Effect of silicon and oxygen dopants on the stability of hydrogenated amorphous carbon under harsh environmental conditions

Harsh environments pose materials durability challenges across the automotive, aerospace, and manufacturing sectors, and beyond. While amorphous carbon materials have been used as coatings in many environmentally-demanding applications owing to their unique mechanical, electrical, and optical properties, their limited thermal stability and high reactivity in oxidizing environments have impeded their use in many technologies. Silicon- and oxygen-containing hydrogenated amorphous carbon (a-C:H:Si:O) films are promising for several applications because of their higher thermal stability and lower residual stress compared to hydrogenated amorphous carbon (a-C:H). However, an understanding of their superior thermo-oxidative stability compared to a-C:H is lacking, as it has been inhibited by the intrinsic challenge of characterizing an amorphous, multi-component material. Here, we show that introducing silicon and oxygen in a-C:H slightly enhances the thermal stability in vacuum, but tremendously increases the thermo-oxidative stability and the resistance to degradation upon exposure to the harsh conditions of low Earth orbit (LEO). The latter is demonstrated by having mounted samples of a-C:H:Si:O on the exterior of the International Space Station via the Materials International Space Station (MISSE) mission 7b. Exposing lightly-doped a-C:H:Si:O to elevated temperatures under aerobic conditions or to LEO causes carbon volatilization in the near-surface region, producing a silica surface layer that protects the underlying carbon from further removal. These findings provide a novel physically-based understanding of the superior stability of a-C:H:Si:O in harsh environments compared to a-C:H. A silicon- and oxygen-containing hydrogenated amorphous carbon (a-C:H:Si:O) coating was exposed to the harsh conditions of the low Earth orbit (LEO) environment (hyperthermal atomic oxygen, thermal cycling, ultraviolet radiation) aboard the International Space Station. X-ray photoelectron spectroscopy measurements indicated degradation of the near-surface region of a-C:H:Si:O through breakage and subsequent oxidation of carbon-carbon bonds as well as formation of a silica layer (shift of the silicon 2p signal to higher binding energies). [Display omitted]