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 and metastability, and highlights hundreds of promising new ternary nitride spaces for experimental investigation-from which we experimentally realized 7 new Zn-and Mg-based ternary nitrides. By extracting the mixed metallicity, ionicity, and covalency of solid-state bonding from the DFTcomputed electron density, we reveal the complex interplay between chemistry, composition, and electronic structure in governing large-scale stability trends in ternary nitride materials.

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 MgxTM1-xN (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 absorption onsets (1.8-2.1 eV). Lattice parameters are compatible with growth on a variety of substrates, and epitaxially grown MgZrN2 exhibits remarkable electron mobilities approaching 100 cm 2 V -1 s -1 . Ab initio calculations reveal that these compounds have disorder-tunable optical properties, large dielectric constants and low carrier effective masses that are insensitive to disorder. Overall, these experimental and theoretical results highlight MgG-3TMNG-2 rocksalts as a new class of semiconductor materials with promising properties for optoelectronic applications.

Nitride materials feature strong chemical bonding character that leads to unique crystal structures, but many ternary nitride chemical spaces remain experimentally unexplored. The search for previously undiscovered ternary nitrides is also an opportunity to explore unique materials properties, such as transitions between cation-ordered and -disordered structures, as well as to identify candidate materials for optoelectronic applications. Here, we present a comprehensive experimental study of MgSnN2, an emerging II–IV–N2 compound, for the first time mapping phase composition and crystal structure, and examining its optoelectronic properties computationally and experimentally. We demonstrate combinatorial cosputtering of cation-disordered, wurtzite-type MgSnN2 across a range of cation compositions and temperatures, as well as the unexpected formation of a secondary, rocksalt-type phase of MgSnN2 at Mg-rich compositions and low temperatures. A computational structure search shows that the rocksalt-type phase is substantially metastable (>70 meV/atom) compared to the wurtzite-type ground state. Spectroscopic ellipsometry reveals optical absorption onsets around 2 eV, consistent with band gap tuning via cation disorder. Finally, we demonstrate epitaxial growth of a mixed wurtzite-rocksalt MgSnN2 on GaN, highlighting an opportunity for polymorphic control via epitaxy. Collectively, these findings lay the groundwork for further exploration of MgSnN2 as a model ternary nitride, with controlled polymorphism, and for device applications, enabled by control of optoelectronic properties via cation ordering.

The compounds ([SnSe]1+δ) m (NbSe2)1, where 1 ≤ m ≤ 10, were prepared from a series of designed precursors. The c-axis lattice parameter systematically increases by 0.577(5) nm as the value of m is increased, which indicates that an additional bilayer of rock salt structured SnSe is inserted for each unit of m. The in-plane structure of both constituents systematically changes as the thickness of SnSe increases. Both X-ray diffraction and electron microscopy studies show the presence of turbostratic disorder between the different constituent layers. The electrical resistivity and Hall coefficient increase systematically as a function of m stronger than would be expected for noninteracting metallic NbSe2 and semiconducting SnSe layers, suggesting the presence of charge transfer between the layers. The temperature dependence of the resistivity changes from metallic behavior for m < 4 to weakly increasing, for higher m, as temperature decreases. Compounds with m > 3 show an upturn in the resistivity below 50 K and a corresponding increase in the Hall coefficient, which both become more pronounced as m increases. This suggests localization of carriers, which is expected in two-dimensional crystals. The extent of charge transfer in ([SnSe]1+δ) m (NbSe2)1 can be tuned as a function of SnSe thickness and spans over the same range as reported in the literature for various NbX2 based intercalated and misfit layer compounds.

A basic summary of thermoelectric principles is presented in a historical context, following the evolution of the field from initial discovery to modern day high-zT materials. A specific focus is placed on nanocomposite materials as a means to solve the challenges presented by the contradictory material requirements necessary for efficient thermal energy harvest. Misfit layer compounds are highlighted as an example of a highly ordered anisotropic nanocomposite system. Their layered structure provides the opportunity to use multiple constituents for improved thermoelectric performance, through both enhanced phonon scattering at interfaces and through electronic interactions between the constituents. Recently, a class of metastable, turbostratically-disordered misfit layer compounds has been synthesized using a kinetically controlled approach with low reaction temperatures. The kinetically stabilized structures can be prepared with a variety of constituent ratios and layering schemes, providing an avenue to systematically understand structure-function relationships not possible in the thermodynamic compounds. We summarize the work that has been done to date on these materials. The observed turbostratic disorder has been shown to result in extremely low cross plane thermal conductivity and in plane thermal conductivities that are also very small, suggesting the structural motif could be attractive as thermoelectric materials if the power factor could be improved. The first 10 compounds in the [(PbSe)1+δ]m(TiSe2)n family (m, n ≤ 3) are reported as a case study. As n increases, the magnitude of the Seebeck coefficient is significantly increased without a simultaneous decrease in the in-plane electrical conductivity, resulting in an improved thermoelectric power factor.

Multivalent ternary nitride materials, which combine two metal cations with a nitrogen anion in equal amounts and charge balanced stoichiometry, tend to have relatively simple structures and promising properties for a broad range of applications. Historically, discovery of such new nitrides has been a bulk synthesis endeavor, following chemical intuition. In the past decade experimental synthesis of theoretically predicted materials, including as thin films, has changed this approach. In this perspective, we discuss progress in the experimental synthesis of theoretically predicted multivalent ternary nitrides, with the focus on Zn-and Mg-based materials. First-principles theoretical calculations predicted structures and properties of many new Zn−M−N and Mg−M−N materials and offered insights into the effects of cation ordering. Thin film and bulk experiments were used to synthesize some of these predicted multivalent ternary nitride compounds such as Zn 3 MoN 4 , Zn 2 SbN 3 , and Zn 2 NbN 3 , as well as MgZrN 2 , Mg 2 NbN 3 , and Mg 2 SbN 3 , and many others. These multivalent ternary nitride success stories should inspire experimental synthesis of other underexplored materials predicted by theoretical calculations.

Combinatorial experiments involve synthesis of sample libraries with lateral composition gradients requiring spatially-resolved characterization of structure and properties.Due to maturation of combinatorial methods and their successful application in many fields, the modern combinatorial laboratory produces diverse and complex data sets requiring advanced analysis and visualization techniques. In order to utilize these large arXiv:1904.07989v2 [cond-mat.mtrl-sci] 30 Apr 2019 data sets to uncover new knowledge, the combinatorial scientist must engage in data science. For data science tasks, most laboratories adopt common-purpose data management and visualization software. However, processing and cross-correlating data from various measurement tools is no small task for such generic programs. Here we describe COMBIgor, a purpose-built open-source software package written in the commercial Igor Pro environment, designed to offer a systematic approach to loading, storing, processing, and visualizing combinatorial data sets. It includes (1) methods for loading and storing data sets from combinatorial libraries, (2) routines for streamlined data processing, and (3) data analysis and visualization features to construct figures. Most importantly, COMBIgor is designed to be easily customized by a laboratory, group, or individual in order to integrate additional instruments and data-processing algorithms.Utilizing the capabilities of COMBIgor can significantly reduce the burden of data management on the combinatorial scientist.

Atomic layer deposited (ALD) high-dielectric-constant (high-k) materials have found extensive applications in a variety of electronic, optical, optoelectronic, and photovoltaic devices. While electrical, optical, and interfacial properties have been the primary consideration for such devices, thermal and mechanical properties are becoming an additional key consideration for many new and emerging applications of ALD high-k materials in electromechanical, energy storage, and organic light emitting diode devices. Unfortunately, a clear correspondence between thermal/mechanical and electrical/optical properties in ALD high-k materials has yet to be established, and a detailed comparison to conventional silicon-based dielectrics to facilitate optimal material selection is also lacking. In this regard, we have conducted a comprehensive investigation and review of the thermal, mechanical, electrical, optical, and structural properties for a series of prevalent and emerging ALD high-k materials including aluminum oxide (Al 2 O 3 ), aluminum nitride (AlN), hafnium oxide (HfO 2 ), and beryllium oxide (BeO). For comparison, more established silicon-based dielectrics were also examined, including thermally grown silicon dioxide (SiO 2 ) and plasma-enhanced chemically vapor deposited hydrogenated silicon nitride (SiN:H). We find that in addition to exhibiting high values of dielectric permittivity and electrical resistance that exceed those of SiO 2 and SiN:H, the ALD high-k materials exhibit equally exceptional thermal and mechanical properties with coefficients of thermal expansion ≤ 6 × 10 -6 / • C, thermal conductivites (κ) of 3-15 W/m K, and Young's modulus and hardness values exceeding 200 and 25 GPa, respectively. In many cases, the observed extreme thermal/mechanical properties correlate with the presence of crystallinity in the ALD high-k films. In contrast, some of the electrical and optical properties correlate more strongly with the percentage of ionic vs. covalent bonds present in the high-k film. Overall, the ALD high-k dielectrics investigated concurrently exhibit compelling thermal/mechanical and electrical/optical properties. The drive to reduce gate leakage currents in highly scaled complementary metal-oxide-semiconductor (CMOS) transistors has led to the exploration and development of a wide variety of high-dielectricconstant (high-k) materials to replace silicon dioxide (SiO 2 ) as the insulating gate dielectric material.1-8 Many of these same high-k materials have found additional applications in future non-CMOS logic and memory storage products such as solid-state electrolytes in resistive switching devices, 9,10 tunnel barriers in spin-transport devices, 11 and as a ferroelectric in magnetoelectric devices. While electrical, physical, and thermodynamic properties have clearly been a key consideration in all of the above applications, thermal properties have become an additional important consideration for higk-k dielectrics as aggressive dimensional scaling of devices has created the need to dissipate ...