Ternary nitride materials hold promise for many optical, electronic, and refractory applications yet their preparation via solid-state synthesis remains challenging. Often, high pressures or reactive gasses are used to manipulate the effective chemical potential of nitrogen, yet these strategies require specialized equipment. Here we report on a simple two-step synthesis using ion-exchange reactions that yield rocksalt-derived MgZrN$_2$ and Mg$_2$NbN$_3$, as well as layered MgMoN$_2$. All three compounds show nearly temperature-independent and weak paramagnetic responses to an applied magnetic field at cryogenic temperatures indicating phase pure products. The key to synthesizing these ternary materials is an initial low-temperature step (300-450 $^{\circ}$C) to promote Mg-M-N bond formation. Then the products are annealed (800-900 $^{\circ}$C) to increase crystalline domains of the ternary product. Calorimetry experiments reveal that initial reaction temperatures are determined by phase transitions of reaction precursors, whereas heating directly to high temperatures results in decomposition. These two-step reactions provide a rational guide to material discovery of other bulk ternary nitrides.
Exploratory synthesis in novel 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 …
Interest in inorganic ternary nitride materials has grown rapidly over the past few decades, as their diversity of chemistries and structures make them appealing for a variety of applications. Due to synthetic challenges posed by the stability of N2, the number of predicted nitride compounds dwarfs those that have been synthesized, offering a breadth of opportunity for exploration. This review summarizes the fundamental properties and structural chemistry of ternary nitrides, leveraging metastability and the impact of nitrogen chemical potential. A discussion of prevalent defects, both detrime…
Binary III-N nitride semiconductors with wurtzite crystal structure such as GaN and AlN have been long used in many practical applications ranging from optoelectronic to telecommunication. The structurally related ZnGeN2 or ZnSnN2 derived from the parent binary compounds by cation mutation (elemental substitution) have recently attracted attention, but such ternary nitride materials are mostly limited to II-IV-N2 compositions. This paper reports on synthesis and characterization of zinc niobium nitride Zn2NbN3 - a previously unreported II2-V-N3 ternary nitride semiconductor. The Zn2NbN3 thin f…
A density functional theory study of atomic defects and dopants in ternary Z-phase transition-metal nitrides CrMN with M=V, Nb, or Ta is presented. Various defect formation energies of native point defects and of substitutional atoms of other metal elements which are abundant in the steel as well, are evaluated. The dependence thereof on the thermodynamic environment, i.e. the chemical conditions of a growing Z-phase precipitate, is studied and different growth scenarios are compared. The results obtained may help to relate results of experimental atomic-scale analysis, by atom probe tomograph…
We present a thorough theoretical study of ordering phenomena in nitride ternary alloys GaInN, AlInN, and AlGaN. Using the Monte Carlo approach and energetics based on the Keating model we analyze the influence of various factors on ordering in bulk crystals and epitaxial layers. We characterize the degree of both short range order (SRO) and long ranger order (LRO) for different compositions, temperatures and for substrates associated with different epitaxial strain. For the description of the SRO the Warren-Cowley parameters related to the first four coordination shells are used. The LRO is d…
Inorganic nitrides with wurtzite crystal structures are well-known semiconductors used in optoelectronic devices. In contrast, rocksalt-based nitrides are known for their metallic and refractory properties. Breaking this dichotomy, here we report on ternary nitride semiconductors with rocksalt crystal structures, remarkable optoelectronic properties, and the general chemical formula Mg$_{x}$TM$_{1-x}$N (TM=Ti, Zr, Hf, Nb). These compounds form over a broad metal composition range and our experiments show that Mg-rich compositions are nondegenerate semiconductors with visible-range optical abso…
We have investigated the effect of piezoelectric (PZ) polarization property on group velocity of phonons in binary as well as in ternary wurtzite nitrides. It is found that with the presence of PZ polarization property, the phonon group velocity is modified. The change in phonon group velocity due to PZ polarization effect directly depends on piezoelectric tensor value. Using different piezoelectric tensor values recommended by different workers in the literature, percent change in group velocities of phonons has been estimated. The Debye temperatures and frequencies of binary nitrides GaN, Al…
Condensed matter systems contain both fermionic and bosonic quasiparticles. Owing to the constraint imposed by the Fermi level, ideal material candidate for the emergent particles with higher-dimensional degeneracy manifold (i.e., nodal lines and nodal surfaces) has not been found in electronic systems. This paper demonstrates that according to the first-principle calculations and symmetry analysis, realistic ternary nitride Li$_6$WN$_4$ features ideal (nearly flat) nodal-surface and nodal-line structures in its phonon spectra. These nodal degeneracies are shaped like lanterns, and their exist…
Composition-dependent Thin-film Synthesis of Layered Ternary Iron Nitrides FeMN2 (M = W, Mo)
National Laboratory of the Rockies（落基山国家实验室）；Korea Advanced Institute of Science and Technology (KAIST)（韩国科学技术院）；Stanford University（斯坦福大学）；Colorado School of Mines（科罗拉多矿业学院）；Idaho National Laboratory（爱达荷国家实验室）
Computationally guided high-throughput synthesis is used to explore the Zn-V-N phase space, resulting in the synthesis of a novel ternary nitride Zn$_2$VN$_3$. Following a combinatorial PVD screening, we isolate the phase and synthesize polycrystalline Zn$_2$VN$_3$ thin films with wurtzite structure on conventional borosilicate glass substrates. In addition, we demonstrate that cation-disordered, but phase-pure (002)-textured, Zn$_2$VN$_3$ thin films can be grown using epitaxial stabilization on α-Al2O3 (0001) substrates at remarkably low growth temperatures well below 200 °C. The structural p…
Zinc-based nitride CaZn2N2 films grown by molecular beam epitaxy (MBE) with a plasma-assisted active nitrogen-radical source are promising candidates of next-generation semiconductors for light-emitting diodes and solar cells. This nitride compound has previously only been synthesized in a bulk form by ultrahigh-pressure synthesis at 5 GPa. Three key factors have been found to enable heteroepitaxial film growth: (i) precise tuning of the individual flux rates of Ca and Zn, (ii) the use of GaN template layers on sapphire c-plane as substrates, and (iii) the application of MBE with an active N-r…
The 4d-transition-metals carbides (ZrC, NbC) and nitrides (ZrN, NbN) in the rocksalt structure, as well as their ternary alloys, have been recently studied by means of a first-principles full potential linearized augmented plane waves method within the local density approximation. These materials are important because of their interesting mechanical and physical properties, which make them suitable for many technological applications. Here, by using a simple theoretical model, we estimate the bulk moduli of their ternary alloys Zr$_x$Nb$_{1-x}$C and Zr$_x$Nb$_{1-x}$N in terms of the bulk modul…
Rapid decline in fossil fuel energy necessitates the immediate need for renewable energy resources. Here, we report a previously unexplored class of nitrides AMN$_2$ keeping renewable energy applications in mind. Using a detailed structure and stability analysis using first principles simulation, we discovered twelve such compounds (few of which are already synthesized before), which are chemically, mechanically and dynamically stable. These twelve compounds were then evaluated for their suitability for three renewable energy applications, (i) photovoltaics, (ii) water splitting, and (iii) the…
Physical Properties and Thermal Stability of Zirconium Platinum Nitride Thin Films
ETH Zurich（苏黎世联邦理工学院）；Laboratory for Nanometallurgy, Department of Materials, ETH Zurich（苏黎世联邦理工学院材料系纳米冶金实验室）；Ion Beam Physics, Department of Physics, ETH Zurich（苏黎世联邦理工学院物理系离子束物理）
We present a data-centric deep learning (DL) approach using neural networks (NNs) to predict the thermodynamics of ternary solid solutions. We explore how NNs can be trained with a dataset of Gibbs free energies computed from a CALPHAD database to predict ternary systems as a function of composition and temperature. We have chosen the energetics of the FCC solid solution phase in 226 binaries consisting of 23 elements at 11 different temperatures to demonstrate the feasibility. The number of binary data points included in the present study is 102,000. We select six ternaries to augment the bin…
In the present work, ternary Special Quasirandom Structures (SQSs) for a fcc solid solution phase are generated at different compositions, $x_A=x_B=x_C=\tfrac{1}{3}$ and $x_A=\tfrac{1}{2}$, $x_B=x_C=\tfrac{1}{4}$, whose correlation functions are satisfactorily close to those of a random fcc solution. The generated SQSs are used to calculate the mixing enthalpy of the fcc phase in the Ca-Sr-Yb system. It is observed that first-principles calculations of all the binary and ternary SQSs in the Ca-Sr-Yb system exhibit very small local relaxation. It is concluded that the fcc ternary SQSs can provi…
Chemical composition is the primary factor that determines the electronic band structure and thus also influences the optical properties of plasmonic ceramics including nitrides and oxides. In this work, the optical and plasmonic properties of TiN, ZrN and their hypothetical intermediate alloys Ti1-xZrxN (x= 0, 0.25, 0.50, 0.75, and 1), are studied by using first-principles density functional theory. We demonstrate the effects of electronic band structure tuning (band engineering) on the dielectric properties by varying the concentration of metallic constituents. Our calculations reveal that b…
Growing energy storage demands on lithium-ion batteries necessitate exploration of new electrochemical materials as next-generation battery electrode materials. In this work, we investigate the previously unexplored electrochemical properties of earth-abundant and tunable Zn1-xSn1+xN2 (x = -0.4 to x = 0.4) thin films, which show high electrical conductivity and high gravimetric capacity for Li insertion. Enhanced cycling performance is achieved compared to previously published end-members Zn3N2 and Sn3N4, showing decreased irreversible loss and increased total capacity and cycle stability. The…
Effect of molar volume of diffusing elements and cross terms of Onsager formalism (vacancy wind effect) on estimated diffusion coefficients in ternary and multicomponent solid solutions
In this manuscript we study luminescence of hexagonal boron nitride (hBN) by means of non-equilibrium Green's functions plus time-dependent perturbation theory. We derive a formula for light emission in solids in the limit of a weak excitation that includes perturbatively the contribution of electron-phonon coupling at the first order. This formula is applied to study luminescence in bulk hBN. This material has attracted interest due to its strong luminescence in the ultraviolet [Watanabe et al., Nature Mat. 3, 404(2004)]. The origin of this luminescence has been widely discussed, but only rec…
A combination of theoretical calculation and the experimental synthesis to explore the new ternary compound is demonstrated in the Sr-Pt-Bi system. Since Pt-Bi is considered as a new critical charge-transfer pair for superconductivity, it inspired us to investigate the Sr-Pt-Bi system. With a thorough calculation of all the known stable/metastable compounds in the Sr-Pt-Bi system and crystal structure predictions, the thermodynamic stability of hypothetical stoichiometry, SrPtBi2, is determined. Followed by the high-temperature synthesis and crystallographic analysis, the first ternary bismuth…
We are reporting a new synthetic strategy to grow large size black phosphorus (Black-P) crystals through a ternary clathrate Sn$_{24}$P$_{22-x}$I$_8$, under lower synthetic temperature and pressure. The Black-P crystals are found grown in situ at the site where the solid clathrate originally resides, which suggests chemical vapor mineralizer does not play a critical role for the Black-P formation. More detailed systematical studies has indicated the P vacancies in the framework of ternary clathrate Sn$_{24}$P$_{22-x}$I$_8$ is important for the subsequent Black-P from phosphorus vapors, and a l…
Two-dimensional materials have attracted tremendous attention for their fascinating electronic, optical, chemical and mechanical properties. However, the band gaps of most 2D materials reported are smaller than 2.0 eV, which greatly restricted their optoelectronic applications in blue and ultraviolet range of the spectrum. Here, we propose a new stable sulfur nitride (S3N2) 2D crystal that is a covalent network composed solely of S-N σ bonds. S3N2 crystal is dynamically stable as confirmed by the computed phonon spectrum and ab initio molecular dynamics simulations in the NPT ensemble. Hybrid …
The properties of the mixed system LiBH4 LiCl P2S5 are studied with respect to all-solid-state batteries. The studied material undergoes an amorphization upon heating above 601C, accompanied with increased Li+ conductivity beneficial for battery electrolyte applications. The measured ionic conductivity is 10-3 Scm-1 at room temperature with an activation energy of 0.40(2) eV after amorphization. Structural analysis and characterization of the material suggest that BH4 groups and PS4 may belong to the same molecular structure, where Cl ions interplay to accommodate the structural unit. Thanks t…
A two-dimensional (2D) monolayer of a novel ternary nitride Zn2VN3 is computationally designed, and its dynamical and thermal stability is demonstrated. A synthesis strategy is proposed based on experimental works on production of ternary nitride thin films, calculations of formation and exfoliation energies, and ab initio molecular dynamics simulations. A comprehensive characterization of 2D Zn2VN3, including investigation of its optoelectronic and mechanical properties, is conducted. It is shown that 2D Zn2VN3 is a semiconductor with an indirect band gap of 2.75 eV and a high work function o…
The fundamental principles underlying the arrangement of elements into solid compounds with an enormous variety of crystal structures are still largely unknown. This study presents a general overview of the structure types appearing in an important subset of the solid compounds, i.e., binary and ternary compounds of the 6A column oxides, sulfides and selenides. It contains an analysis of these compounds, including the prevalence of various structure types, their symmetry properties, compositions, stoichiometries and unit cell sizes. It is found that these compound families include preferred st…
Nitride hydrides are a largely unexplored class of materials with promising applications in solid-state hydrogen fuel cells. Here, we use first-principles calculations to characterize defects and ionic mobility in Sr$_2$LiH$_2$N (SLHN), a nitride hydride with high hydride conductivity. Calculating defect formation energies, we find that SLHN contains high concentrations of hydrogen interstitials (H$_i$). H$_i^-$ migrates with very low energetic barriers, which, together with its low formation energy, implies that SLHN will have excellent hydride kinetics, potentially surpassing those of other …
Unlike c-plane nitrides, ``non-polar" nitrides grown in e.g. the a-plane or m-plane orientation encounter anisotropic in-plane strain due to the anisotropy in the lattice and thermal mismatch with the substrate or buffer layer. Such anisotropic strain results in a distortion of the wurtzite unit cell and creates difficulty in accurate determination of lattice parameters and solid phase group-III content (x_solid) in ternary alloys. In this paper we show that the lattice distortion is orthorhombic, and outline a relatively simple procedure for measurement of lattice parameters of non-polar grou…
As an aid to the development of hydrogen separation membranes, we predict the temperature dependent phase diagrams using first principles calculations combined with thermodynamic principles. Our method models the phase diagram without empirical fitting parameters. By applying thermodynamic principles and solid solution models, temperature-dependent features of the Cu-Pd-S system can be explained, specifically solubility ranges for substitutions in select crystalline phases. Electronic densities of states calculations explain the relative favorability of certain chemical substitutions. In addit…
Universal effect of ammonia pressure on synthesis of colloidal metal nitrides in molten salts
Pritzker School of Molecular Engineering, University of Chicago（芝加哥大学普里茨克分子工程学院）；Interdisciplinary Materials Science Program, Vanderbilt University（范德堡大学交叉材料科学项目）；Department of Chemistry and James Franck Institute, University of Chicago（芝加哥大学化学系和詹姆斯·弗兰克研究所）；Department of Chemistry, Northwestern University（西北大学化学系）；Center for Nanoscale Materials, Argonne National Laboratory（阿贡国家实验室纳米材料中心）；Department of Chemical and Biomolecular Engineering, Vanderbilt University（范德堡大学化学与生物分子工程系）
Comprehensive Mapping of Tracer Diffusivities Across Composition Space in Ternary NiAlTi and Quinary NiCoFeAlTi High-Entropy Alloy Using Diffusion Couple Experiments and Physics Informed Neural Network Inversion
Transition metal nitrides have received significant interest for use within plasmonic and optoelectronic devices. However, deposition temperature remains a significant barrier to the integration of transition metal nitrides as plasmonic materials within CMOS fabrication processes. Binary, ternary and layered transition metal nitride thin films based on titanium and niobium nitride are deposited using High Power Impulse Magnetron Sputtering (HIPIMS). The increased plasma densities achieved in the HIPIMS process allow high quality plasmonic thin films to be deposited at CMOS compatible temperatu…
The ternary nitride CaZn2N2, composed only of earth-abundant elements, is a novel semiconductor with a band gap of 1.8 eV. First-principles calculations predict that continuous Mg substitution at the Zn site will change the optical band gap in a wide range from ~3.3 eV to ~1.9 eV for Ca(Mg1-xZnx)2N2 (x = 0-1). In this study, we demonstrate that a solid-state reaction at ambient pressure and a high-pressure synthesis at 5 GPa produce x = 0 and 0.12, and x = 0.12-1 polycrystalline samples, respectively. It is experimentally confirmed that the optical band gap can be continuously tuned from ~3.2 …
Are diffusion models ready for materials discovery in unexplored chemical space?
Korea Institute of Science and Technology (KIST)（韩国科学技术院）；Seoul National University（首尔大学）；Korea Institute of Ceramic Engineering and Technology (KICET)（韩国陶瓷工程技术研究院）；Korea Institute of Advanced Study（韩国高等研究院）；University of Science and Technology (UST)（韩国科学技术院）；Kumho Petrochemical（锦湖石化）
Lithium salts with low coordinating anions like bis(trifluoromethanesulfonyl)imide (TFSI) have been the state-of-the-art for PEO-based 'dry' polymer electrolytes for three decades. Plasticizing PEO with TFSI-based ionic liquids (ILs) to form ternary solid polymer electrolytes (TSPEs) increases conductivity and Li$^+$ diffusivity. However, the Li$^+$ transport mechanism is unaffected compared to their 'dry' counterpart and essentially coupled to the dynamics of the polymer host matrix, which limits Li$^+$ transport improvement. Thus, a paradigm shift is hereby suggested: The utilization of more…
Among the wide-bandgap compound semiconductors, gallium nitride is the most widely available material due to its prevalence in the solid state lighting and high-speed/high-power electronics industries. It is now known that GaN is one of only a handful of materials to host color centers that emit quantum light at room temperature. In this paper, we report on a bright color center in a semi-polar gallium nitride substrate, emitting at room temperature in the near-infrared. We show that a hemispherical solid immersion lens, near index matched to the semiconductor, can be used to enhance the photo…
The control over the structural homogeneity is of paramount importance for ternary nitride compounds - the second most important semiconducting material-class after Si, due to its unrivalled applicability in optoelectronics, and high power/high frequency electronics. Therefore it is timely to investigate possible mechanisms influencing the crystallographic constitution of the material. In this work the diffusion mechanism of manganese in gallium nitride is investigated in two types of epilayers: Mn implanted metalorganic vapour phase epitaxy grown GaN and (Ga,Mn)N solid solution grown by molec…
The vibrational excitations of crystalline solids corresponding to acoustic or optic one phonon modes appear as sharp features in measurements such as neutron spectroscopy. In contrast, many-phonon excitations generally produce a complicated, weak, and featureless response. Here we present time-of-flight neutron scattering measurements for the binary solid uranium nitride (UN), showing well-defined, equally-spaced, high energy vibrational modes in addition to the usual phonons. The spectrum is that of a single atom, isotropic quantum harmonic oscillator and characterizes independent motions of…
Spin defects in wide-band gap semiconductors are promising systems for the realization of quantum bits, or qubits, in solid-state environments. To date, defect qubits have only been realized in materials with strong covalent bonds. Here, we introduce a strain-driven scheme to rationally design defect spins in functional ionic crystals, which may operate as potential qubits. In particular, using a combination of state-of-the-art ab-initio calculations based on hybrid density functional and many-body perturbation theory, we predicted that the negatively charged nitrogen vacancy center in piezoel…
Covalent functionalization is a way to tune the electrochemical properties of hexagonal boron nitride (h-BN) monolayers. The wide band gap insulator h-BN may become metallic conductor upon functionalization with strong oxidants, such as fluorosulfonyl radicals ($\cdot$OSO$_2$F), as known since 1978 [N. Bartlett et al., J. Chem. Soc. Chem. Comm. {\bf 5}, 200 (1978)], with electrical conductivity of 1.5 S/cm [C. Shen et al., J. Solid State Chem. {\bf 147}, 74 (1999)] that greatly surpasses commercial cathode material Li$_{x}$CoO$_{2}$ while retaining excellent ionic conductivity. Functionalized …
This paper reports on the growth and characterization of hexagonal boron nitride (hBN) and its use for solid-state thermal neutron detection. The hBN epilayers were grown by metalorganic chemical vapor deposition on sapphire substrates at a temperature of 1350 C. X-ray diffraction peak from the (002) hBN plane at a 2theta angle of 26.7 deg exhibited the c-lattice constant of 6.66 Å for these films. A strong peak corresponding to the high frequency Raman active mode of hBN was found for the films at 1370.5/cm. hBN-based solid-state neutron detectors were fabricated and tested with a metal-semic…
A ternary type-I Si clathrate, K8AlxSi46-x, which is a candidate functional material composed of abundant non-toxic elements, was synthesized and its transport properties were investigated at temperatures ranging from 10 to 320 K. The synthesized compound is confirmed to be the ternary type-I Si clathrate K8Al7Si39 with a lattice parameter of a = 10.442 A using neutron powder diffractometry and inductively coupled plasma optical emission spectrometry. Electrical resistivity and Hall coefficient measurements revealed that K8Al7Si39 is a metal with electrons as the dominant carriers at a density…
Eutectic two-phase cells, also known as eutectic colonies, are commonly observed during the solidification of ternary alloys when the composition is close to a binary eutectic valley. In analogy with the solidification cells formed in dilute binary alloys, colony formation is triggered by a morphological instability of a macroscopically planar eutectic solidification front due to the rejection by both solid phases of a ternary impurity that diffuses in the liquid. Here we develop a phase-field model of a binary eutectic with a dilute ternary impurity and we investigate by dynamical simulations…
Using combination of Density Functional Theory and Monte Carlo simulation, we study the phase stability and electronic properties of two dimensional hexagonal composites of boron nitride and graphene, with a goal to uncover the role of the interface geometry formed between the two. Our study highlights that preferential creation of extended armchair interfaces may facilitate formation of solid solution of boron nitride and graphene within a certain temperature range. We further find that for band-gap engineering, armchair interfaces or patchy interfaces with mixed geometry are most suitable. E…
Friction is one of the main sources of dissipation at liquid water/solid interfaces. Despite recent progress, a detailed understanding of water/solid friction in connection with the structure and energetics of the solid surface is lacking. Here we show for the first time that \textit{ab initio} molecular dynamics can be used to unravel the connection between the structure of nanoscale water and friction for liquid water in contact with graphene and with hexagonal boron nitride. We find that whilst the interface presents a very similar structure between the two sheets, the friction coefficient …
