Zirconium diboride thin films for use in high temperature sensors and MEMS devices

Sensors and MEMS devices operating in high temperature environments require stable thin films with high electrical conductivity for use as electrodes, bond pads, and other components. Metal films are unreliable because of thermodynamically driven morphological instability and agglomeration over long times. Zirconium diboride (ZrB2) is an ultra-high temperature conducting ceramic with a melting point of 3245°C, with low atomic diffusion rates compared to other materials. To evaluate ZrB2 as a high temperature film, 200 nm thick ZrB2 films were synthesized on r-sapphire substrates using e-beam co-evaporation of elemental Zr and B sources. Film stability was characterized after post-deposition thermal treatments from 600-1000°C in both reducing (vacuum) and oxidizing (air) environments. ZrB2 films deposited at room temperature are amorphous, but have short-range order characteristic of ZrB2 bonding. ZrB2 films grown at 600°C are polycrystalline with preferred <0001< texture, whereas at 850°C grains with preferred <10-10< and <10-11< texture become dominant. Negligible grain growth or morphology changes occur after annealing at 850°C for 55 hours in vacuum, and film electrical conductivity remains <105 S/m. Annealing in air, however, leads to ZrB2 film decomposition into ZrO2 and B2O3 phases, the latter of which is volatile. X-ray diffraction indicates that a 50 nm thick hexagonal boron nitride (h-BN) capping layer grown on top of ZrB2 via magnetron sputtering hinders oxidation, but the ZrB2 eventually transforms to ZrO2. These results indicate that ZrB2 films are attractive for potential use in sensors and MEMS devices in high temperature reducing environments, and for short times in oxidizing environments when covered with a h-BN capping layer.