Recent progress has been made on the synthesis and characterization of metal halide perovskite magic-sized clusters (PMSCs) with ABX3 composition (A=CH3NH3+ or Cs+, B=Pb2+, and X=Cl−, Br-, or I-). However, their mechanism of growth and structure is still not well understood. In our effort to understand their structure and growth, we discovered that a new species can be formed without the CH3NH3+ component, which we name as molecular clusters (MCs). Specifically, CH3NH3PbBr3 PMSCs, with a characteristic absorption peak at 424 nm, are synthesized using PbBr2 and CH3NH3Br as precursors and butylamine (BTYA) and valeric acid (VA) as ligands, while MCs, with an absorption peak at 402 nm, are synthesized using solely PbBr2 and BTYA, without CH3NH3Br. Interestingly, PMSCs are converted spontaneously overtime into MCs. An isosbestic point in their electronic absorption spectra indicates a direct interplay between the PMSCs and MCs. Therefore, we suggest that the MCs are precursors to the PMSCs. From spectroscopic and extended X-ray absorption fine structure (EXAFS) results, we propose some tentative structural models for the MCs. The discovery of the MCs is critical to understanding the growth of PMSCs as well as larger perovskite quantum dots (PQDs) or nanocrystals (PNCs).

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Methylammonium lead bromide perovskite magic-sized clusters and quantum dots were synthesized using a new heated ligand assisted reprecipitation (HLARP) technique using organic amines and acids as capping ligands. The optical properties of these nanoparticles were analyzed using UV−vis electronic absorption and photoluminescent spectroscopy. Varying the temperature of the precursor solution while keeping the antisolvent temperature consistent allows for tuning between perovskite magic-sized clusters (MSCs) and quantum dots (PQDs) without the need to use excessive concentrations of capping ligand. Higher precursor solution temperatures favor MSCs, while lower temperatures favor PQDs. Furthermore, increasing the temperature of the system shifts the original emission band from 436 to 453 nm, by increasing the size and potentially through the introduction of surface defects. Low frequency Raman spectroscopy reveals that MSCs have vibrational frequencies that are similar to those of bulk perovskite. Electrospray mass spectrometry and infrared spectroscopy were used to probe the ligands on the surface of the MSCs, indicating that amine is the primary capping ligand and the surface is presumably cation rich.

Perovskite solar cells have garnered exponential research interest due to their facile fabrication, solution processability, and low cost. However, there have been limited efforts to integrate this class of materials into the undergraduate laboratory curriculum. Therefore, we designed an integrated laboratory experiment in our upper-division integrated laboratory sequence to teach students about research procedures and tools used in physical, organic, inorganic, and materials chemistry. This laboratory sequence involves conversion of sunlight to electricity, which is one of the most challenging renewable energy issues we are facing as a society. In this work, upper-level undergraduates study four variables affecting the morphology and optical properties of perovskites: solvent treatment, percent of water added to a precursor mixture, cation substitution, and precursor temperature. To do so, students deposit uniform films of the material using spin-coating and annealing, and then probe the resulting film properties via scanning electron microscopy, X-ray diffraction, solid-state UV–vis spectroscopy, and current–voltage measurements. Students are able to execute the simple experimental setups and critically interpret, and compare, their results. Further, students are asked to question and understand structure–property relationships to arrive at a fuller understanding of the light-to-electricity conversion process. Importantly, this laboratory prepares students for cutting-edge inorganic and materials research topics.

We investigate the mechanisms of energy transfer in Mn2+-doped ethylammonium lead bromide (EA2PbBr4:Mn2+), a two-dimensional layered perovskite (2DLP), using cryogenic optical spectroscopy. At temperature T > 120 K, photoluminescence (PL) is dominated by emission from Mn2+, with complete suppression of band edge (BE) emission and self-trapped exciton (STE) emission. However, for T < 120 K, in addition to Mn2+ emission, PL is observed from BE and STEs. Data further reveal that for 20 K < T < 120 K, STEs form the most dominant routes in assisting energy transfer (ET) from 2DLP to Mn2+ dopants. However, at higher Mn2+ concentration, higher activation energies indicate defect states come into play, successfully competing with STEs for ET both from BE to STE states and from STE to Mn2+. Finally, using polarization-resolved spectroscopy, we demonstrate optical spin orientation of the Mn2+ ions via ET from 2DLP excitons at zero magnetic field. Our results reveal fundamental insights on the interactions between quantum confined charge carriers and dopants in organometal halide perovskites.