A stable, quasi-2D modification of silver: optical, electronic, vibrational and mechanical properties, and first principles calculations

Abstract

We report the optical, electronic, vibrational and mechanical properties of a stable, anisotropic, hexagonal (4H) form of silver. First principles calculations based on density functional theory were used to simulate the phonon dispersion curves and electronic band structure of 4H-Ag. The phonon dispersion data at 0 K do not contain unstable phonon modes, thereby confirming that it is a locally stable structure. The Fermi surface of the 4H phase differs in a subtle way from that of the cubic phase. Experimental measurements indicate that, when compared to the commonly known face-centered cubic (3C) form of silver, the 4H-Ag form shows a 130-fold higher, strongly anisotropic, in-plane resistivity and a much lower optical reflectance with a pronounced surface plasmon contribution that imparts a distinctive golden hue to the material. Unlike common silver, the lower symmetry of the 4H-Ag structure allows it to be Raman active. Mechanically, 4H-Ag is harder, more brittle and less malleable. Overall, this novel, poorly metallic, anisotropic, darker and harder crystallographic modification of silver bears little resemblance to its conventional counterpart.