Tuning of Bi3+-related excitation and emission positions through crystal field modulation in the perovskite-structured La2(Znx, Mg1-x)TiO6 (0 ≤ x ≤ 1):Bi3+ solid solution for white LEDs

In the past year, emission-tunable crystals based on the rare-earth (RE) ions as luminescent center have been frequently reported for use in UV and blue converted white LEDs, but so far tuning the non-RE Bi³⁺ related emissions through the crystal field modulation is still not discovered in the perovskite crystals. In this work, we design and report a type of Bi³⁺ doped La₂(Zn_x,Mg_1-x)TiO₆ (0 ≤ x ≤ 1) perovskite solid solutions, which enable showing the tunable Bi³⁺ excitation and emission positions. The XRD results show that gradual substitution of smaller Mg²⁺ ions with larger Zn²⁺ ions can lead to the blue-shifting of X-ray diffraction (XRD) position, revealing the expansion of cell lattice. Together with structural analysis, our refined XRD and time-resolved spectral results reveal that there is only one type of La site available for Bi³⁺ substitution. With this regular crystal lattice change, the crystal field strength around Bi³⁺ ions is found to vary regularly, allowing to realization of the excitation and emission spectral tuning, i.e., the Bi³⁺ excitation and emission positions as the Mg ions are replaced by the Zn ions can tune from 348?nm to 392?nm and from 405?nm to 433?nm, respectively. This Bi³⁺ spectral tuning peak after calculated by the dielectric chemical bond theory features a linear relationship with the crystal field strength and, thus, is ascribed to the crystal field modulation. On basis of the La₂(Zn_0.4,Mg_0.6)TiO₆ blue, SrGa₂S₄:Eu²⁺ green and Y₂O₃:Eu³⁺ red phosphors, a UV converted warm white LED device with desirable color rendering index (CRI) of 78, correlated color temperature (CCT) of 3650 K and good luminous efficacy of 118.13?lm/W, is fabricated. This work provides new insights into using the crystal-field modulation to discover more Bi³⁺ emission-tunable crystals for white LEDs in the future.