Phosphorene is a new family member of two-dimensional materials. We observed strong and highly layer-dependent photoluminescence in few-layer phosphorene (two to five layers). The results confirmed the theoretical prediction that few-layer phosphorene has a direct and layer-sensitive band gap. We also demonstrated that few-layer phosphorene is more sensitive to temperature modulation than graphene and MoS₂ in Raman scattering. The anisotropic Raman response in few-layer phosphorene has enabled us to use an optical method to quickly determine the crystalline orientation without tunneling electron microscopy or scanning tunneling microscopy. Our results provide much needed experimental information about the band structures and exciton nature in few-layer phosphorene.

Monolayer phosphorene provides a unique two-dimensional (2D) platform to investigate the fundamental dynamics of excitons and trions (charged excitons) in reduced dimensions. However, owing to its high instability, unambiguous identification of monolayer phosphorene has been elusive. Consequently, many important fundamental properties, such as exciton dynamics, remain underexplored. We report a rapid, noninvasive, and highly accurate approach based on optical interferometry to determine the layer number of phosphorene, and confirm the results with reliable photoluminescence measurements. Furthermore, we successfully probed the dynamics of excitons and trions in monolayer phosphorene by controlling the photo-carrier injection in a relatively low excitation power range. Based on our measured optical gap and the previously measured electronic energy gap, we determined the exciton binding energy to be ~0.3 eV for the monolayer phosphorene on SiO₂/Si substrate, which agrees well with theoretical predictions. A huge trion binding energy of ~100 meV was first observed in monolayer phosphorene, which is around five times higher than that in transition metal dichalcogenide (TMD) monolayer semiconductor, such as MoS₂. The carrier lifetime of exciton emission in monolayer phosphorene was measured to be ~220 ps, which is comparable to those in other 2D TMD semiconductors. Our results open new avenues for exploring fundamental phenomena and novel optoelectronic applications using monolayer phosphorene.

Thermal quenching, in which light emission experiences a loss with increasing temperature, broadly limits luminescent efficiency at higher temperature in optical materials, such as lighting phosphors^1,2,3 and fluorescent probes^4,5,6. Thermal quenching is commonly caused by the increased activity of phonons that leverages the non-radiative relaxation pathways. Here, we report a kind of heat-favourable phonons existing at the surface of lanthanide-doped upconversion nanomaterials to combat thermal quenching. It favours energy transfer from sensitizers to activators to pump up the intermediate excited-state upconversion process. We identify that the oxygen moiety chelating Yb³⁺ ions, [Yb···O], is the key underpinning this enhancement. We demonstrate an approximately 2,000-fold enhancement in blue emission for 9.7 nm Yb³⁺-Tm³⁺ co-doped nanoparticles at 453 K. This strategy not only provides a powerful solution to illuminate the dark layer of ultra-small upconversion nanoparticles, but also suggests a new pathway to build high-efficiency upconversion systems.