Cu+ → Mn2+ Energy Transfer in Cu, Mn Coalloyed Cs3ZnCl5 Colloidal Nanocrystals

Abstract

In this work, we report the hot-injection synthesis of Cs₃ZnCl₅ colloidal nanocrystals (NCs) with tunable amounts of Cu⁺ and Mn²⁺ substituent cations. All the samples had a rodlike morphology, with a diameter of ∼14 nm and a length of ∼30-100 nm. Alloying did not alter the crystal structure of the host Cs₃ZnCl₅ NCs, and Cu ions were mainly introduced in the oxidation state +1 according to X-ray photoelectron and electron paramagnetic resonance spectroscopies. The spectroscopic analysis of unalloyed, Cu-alloyed, Mn-alloyed, and Cu, Mn coalloyed NCs indicated that (i) the Cs₃ZnCl₅ NCs have a large band gap of ∼5.35 eV; (ii) Cu(I) aliovalent alloying leads to an absorption shoulder/peak at ∼4.8 eV and cyan photoluminescence (PL) peaked at 2.50 eV; (iii) Mn(II) isovalent alloying leads to weak Mn PL, which intensifies remarkably in the coalloyed samples, prompted by an energy transfer (ET) process between the Cu and Mn centers, favored by the overlap between the lowest (⁶A₁ → ⁴T₁) transition for tetrahedrally coordinated Mn²⁺ and the PL profile from Cu(I) species in the Cs₃ZnCl₅ NCs. The efficiency of this ET process reaches a value of 61% for the sample with the highest extent of Mn alloying. The PL quantum yield (QY) values in these Cu, Mn coalloyed NCs are lower at higher Mn contents. The analysis of the Mn PL dynamics in these samples indicates that this PL drop stems from inter-Mn exciton migration, which increases the likelihood of trapping in defect sites, in agreement with previous studies.