Enhanced Optical Nonlinearity in Bi3+-Doped CePO4 Nanostructures for Optical Limiting Applications

Abstract

Pure and Bi3+-doped CePO4 were synthesized by the simple co-precipitation method. Successful dopant incorporation into the host lattice of orthophosphate without altering the crystalline structure was confirmed by structure analysis, X-ray diffraction, and Raman characterization. Morphological investigation was done using HR-SEM which portrays the co-existence of nanospheres and nanorods in doped CePO4 and only nanospheres in pure CePO4. X-ray photoelectron spectroscopy studies confirm the +3 oxidation state of Ce3+ and Bi3+ with the presence of a trace amount of Ce4+ in the as-prepared nanoparticles. Vibration sample magnetometer studies show weak ferromagnetic behavior of the nanostructures at room temperature. The absorption band in the wavelength range 200–300 nm accounts for 4f–5d electronic transition, and a red shift in the band edge is due to the increase in the band gap with the addition of the dopant. Photoluminescence emission spectra show broad blue-green emission owing to transition of Ce3+ from the excited state to the ground state and also due to oxygen vacancy. The nonlinear optical absorption and optical limiting (OL) behaviors of Bi3+-doped cerium orthophosphate (CePO4) were investigated using an open-aperture (OA) Z-scan technique under an excitation source of 532 nm nanopulsed lasers. The recorded OA transmittance curve reveals a transition from saturable absorption to reverse saturable absorption in pure CePO4 at 2.46 GW/m2, whereas all the doped samples exhibit RSA attributed to 2PA. The increase in the nonlinear absorption (NLA) coefficient with on-axis intensity and the availability of the near resonant energy state due to the Bi3+ dopant ensure the sequential 2PA (1PA + ESA) phenomenon. Compared to pure CePO4, doped nanostructures show improved NLA coefficients due to the availability of the defect state and oxygen vacancies in Bi3+-doped CePO4. Interestingly, a lower OL threshold (OLT) of 0.14 × 10–13 W/m2 is observed in 0.3% Bi3+-doped CePO4. The lower OLT value of Bi3+-doped CePO4 ensures its potential candidature for OL applications in protecting optical sensors and human eyes.