Flux Growth of Phosphide and Arsenide Crystals

Flux crystal growth has been widely applied to explore new phases and grow crystals of emerging materials. To accommodate the needs of high-quality single crystals, the flux crystal growth should be reliable, controllable, and predictable. The selections of suitable flux and growth conditions remain empirical due to the lack of systematic investigation especially for reactions, which involve highly volatile components, such as P and As. Considering the flux elements, often the system in question is a quaternary or a higher multinary system, which drastically increases complexity. In this manuscript, on the examples of flux growth of phosphides and arsenides, guidelines of flux selections, existing challenges, and future directions are discussed. We expect that the field will be further developed by applying in situ techniques and computational modeling of the nucleation and growth kinetics. Additionally, leveraging variables other than temperature, such as applied pressure, will make flux growth a more powerful tool in the future

Noncentrosymmetric Tetrel Pnictides RuSi4P4 and IrSi3P3: Nonlinear Optical Materials with Outstanding Laser Damage Threshold

Noncentrosymmetric (NCS) tetrel pnictides have recently generated interest as nonlinear optical (NLO) materials due to their second harmonic generation (SHG) activity and large laser damage threshold (LDT). Herein nonmetal‐rich silicon phosphides RuSi4P4 and IrSi3P3 are synthesized and characterized. Their crystal structures are reinvestigated using single crystal X‐ray diffraction and 29Si and 31P magic angle spinning NMR. In agreement with previous report RuSi4P4 crystallizes in NCS space group P1, while IrSi3P3 is found to crystallize in NCS space group Cm, in contrast with the previously reported space group C2. A combination of DFT calculations and diffuse reflectance measurements reveals RuSi4P4 and IrSi3P3 to be wide bandgap (Eg) semiconductors, Eg = 1.9 and 1.8 eV, respectively. RuSi4P4 and IrSi3P3 outperform the current state‐of‐the‐art infrared SHG material, AgGaS2, both in SHG activity and laser inducer damage threshold. Due to the combination of high thermal stabilities (up to 1373 K), wide bandgaps (≈2 eV), NCS crystal structures, strong SHG responses, and large LDT values, RuSi4P4 and IrSi3P3 are promising candidates for longer wavelength NLO materials

Discovery of the Zintl-phosphide BaCd2_{2}P2_{2} as a long carrier lifetime and stable solar absorber

Thin-film photovoltaics offers a path to significantly decarbonize our energy production. Unfortunately, current materials commercialized or under development as thin-film solar cell absorbers are far from optimal as they show either low power conversion efficiency or issues with earth-abundance and stability. Entirely new and disruptive materials platforms are rarely discovered as the search for new solar absorbers is traditionally slow and serendipitous. Here, we use first principles high-throughput screening to accelerate this process. We identify new solar absorbers among known inorganic compounds using considerations on band gap, carrier transport, optical absorption but also on intrinsic defects which can strongly limit the carrier lifetime and ultimately the solar cell efficiency. Screening about 40,000 materials, we discover the Zintl-phosphide BaCd$_{2}$P$_{2}$ as a potential high-efficiency solar absorber. Follow-up experimental work confirms the predicted promises of BaCd$_{2}$P$_{2}$ highlighting an optimal band gap for visible absorption, bright photoluminescence, and long carrier lifetime of up to 30 ns even for unoptimized powder samples. Importantly, BaCd$_{2}$P$_{2}$ does not contain any critical elements and is highly stable in air and water. Our work opens an avenue for a new family of stable, earth-abundant, high-performance Zintl-based solar absorbers. It also demonstrates how recent advances in first principles computation can accelerate the search of photovoltaic materials by combining high-throughput screening with experiment

Intermetallic Nanocatalysts from Heterobimetallic Group 10–14 Pyridine-2-thiolate Precursors

Intermetallic compounds are atomically ordered inorganic materials containing two or more transition metals and main-group elements in unique crystal structures. Intermetallics based on group 10 and group 14 metals have shown enhanced activity, selectivity, and durability in comparison to simple metals and alloys in many catalytic reactions. While high-temperature solid-state methods to prepare intermetallic compounds exist, softer synthetic methods can provide key advantages, such as enabling the preparation of metastable phases or of smaller particles with increased surface areas for catalysis. Here, we study a generalized family of heterobimetallic precursors to binary intermetallics, each containing a group 10 metal and a group 14 tetrel bonded together and supported by pincer-like pyridine-2-thiolate ligands. Upon thermal decomposition, these heterobimetallic complexes form 10–14 binary intermetallic nanocrystals. Experiments and density functional theory (DFT) computations help in better understanding the reactivity of these precursors toward the synthesis of specific intermetallic binary phases. Using Pd2Sn as an example, we demonstrate that nanoparticles made in this way can act as uniquely selective catalysts for the reduction of nitroarenes to azoxyarenes, which highlights the utility of the intermetallics made by our method. Employing heterobimetallic pincer complexes as precursors toward binary nanocrystals and other metal-rich intermetallics provides opportunities to explore the fundamental chemistry and applications of these materials

Exploratory synthesis of extended covalent pnictide frameworks

Pnictogens (phosphorus and arsenic in particular) are very flexible with respect to their bonding capabilities, forming binary compounds with a majority of the periodic table, and exhibiting a variety of bonding coordination. Consequently, pnictogen-based materials exhibit the full scale of structural dimensionalities from molecular clusters (0D) to isolated chains (1D), layers (2D), and finally, extended 3 dimensional (3D) networks. The variety of structural dimensionalities and physical properties these compounds exhibit encourage the pursuit of new compounds via exploratory synthesis. Utilizing advanced synthetic methods such as flux synthesis to obtain crystal for structural analysis and in-situ powder X-ray diffraction to optimize the synthetic parameters, has unveiled several novel pnictide materials with extended covalent networks. Subsequently, the properties of these materials have been studied both theoretically and experimentally

Flux Growth of Phosphide and Arsenide Crystals

Flux crystal growth has been widely applied to explore new phases and grow crystals of emerging materials. To accommodate the needs of high-quality single crystals, the flux crystal growth should be reliable, controllable, and predictable. The selections of suitable flux and growth conditions remain empirical due to the lack of systematic investigation especially for reactions, which involve highly volatile components, such as P and As. Considering the flux elements, often the system in question is a quaternary or a higher multinary system, which drastically increases complexity. In this manuscript, on the examples of flux growth of phosphides and arsenides, guidelines of flux selections, existing challenges, and future directions are discussed. We expect that the field will be further developed by applying in situ techniques and computational modeling of the nucleation and growth kinetics. Additionally, leveraging variables other than temperature, such as applied pressure, will make flux growth a more powerful tool in the future.</p

Unprecedented superstructure in the type I family of clathrates.

The first arsenic-based clathrate exhibiting superstructural ordering due to optimization of Au-As, As-As, and Ba-Au bonding is reported. Ba8Au16As30 crystallizes in a unique P21/c monoclinic clathrate structure. The synthesis, crystal and electronic structure, and transport properties are discussed

Clathrate XI K 58 Zn 122 Sb 207 : A New Branch on the Clathrate Family Tree

International audienceChemical bonding preferences to optimize Ba–Au, Au–As, and As–As interactions lead to a new superstructure in type I clathrate Ba 8 Au 16 As 30 , which exhibits ultralow thermal conductivity