTA. Synchrotron GIWAXS on films annealed at 1200 {\deg}C for 20 min reveals the nucleation of the layered structure (P63/mmc) within a composition window of x = Sc/(Sc+Ta) = 0.2-0.5. We estimate the long-range order parameter in stoichiometric ScTaN2 films to be 0.86, corresponding to a fraction of antisites of 7%. Interestingly, we find that the structure can accommodate large off-stoichiometry in the Ta-rich region (x < 0.5), facilitated by making an alloy with the nearly isostructural Ta5N6 compound that exists on a composition tie-line. Transport measurements on ScTaN2 reveal a nearly temperature-independent high carrier density (1021 cm-3), suggesting a heavily doped semiconductor or semimetallic character. The carrier mobility is relatively small (9.5 cm2V-1s-1 at 2 K) and the residual-resistivity ratio is small, suggesting that electrical conduction is dominated by defects or disorder. Measured magnetoresistance is indicative of weak antilocalization at low temperatures. We highlight the interplay between ScTaN2 and Ta5N6 in stabilizing layered structures, emphasizes the importance of cation order/disorder for potential tunable alloys, and suggests that ScTaN2 is promising platform for exploring electronic properties in a tie line of stoichiometry.

cond-mat.mtrl-sci

Stability, growth, and doping of In$_{2}$(Si, Ge)$_{2}$O$_{7}$ as promising n-type wide-gap semiconductors

In this paper we investigate, computationally and experimentally, the phase stability, electronic structure properties, and the propensity for n-type doping of In$_{2}$X$_{2}$O$_{7}$ (X=Si, Ge) ternary oxides. This family of materials contains promising novel wide-gap semiconductors based on their estimated high $n$-type Baliga figures of merit and acceptable thermal conductivity for power electronics applications. Here, we find that both In$_{2}$Si$_{2}$O$_{7}$ and In$_{2}$Ge$_{2}$O$_{7}$ to be n-type dopable, with Zr providing between 10$^{16}$ and above 10$^{21}$ cm$^{-3}$ net donor concentrations under O-poor conditions, depending on the chemistry, structure (ground-state thorvetite or high-pressure pyrochlore) and synthesis temperature. Initial thin-film growth and annealing leads to polycrystalline In$_{2}$Ge$_{2}$O$_{7}$ thin films in thorvetite structure with band gap over 4 eV, and confirms Zr doping predictions by achieving electron concentrations at 10$^{14}$-10$^{16}$ cm$^{-3}$ under O-rich condition. While future epitaxial growth development is still needed, this study establishes In$_{2}$X$_{2}$O$_{7}$ as promising n-type wide-gap semiconductors for power electronic applications.

cond-mat.mtrl-sci

A Map of the Zintl AM2Pn2 Compounds: Influence of Chemistry on Stability and Electronic Structure

The AM2Pn2 (A= Ca, Sr, Ba, Yb, Mg; M= Mn, Zn, Cd, Mg; and Pn=N, P, As, Sb, Bi) family of Zintl phases has been known as thermoelectric materials and has recently gained much attention for highly promising materials for solar absorbers in single junction and tandem solar cells. In this paper we will, from first-principles, explore the entire family of AM2Pn2 compounds in terms of their ground state structure, thermodynamic stability, and electronic structure. We also perform photoluminescence spectroscopy on bulk powder and thin film samples to verify our results, including the first measurements of the bandgaps of SrCd2P2 and CaCd2P2. The AM2Pn2 compounds exhibit broad stability, are mostly isostructural in the CaAl2Si2-type structure (P3m1), and cover a wide range of bandgaps from 0 to beyond 3 eV. This could make them useful for a variety of purposes, for which we propose several candidates, such as CaZn2N2 for tandem top cell solar absorbers and SrCd2Sb2 and CaZn2Sb2 for infrared detectors. By examining the band structures of the AM2Pn2, we find that Mg3Sb2 has the most promise as a thermoelectric material due to several off-{\Gamma} valence band pockets which are unique to it among the compositions studied here.

cond-mat.mtrl-sci

Ion exchange synthesizes layered polymorphs of MgZrN$_2$ and MgHfN$_2$, two metastable semiconductors

The synthesis of ternary nitrides is uniquely difficult, in large part because elemental N$_2$ is relatively inert. However, lithium reacts readily with other metals and N$_2$, making Li-M-N the most numerous sub-set of ternary nitrides. Here, we use Li$_2$ZrN$_2$, a ternary with a simple synthesis recipe, as a precursor for ion exchange reactions towards AZrN$_2$ (A = Mg, Fe, Cu, Zn). In situ synchrotron powder X-ray diffraction studies show that Li$^+$ and Mg$^{2+}$ undergo ion exchange topochemically, preserving the layers of octahedral [ZrN$_6$] to yield a metastable layered polymorph of MgZrN$_2$ (spacegroup $R\overline{3}m$) rather than the calculated ground state structure ($I41/amd$). UV-vis measurements show an optical absorption onset near 2.0 eV, consistent with the calculated bandgap for this polymorph. Our experimental attempts to extend this ion exchange method towards FeZrN$_2$, CuZrN$_2$, and ZnZrN$_2$ resulted in decomposition products (A + ZrN + 1/6 N$_2$), an outcome that our computational results explain via the higher metastability of these phases. We successfully extended this ion exchange method to other Li-M-N precursors by synthesizing MgHfN$_2$ from Li$_2$HfN$_2$. In addition to the discovery of metastable $R\overline{3}m$ MgZrN$_2$ and MgHfN$_2$, this work highlights the potential of the 63 unique Li-M-N phases as precursors to synthesize new ternary nitrides.

cond-mat.mtrl-sci

Synthesis pathways to thin films of stable layered nitrides

Controlled synthesis of metastable materials away from equilibrium is of interest in materials chemistry. Thin film deposition methods with rapid condensation of vapor precursors can readily synthesize metastable phases, but often struggle to yield the thermodynamic ground state. Growing thermodynamically-stable structures using kinetically-limited synthesis methods in important for practical applications in electronics and energy conversion. Here, we reveal a synthesis pathway to thermodynamically-stable ordered layered ternary nitride materials, and discuss why disordered metastable intermediate phases tend to form. We show that starting from elemental vapor precursors leads to a 3D long-range disordered MgMoN2 thin film metastable intermediate structure, with a layered short-range order that has a low-energy transformation barrier to the layered 2D-like stable structure. This synthesis approach is extended to ScTaN2, MgWN2 and MgTa2N3, and may lead to the synthesis of other layered nitride thin films with unique semiconducting and quantum properties.

cond-mat.mtrl-sci