Proteinogenic Amino Acid Assisted Preparation of Highly Luminescent Hybrid Perovskite Nanoparticles

Abstract

Versatile approaches to nanoparticle synthesis offer unprecedented opportunities for the development of optoelectronics, photonics, as well as bio sciences. With the current advancement of hybrid organic-inorganic metal halide perovskites, the next step is to expand their field of applications via utilization of functional and modifiable ligand chemistry. Here, we present a ligand assisted reprecipitation approach for highly luminescent perovskite nanoparticle synthesis using for the first time L-lysine and L-arginine for surface passivation. These nanoparticles exhibit emission within a narrow bandwidth of the visible spectrum and photoluminescence quantum yield close to 100%. Additionally, preferential ligand orientation is achieved via amino acids α-amino group blocking which results in blueshifted emission as well as smaller and more uniform particle size. These experimental results demonstrate the effectiveness of naturally occurring proteinogenic amino acids as surface ligands and offer possibilities for versatile modification of perovskite nanoparticle properties via well-studied amino acid chemistry.

Synthesis conditions influencing formation of MAPbBr3 perovskite nanoparticles prepared by the ligand-assisted precipitation method

“…These colloidal solutions were further characterized by optical spectroscopy techniques to evaluate the changes in optical properties. In particular, the use of chloroform as an antisolvent resulted in the formation of colloidal solutions with the most blue-shifted emission spectrum with a maximum of 509 nm, in agreement with our previously reported work 27 . Besides, a strong photoluminescence quenching effect 39 was observed in the case of the sample prepared in chloroform where the PLQY was found <1%.…”

“…In the precursor, the signals at 2930 and 2855 cm −1 were attributed to the alkyl groups and the signal detected at 1705 cm −1 was assigned to the C = O stretching band from the carboxylic acid group presented in the ligand hexanoic acid, introduced here as a stabilizer. Furthermore, the signal at 1595 cm −1 from the amine of the capping agent AdNH 2 was shifted to a lower wavenumber 1579 cm −1 attributed to the possible coordination with the PbBr 3 − from the amino groups 27 . The aforesaid is in agreement with preferential stabilization of nanoparticles with the selected ligands (Fig.…”

“…In general, perovskite precursors are soluble in highly polar aprotic solvents such as N,N-dimethylformamide (DMF), dimethylsulfoxide (DMSO) and γ-butyrolactone (GBL) 32 . Encouraged by previous experiments, we tested DMSO 30 and DMF 27 as solvents for the preparation of precursor solutions. The precursors were soluble in both DMSO and DMF.…”

“…However, there are several important parameters which need to be controlled during this ligand-assisted precipitation technique. Hence, the resulting final properties of the nanomaterials depend on the precipitation temperature 26 , the choice of solvent system 27 , the choice of capping agents 8 , 27 and their concentration 28 and on the water concentration in the precursor solutions 11 . However, a detailed understanding of the interplay of all these parameters is currently missing.…”

Rapid synthesis of cesium lead halide perovskite nanocrystals by l-lysine assisted solid-phase reaction at room temperature

“…So far, the method of directly assisting the synthesis of luminescent PNCs by amino acids still requires the participation of organic solvents. 28 Under the premise of discarding both the vacuum grinding environment 31,35 and the organic solvent to obtain green luminescent nanoparticles, the method greatly simplies the synthesis step and further realizes green chemistry in the eld of perovskite synthesis. Furthermore, we studied three different types of solid-phase synthesis methods: grinding by mortar and pestle (grinding synthesis), knocking by magnetic stirrer bar (knocking synthesis) and stirring by vortex mixer (stirring synthesis).…”