Reverse Micelle Templating Route to Ordered Monodispersed Spherical Organo-Lead Halide Perovskite Nanoparticles for Light Emission

Abstract

Hybrid organic–inorganic halide perovskites have emerged as a disruptive technology in a number of fields, and recently, there has been increased interest in developing nanostructured perovskite materials, due to their extremely high photoluminescence quantum yields, optical absorption, and tolerance for defects. In this study, we report on the development of a facile room temperature synthesis method for high density monodispersed metal–organic halide perovskite nanoparticles using a diblock copolymer reverse micelle deposition (RMD) method. Compared to traditional ligated methods, we show that diblock copolymer micelle templating allows greater control over the size distribution due to controlled nucleation and crystal growth. By separating the precursor solvation and reaction steps through micelle templating, we show that micelle templating is a universal, atmospheric approach to producing a variety of perovskite nanoparticles, including methylammonium lead iodide (MAPbI3), methylammonium lead bromide (MAPbBr3), and formamidinium lead iodide (FAPbI3) at room temperature. Additionally, using micellar nanoreactors rather than dynamically stabilizing ligands allows the formation of monodisperse spherical 0D nanoparticles rather than nanoplatelets or nanorods, as is common with most approaches. Knowledge of the synthesis behavior of a facile versatile approach for monodisperse nanoparticles with narrow band emission will open up new avenues for the development of nanoparticle based applications as integral parts of next-generation displays and optoelectronic devices.

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

“…The shape and size can be controlled by changing the reaction conditions and the solvent during hot-injection 17 – 19 or ligand-assisted precipitation methods, where also the choice of the capping agents plays a crucial role 20 . Furthermore, perovskite nanoparticles can also be grown within nanopores 21 , or in templates of diblock copolymer micelles 22 .…”

Universal Transfer Printing of Micelle-Templated Nanoparticles Using Plasma-Functionalized Graphene

“…The reverse micelle deposition (RMD) process requires sustained plasma etching to produce monodisperse nanoparticles with a high degree of two-dimensional order, as shown in Figure 2 . Here, MAPbBr 3 nanoparticles are shown, but RMD is able to produce similar nanoparticle dispersions of a wide variety of materials under similar etching conditions 2 , 6 , 12 , 43 , 44 (see Figure SI-2 for AFM of γ-Fe 2 O 3 nanoparticles produced under similar conditions as MAPbBr 3 ).…”

“…Using these micelles as “nanoreactors” allows the formation of highly size controllable nanoparticles, with less than 2% deviation in the average particle diameter. 2 , 6 , 12 , 43 , 44 The other advantage of reverse micelle deposition (RMD) is the control over the 2D dispersion: highly ordered periodic arrays with varying spacing and organization are achieved with the simple tuning of deposition parameters. 10 , 12 To produce RMD nanoparticles, poly(styrene- b -2-vinyl pyridine) (PS- b -P2VP) diblock copolymer reverse micelles are formed in a nonpolar solvent.…”

“…Figure 3 b shows a TEM image of the MAPbBr 3 nanoparticles, with the inset energy-dispersive X-ray spectrometry (EDX) line profile showing the presence of C, Pb, and Br, confirming the successful formation of the MAPbBr 3 nanoparticles by RMD. 12 …”

Modular Zwitterion-Functionalized Poly(Isopropyl Methacrylate) Polymers for Hosting Luminescent Lead-Halide Perovskite Nanocrystals

“…The interface modifier approach has been demonstrated by direct synthesis of perovskite NCs in a hydrophobically stabilized micelle of lauryl methacrylate 40 and by using custom polymers that form micelles to stabilize the NCs in different hosts, 44,[51][52][53][54] with varying levels of success.…”