Laser-induced down-conversion and infrared phosphorescence emissivity of novel ligand-free perovskite nanomaterials

摘要

For the first time, standalone and ligand-free series of novel rare-earth-based perovskite nanomaterials are used as near infrared (NIR) and mid infrared (MIR) emitters. Nano-sized La0.7Sr0.3M0.1Fe0.9O_3; where M = 0, Mn~(2+), Co~(2+) or Ni~(2+) were synthesized using the flash auto-combustion method and characterized using FTIR, FT-Raman, SEM and EDX. Photoluminescence spectra were spontaneously recorded during pumping the samples with 0.5mW of green laser emitting continuously at 532 nm. La_(0.7)Sr_(0.3)FeO_3 (where M = 0) did not result in any infrared emissivity, while intense near and mid infrared down-converted phosphorescence was released from the M-doped samples. The released phosphorescence greatly shifted among the infrared spectral region with changing the doping cation. Ni~(2+)-doped perovskite emitted at the short-wavelength near-infrared region, while Mn~(2+) and Co~(2+)-doped perovskites emitted at the mid-wavelength infrared region. The detected laser-induced spontaneous parametric down-conversion phosphorescence (SPDC) occurred through a two-photon process by emitting two NIR or MIR photons among a cooperative energy transfer between the La3+ cations and the M~(2+) cations. Combining SrFeO_3 ceramic with both a rare earth cation (RE3+) and a transition metal cation (Mn~(2+), Co~(2+) or Ni~(2+)), rather than introducing merely RE3+ cations, greatly improved and controlled the infrared emissivity properties of synthesized perovskites through destroying their crystal symmetry and giving rise to asymmetrical lattice vibration and the nonlinear optical character. The existence of SPDC in theM~(2+)-doped samples verifies their nonlinear character after the absence of this character in La_(0.7)Sr_(0.3)FeO_3. Obtained results verify that, for the first time, perovskite nanomaterials are considered as nonlinear optical crystals with intense infrared emissivity at low pumping power of visible wavelengths, which nominates them for photonic applications and requires further studies regarding their lasing ability as laser active components. Such a single infrared-emitting-perovskite nanomaterial replaced, for the first time, the need for a polymeric ligand, which was a routine approach in such an application. Also, it avoided the complicated synthesis of organic-inorganic hybrids, prevented wide spectral-range emissions usually produced by polymers, facilitated obtaining near-infrared emission spectra within certain limits of wavelengths, and is considered as a new approach for fabricating a standalone perovskite nanomaterial for phosphorescent optoelectronic components and military uses.