Organolead halide perovskites have emerged as a promising optoelectronic material for lighting due to its high quantum yield, color-tunable, and narrow emission. Despite their unique properties, toxicity has intensified the search for ecofriendly alternatives through partial or complete replacement of lead. Herein, we report a roomtemperature synthesized Mn 2+ -substituted 3D-organolead perovskite displacing ∼90% of lead, simultaneously retaining its unique excitonic emission, with an additional orange emission of Mn 2+ via energy transfer. A high Mn solubility limit of 90% was attained for the first time in lead halide perovskites, facilitated by the flexible organic cation (CH 3 NH 3 ) + network, preserving the perovskite structure. The emission intensities of the exciton and Mn were influenced by the halide identity that regulates the energy transfer to Mn. Homogeneous emission and electron spin resonance characteristics of Mn 2+ indicate a uniform distribution of Mn. These results suggest that low-toxicity 3D-CH 3 NH 3 Pb 1−x Mn x Br 3−(2x+1) Cl 2x+1 nanocrystals may be exploited as magnetically doped quantum dots with unique optoelectronic properties.

Zero-dimensional (0D) inorganic perovskites have recently emerged as an interesting class of material owing to their intrinsic Pb2+ emission, polaron formation, and large exciton binding energy. They have a unique quantum-confined structure, originating from the complete isolation of octahedra exhibiting single-molecule behavior. Herein, we probe the optical behavior of single-molecule-like isolated octahedra in 0D Cesium lead halide (Cs4PbX6, X = Cl, Br/Cl, Br) nanocrystals through isovalent manganese doping at lead sites. The incorporation of manganese induced phase stabilization of 0D Cs4PbX6 over CsPbX3 by lowering the symmetry of PbX6 via enhanced octahedral distortion. This approach enables the synthesis of CsPbX3 free Cs4PbX6 nanocrystals. A high photoluminescence quantum yield for manganese emission was obtained in colloidal (29%) and solid (21%, powder) forms. These performances can be attributed to structure-induced confinement effects, which enhance the energy transfer from localized host exciton states to Mn2+ dopant within the isolated octahedra.

A series of britholite compounds were synthesized by simultaneous introduction of trivalent La and Si ions into an apatite structure. The variations in the average structure, electronic band structure, and microstructural properties resulting from the introduction of cation pairs were analyzed as a function of their concentration. The effects of the structural variance and microstructural properties on the broad-band-emitting activator ions were studied by introducing Eu ions as activators. For the resulting compound, which had dual emission bands in the blue and yellow regions of the spectrum, the emission peak position and strength were dependent upon the concentration of La-Si pairs. By engineering the relative sizes of the two possible activator sites in the structure, 4f and 6h, through the introduction of a combination of trivalent La and a polyanion, the preferential site occupancy of the activator ions was favorably altered. Additionally, the activator ions responsible for the lower-Stokes-shifted blue component of the emission functioned as a sensitizer of the larger-Stokes-shifted yellow-emitting activators, and predominantly yellow-emitting phosphors were achieved. The feasibility of developing a white light-emitting solid-state device using the developed phosphor was also demonstrated.

The original version of this Article contained an error in the title, which incorrectly read ‘Probing molecule-like isolated octahedra via—phase stabilization of zero-dimensional cesium lead halide nanocrystals.’ The correct version states ‘via phase stabilization’ in place of ‘via—phase stabilization’. This has been corrected in both the PDF and HTML versions of the Article.