Tris(phosphino)borato Silver(I) Complexes as Precursors for Metallic Silver Aerosol-Assisted Chemical Vapor Deposition

A series of light- and air-stable tris(phosphino)borato silver(I) complexes has been synthesized, structurally and spectroscopically characterized, and implemented in the growth of low resistivity metallic silver thin films by aerosol-assisted chemical vapor deposition (AACVD). Of the four complexes in the series, [RB(CH<sub>2</sub>PR′<sub>2</sub>)<sub>3</sub>]AgPEt<sub>3</sub> (R = Ph (<b>1</b>, <b>3</b>), <i><sup>n</sup></i>Bu (<b>2</b>, <b>4</b>); R′ = Ph (<b>1</b>, <b>2</b>), <i><sup>i</sup></i>Pr (<b>3</b>, <b>4</b>), complexes <b>1</b> and <b>2</b> have been characterized by single-crystal X-ray diffraction. Complex <b>2</b> represents a significant improvement over previously available nonfluorinated Ag precursors, owing to ease of handling and efficient film deposition characteristics. Thermogravimetric analysis (TGA) shows that the thermolytic properties of these complexes can be significantly modified by altering the ligand structure. Polycrystalline cubic-phase Ag thin films were grown on glass, MgO(100), and 52100 steel substrates. Ag films of thicknesses 3 µm, grown at rates of 14–18 nm/min, exhibit low levels of extraneous element contamination by X-ray photoelectron spectroscopy (XPS). Atomic force microscopy (AFM) and scanning electron microscopy (SEM) indicate that film growth proceeds primarily via an island growth (Volmer–Weber) mechanism.