Theoretical study of metal borides stability.pdfVIP

a r X i v : c o n d - m a t / 0 6 0 7 6 5 4 v 1 [ c o n d - m a t .s u p r - c o n ] 2 5 J u l 2 0 0 6 Theoretical study of metal borides stability Aleksey N. Kolmogorov and Stefano Curtarolo Department of Mechanical Engineering and Materials Science, Duke University, Durham, NC 27708 (Dated: February 6, 2008) We have recently identified metal-sandwich (MS) crystal structures and shown with ab initio calculations that the MS lithium monoboride phases are favored over the known stoichiometric ones under hydrostatic pressure [Phys. Rev. B 73, 180501(R) (2006)]. According to previous studies synthesized lithium monoboride tends to be boron-deficient, however the mechanism leading to this phenomenon is not fully understood. We propose a simple model that explains the experimentally observed off-stoichiometry and show that compared to such boron-deficient phases the MS-LiB compounds still have lower formation enthalpy under high pressures. We also investigate stability of MS phases for a large class of metal borides. Our ab initio results suggest that MS noble metal borides are less unstable than the corresponding AlB2-type phases but not stable enough to form under equilibrium conditions. 1. INTRODUCTION The interest in the AlB2 family of metal diborides re-emerged after the discovery of superconductivity in MgB2 with a surprisingly high transition temperature of 39 K[1]. Boron p-states have been shown to be key for both stability and superconductivity in these compounds[2, 3, 4]. MgB2 is a unique metal diboride because it has a significant density of boron pσ-states at the Fermi level which give rise to the high Tc super- conductivity, and yet enough of them are filled for the compound to be structurally stable[2, 3, 4]. The effec- tively hole-doped noble- and alkali-metal diborides would have higher pσ density of states (DOS) at EF , but they have been demonstrated to be unstable under normal conditions[4]. The effort to achieve higher Tc has thus primarily fo