Thermal effects on the Raman phonon of few-layer phosphorene

Two-dimensional phosphorene is a promising channel material for next generation transistor applications due to its superior carrier transport property. Here, we report the influence of thermal effects on the Raman phonon of few-layer phosphorene formed on hafnium-dioxide (HfO₂) high-k dielectric. When annealed at elevated temperatures (up to 200 °C), the phosphorene film was found to exhibit a blue shift in both the out-of-plane (A¹_g) and in-plane (B_2g and A²_g) phonon modes as a result of compressive strain effect. This is attributed to the out-diffusion of hafnium (Hf) atoms from the underlying HfO₂ dielectric, which compresses the phosphorene in both the zigzag and armchair directions. With a further increase in thermal energy beyond 250 °C, strain relaxation within phosphorene eventually took place. When this happens, the phosphorene was unable to retain its intrinsic crystallinity prior to annealing, as evident from the broadening of full-width at half maximum of the Raman phonon. These results provide an important insight into the impact of thermal effects on the structural integrity of phosphorene when integrated with high-k gate dielectric