Power-Dependent Photoluminescence Efficiency in Manganese-Doped 2D Hybrid Perovskite Nanoplatelets

Substitutional metal doping is a powerful strategy for manipulating the emission spectra and excited state dynamics of semiconductor nanomaterials. Here, we demonstrate the synthesis of colloidal manganese (Mn2+)-doped organic-inorganic hybrid perovskite nanoplatelets (chemical formula: L-2[APb(1-x)Mn(x)Br(3)](n-1)Pb1-xMnxBr4; L, butylammonium; A, methylammonium or formamidinium; n (= 1 or 2), number of Pb1-xMnxBr64- octahedral layers in thickness) via a ligand-assisted reprecipitation method. Substitutional doping of manganese for lead introduces bright (approaching 100% efficiency) and long-lived (>500 mu s) midgap Mn2+ atomic states, and the doped nanoplatelets exhibit dual emission from both the band edge and the dopant state. Photoluminescence quantum yields and band-edge-to-Mn intensity ratios exhibit strong excitation power dependence, even at a very low incident intensity (<100 mu W/cm(2)). Surprisingly, we find that the saturation of long-lived Mn-2(+) dopant sites cannot explain our observation. Instead, we propose an alternative mechanism involving the cross-relaxation of long-lived Mn-site excitations by freely diffusing band-edge excitons. We formulate a kinetic model based on this cross-relaxation mechanism that quantitatively reproduces all of the experimental observations and validate the model using time-resolved absorption and emission spectroscopy. Finally, we extract a concentration-normalized microscopic rate constant for band edge-to-dopant excitation transfer that is similar to 10x faster in methylammonium-containing nanoplatelets than in formamidinium-containing nanoplatelets. This work provides fundamental insight into the interaction of mobile band edge excitons with localized dopant sites in 2D semiconductors and expands the toolbox for manipulating light emission in perovskite nanomaterials.

Automated summary

Substitutional metal doping is a powerful strategy for manipulating the emission spectra and excited state dynamics of semiconductor nanomaterials. The synthesis of colloidal manganese (Mn2+)-doped organic-inorganic hybrid perovskite nanoplatelets via a ligand-assisted reprecipitation method introduces bright and long-lived midgap Mn2+ atomic states, with dual emission from the band edge and the dopant state. The interaction of mobile band edge excitons with localized dopant sites in 2D semiconductors is analyzed, providing fundamental insight and expanding the toolbox for manipulating light emission in perovskite nanomaterials.