Magnetic polaronic and bipolaronic excitons in Mn(II) doped (TDMP)PbBr4 and their high emission

Abstract

If we introduce transition metal ions with spins into an organic-inorganic halide perovskite compounds, interesting spin dependent optical properties may be seen in this system. This paper reports an organic-inorganic hybrid manganese ion doped lead halide crystal incorporated by TDMP (trans-2,5-dimethylpiperazinium), it gives not only the STE1 (polaronic exciton), usually brought up by the enhanced electron-phonon coupling in the amine incorporated compound, but also give a novel bipolaronic exciton (STE2) for the paired charge state formation due to the incorporation of bi-amine cationic molecules, a excitation by the polaronic molecule due to enhanced electron-phonon coupling and neighboring correlation out of the Mn ion ferromagnetic spin coupling in the lattice at slightly high doping. Such magnetic bipolaron state could often be accompanied by several multiphonon Raman modes and ferromagnetism. It is even interesting that this state can give super-high red emission with PLQY at ~92.5% at room temperature. Moreover, the emission color and intensity could also be modulated by the Mn doping concentration, temperature, and laser excitation power. The low doping products can give green emission out of single Mn d-d transition at very low temperature or high laser excitation power. The intermediately doped products can give white emission out of STE1 and STE2. The highly doping products give red emission out of STE2 (bipolaron states) at room temperature or low laser power. These interesting phenomena reflected the microscopic interactions between spins, carriers and phonons in the products, which can be found applications in the future fields of photonics and spintronics.