Crystallize It before It Diffuses: Kinetic Stabilization of Thin-Film Phosphorus-Rich Semiconductor CuP(2)

[Image: see text] Numerous phosphorus-rich metal phosphides containing both P–P bonds and metal–P bonds are known from the solid-state chemistry literature. A method to grow these materials in thin-film form would be desirable, as thin films are required in many applications and they are an ideal platform for high-throughput studies. In addition, the high density and smooth surfaces achievable in thin films are a significant advantage for characterization of transport and optical properties. Despite these benefits, there is hardly any published work on even the simplest binary phosphorus-rich phosphide films. Here, we demonstrate growth of single-phase CuP(2) films by a two-step process involving reactive sputtering of amorphous CuP(2+x) and rapid annealing in an inert atmosphere. At the crystallization temperature, CuP(2) is thermodynamically unstable with respect to Cu(3)P and P(4). However, CuP(2) can be stabilized if the amorphous precursors are mixed on the atomic scale and are sufficiently close to the desired composition (neither too P poor nor too P rich). Fast formation of polycrystalline CuP(2), combined with a short annealing time, makes it possible to bypass the diffusion processes responsible for decomposition. We find that thin-film CuP(2) is a 1.5 eV band gap semiconductor with interesting properties, such as a high optical absorption coefficient (above 10(5) cm(–1)), low thermal conductivity (1.1 W/(K m)), and composition-insensitive electrical conductivity (around 1 S/cm). We anticipate that our processing route can be extended to other phosphorus-rich phosphides that are still awaiting thin-film synthesis and will lead to a more complete understanding of these materials and of their potential applications.