Structural refinement and photoluminescence properties of irregular cube-like (Ca_(1_x)Cu_x)TiO_3 microcrystals synthesized by the microwave-hydrothermal method

摘要

In this paper, calcium copper titanate (Ca_(1_x)Cu)x)TiO_3 microcrystals with (x = 0, 0.01 and 0.02) were synthesized by the microwave-hydrothermal method at 140 ℃ for 30 min. These crystals were analyzed by X-ray diffraction (XRD), Rietveld refinement, X-ray absorption near-edge structure spectroscopy (XANES), micro-Raman spectroscopy, field emission scanning electron microscopy (FE-SEM). Its optical properties were investigated by ultraviolet-visible (UV-vis) absorption and photoluminescence (PL) measurements. XRD patterns, Rietveld refinement and micro-Raman spectroscopy indicated that these crystals present a perovskite-type orthorhombic structure. The Rietveld refinement data, micro-Raman and XANES spectra suggested that the substitution of Ca by Cu in A-site promoted a displacement of Ti atoms to off-center symmetric, which leads distortions on the cuboctahedral [CaO_(12)] clusters neighboring and consequently promotes a strain into the CaTiO_3 lattice. FE-SEM images showed that these cube-like microcrystals have an irregular shape due to Ostwald-ripening and self-assembly of plates and cubes in growth process. The defects and distortions into lattice at medium- and short-range on the [CaO_(12)]/[TiO_6] clusters promotes the structural order-disorder responsible by the intense PL properties of these microcrystals. The microcrystals are promising candidates for future applications in optical devices.