Crystallize it before it diffuses: Kinetic stabilization of thin-film phosphorus-rich semiconductor CuP2

Abstract

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, since 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 phosphides. Here, we demonstrate growth of single-phase CuP2 films by a two-step process involving reactive sputtering of amorphous CuP{2+x} and rapid annealing in an inert atmosphere. At the temperature required for crystallization, CuP2 tends to decompose into Cu3P and gaseous phosphorus. However, CuP2 can still be synthesized 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 CuP2, combined with a short annealing time, makes it possible to bypass the diffusion processes responsible for decomposition. We find that thin-film CuP2 is a 1.5 eV band gap semiconductor with interesting properties, such as a high optical absorption coefficient (above 1e5 cm-1), low thermal conductivity (1.1 W/Km), 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 more complete understanding of these materials and of their potential applications.

Indirect Band Gap Semiconductors for Thin-Film Photovoltaics: High-Throughput Calculation of Phonon-Assisted Absorption

“…They had hardly been grown in the thinfilm form until a very recent report of single-phase CuP 2 films in the P2 1 /c structure by reactive sputtering and soft annealing in an inert atmosphere. 64 In a similar spirit, TiS 3 can be classified as a sulfur-rich sulfide due to the presence of both metal−S and S−S bonds. TiS 3 has only been minimally investigated in photoelectrochemical cells and not in the thin-film form.…”