High Pressure Induced Local Ordering and Tunable Luminescence of La2Hf2O7:Eu3+ Nanoparticles

High pressure spectroscopy is of immense importance in understanding materials for their high pressure phases, structural phase transitions, designing pressure sensors, etc. With this objective in mind, we have carried out time resolved photoluminescence and Raman spectroscopy on La2Hf2O7:Eu3+ (LHOE) nanoparticles (NPs) under applied high pressure. High pressure Raman spectra of the LHOE NPs suggest enhanced disordering at high pressure and shifting of the most intense F2g Raman band to higher wavenumber. High pressure excitation photoluminescence spectra of the LHOE NPs demonstrate that the O2-→Eu3+ charge transfer band quenches beyond 2.7 GPa whereas much changes could not be oberved from the intra-configurational f-f excitation bands of Eu3+ ion. High pressure emission photoluminescence spectra of the LHOE NPs show gradual lowering of asymetry ratio value, reduced Stark component in magnetic dipole transition, and the disappearance of the 5D0→7F0 transition of Eu3+ ion at high pressure. These observations suggest significant improvement in Eu3+ symmetry. These results are further corroborated with lifetime spectroscopy, which indicates high pressure induced tunneling of Eu3+ ion from La3+ to Hf4+ sites. These changes are visualized by beautiful color tunability of the LHOE NPs from red to orange to yellow and correlated color temperature from 1900 to 2600 K. This work demonstates a new mode of designing optically tunable luminescent nanomaterials and understanding high pressure induced changes in photonic materials.