In the last few years, there has been a rising interest in metal-organic frameworks (MOF) for the purpose of enclosing guest molecules. These nanoporous MOF structures consist of a metallic ion connected by organic ligands. In addition, in recent times, there has been also an interest in halide perovskites which have excellent optoelectronic properties. However, two major problems have plagued the development of halide perovskites for optical applications namely: the presence of hazardous lead and stability. In this work, we have tried to address both these problems with the help of metal-organic frameworks and double halide perovskites. Recently, double halide perovskites” have been developed in which two divalent ‘Pb2+’ cations are replaced with one monovalent and trivalent cation, generating quaternary A2M+M3+X6 compounds. The problems in double perovskite structures are the same as that of normal halide perovskite. In this work, we have tried to encapsulate double perovskite quantum dots within nanoporous metal-organic frameworks. To fabricate Cs2AgInCl6 quantum dots(QD), we have followed an earlier reported process by Manna et al. MOF thin films were deposited on a clean ITO substrate via LBL process. Zinc Nitrate and TCPP solution in DMF were spin-coated on ITO substrate. The deposited MOF was annealed at a temperature of 80 degrees to remove any residual solvent. Coated substrates were immersed for 10 mins in a solution comprising of ligands, Ag and In chloride salts. Diffusion of perovskite precursor in the micropores of MOF takes place which allows confined reaction and growth of the perovskite quantum dots. After washing with ethanol, the coated substrates were dipped in hot Cs-Oleate Solution, leading to the formation of confined quantum dots in the size range of MOF nanopores. Structural characterization of the sample was done by XRD which revealed strong peaks identical to the one reported before. Optical properties were determined by UV-vis spectrometry and PL spectrometry. Stability measurements showed significant PL emission for more than 20 days. Relatively, as-synthesized QDs decompose within hours due to agglomeration of nanoparticles, thereby losing their properties. At room temperature, Cs2AgInCl6 @Zn-TCPP thin film shows emission at 470-490 nm, upon excitation at 350 nm, which is a 70 nm blue-shift from its powder sample (560 nm). The blue shift in the thin films confirms the encapsulating nature of the metal-organic frameworks.

Confined fabrication of double perovskite quantum dots in metal-organic framework: Applications in solar photovoltaics

Macromolecular Chemistry: The Second Century

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ACS Spring 2020 National Meeting & Expo

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.