Understanding Antiferromagnetic Coupling in Lead-Free Halide Double Perovskite Semiconductors.

Solution-processable semiconductors with antiferromagnetic (AFM) order are attractive for future spintronics and information storage technology. Halide perovskites containing magnetic ions have emerged as multifunctional materials, demonstrating a cross-link between structural, optical, electrical, and magnetic properties. However, stable optoelectronic halide perovskites that are antiferromagnetic remain sparse, and the critical design rules to optimize magnetic coupling still must be developed. Here, we combine the complementary magnetometry and electron-spin-resonance experiments, together with first-principles calculations to study the antiferromagnetic coupling in stable Cs2(Ag:Na)FeCl6 bulk semiconductor alloys grown by the hydrothermal method. We show the importance of nonmagnetic monovalence ions at the BI site (Na/Ag) in facilitating the superexchange interaction via orbital hybridization, offering the tunability of the Curie-Weiss parameters between -27 and -210 K, with a potential to promote magnetic frustration via alloying the nonmagnetic BI site (Ag:Na ratio). Combining our experimental evidence with first-principles calculations, we draw a cohesive picture of the material design for B-site-ordered antiferromagnetic halide double perovskites.

First-principles demonstration of band filling-induced significant improvement in thermodynamic stability and mechanical properties of Sc[Formula: see text]Ta[Formula: see text]B[Formula: see text] solid solutions.

Mixtures of different metal diborides in the form of solid solutions are promising materials for hard-coating applications. Herein, we study the mixing thermodynamics and the mechanical properties of AlB[Formula: see text]-structured Sc[Formula: see text]Ta[Formula: see text]B[Formula: see text] solid solutions using the first-principles method, based on the density functional theory, and the cluster-expansion formalism. Our thermodynamic investigation reveals that the two diborides readily mix with one another to form a continuous series of stable solid solutions in the pseudo-binary TaB[Formula: see text] [Formula: see text]ScB[Formula: see text] system even at absolute zero. Interestingly, the elastic moduli as well as the hardness of the solid solutions show significant positive deviations from the linear Vegard's rule evaluated between those of ScB[Formula: see text] and TaB[Formula: see text]. In case of Sc[Formula: see text]Ta[Formula: see text]B[Formula: see text], the degrees of deviation from such linear trends can be as large as 25, 20, and 40% for the shear modulus, the Young's modulus, and the hardness, respectively. The improvement in the stability as well as the mechanical properties of Sc[Formula: see text]Ta[Formula: see text]B[Formula: see text] solid solutions relative to their constituent compounds is found to be related to the effect of electronic band filling, induced upon mixing TaB[Formula: see text] with ScB[Formula: see text]. These findings not only demonstrate the prominent role of band filling in enhancing the stability and the mechanical properties of Sc[Formula: see text]Ta[Formula: see text]B[Formula: see text], but also it can potentially open up a possibility for designing stable/metastable metal diboride-based solid solutions with superior and widely tunable mechanical properties for hard-coating applications.