In situ reactivation of low-temperature thermionic electron emission from nitrogen doped diamond films by hydrogen exposure

Abstract

Nitrogen doped, hydrogen terminated diamond films have shown a work function of less than 1.5eV and thermionic electron emission (TE) has been detected at temperatures less than 500°C. However, ambient exposure or extended operation leads to a deterioration of the emission properties. In this study thermionic electron emission has been evaluated for as-received surfaces and for surfaces after 18months of ambient exposure. The initial TE current density of the freshly deposited diamond film was ~5×10−5A/cm2 at 500°C. In contrast, the initial TE current density of a film aged for 18months was ~1.8×10−9A/cm2 at 500°C. The decreased emission current density is presumed to be a consequence of oxidation, surface adsorption of contaminants and hydrogen depletion from the surface layer. In situ reactivation of the aged film surface was achieved by introducing hydrogen at a pressure of 1.3×10−4mbar and using a hot filament of a nearby ionization gauge to generate atomic and/or excited molecular hydrogen. After 2h of exposure with the sample at 500°C, the surface exhibited a stable emission current density of ~2.3×10−6A/cm2 (an increase by a factor of ~1300). To elucidate the reactivation process thermionic electron energy distribution (TEED) and XPS core level spectra were measured during in situ hydrogen exposure at 5×10−8mbar. During the isothermal exposure it was determined that atomic or excited hydrogen resulted in a much greater increase of the TE in comparison to exposure to molecular hydrogen. During exposure at 400°C the surface oxygen was substantially reduced, the TEED cut-off energy, which indicates the effective work function, decreased by ~200meV, and the TE intensity increased by a factor of ~100. The increase in thermionic emission with hydrogen was ascribed to the reactivation of the surface through the formation of a uniform surface dipole layer and a reduction of the surface work function.