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      Zero-Dimensional Cesium Lead Halides: History, Properties, and Challenges

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          Abstract

          Over the past decade, lead halide perovskites (LHPs) have emerged as new promising materials in the fields of photovoltaics and light emission due to their facile syntheses and exciting optical properties. The enthusiasm generated by LHPs has inspired research in perovskite-related materials, including the so-called “zero-dimensional cesium lead halides”, which will be the focus of this Perspective. The structure of these materials is formed of disconnected lead halide octahedra that are stabilized by cesium ions. Their optical properties are dominated by optical transitions that are localized within the individual octahedra, hence the title “‘zero-dimensional perovskites”. Controversial results on their physical properties have recently been reported, and the true nature of their photoluminescence is still unclear. In this Perspective, we will take a close look at these materials, both as nanocrystals and as bulk crystals/thin films, discuss the contrasting opinions on their properties, propose potential applications, and provide an outlook on future experiments.

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          Most cited references103

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          Tuning the Optical Properties of Cesium Lead Halide Perovskite Nanocrystals by Anion Exchange Reactions

          We demonstrate that, via controlled anion exchange reactions using a range of different halide precursors, we can finely tune the chemical composition and the optical properties of presynthesized colloidal cesium lead halide perovskite nanocrystals (NCs), from green emitting CsPbBr3 to bright emitters in any other region of the visible spectrum, and back, by displacement of Cl– or I– ions and reinsertion of Br– ions. This approach gives access to perovskite semiconductor NCs with both structural and optical qualities comparable to those of directly synthesized NCs. We also show that anion exchange is a dynamic process that takes place in solution between NCs. Therefore, by mixing solutions containing perovskite NCs emitting in different spectral ranges (due to different halide compositions) their mutual fast exchange dynamics leads to homogenization in their composition, resulting in NCs emitting in a narrow spectral region that is intermediate between those of the parent nanoparticles.
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            Materials processing routes to trap-free halide perovskites.

            Photovoltaic devices based on lead iodide perovskite films have seen rapid advancements, recently achieving an impressive 17.9% certified solar power conversion efficiency. Reports have consistently emphasized that the specific choice of growth conditions and chemical precursors is central to achieving superior performance from these materials; yet the roles and mechanisms underlying the selection of materials processing route is poorly understood. Here we show that films grown under iodine-rich conditions are prone to a high density of deep electronic traps (recombination centers), while the use of a chloride precursor avoids the formation of key defects (Pb atom substituted by I) responsible for short diffusion lengths and poor photovoltaic performance. Furthermore, the lowest-energy surfaces of perovskite crystals are found to be entirely trap-free, preserving both electron and hole delocalization to a remarkable degree, helping to account for explaining the success of polycrystalline perovskite films. We construct perovskite films from I-poor conditions using a lead acetate precursor, and our measurement of a long (600 ± 40 nm) diffusion length confirms this new picture of the importance of growth conditions.
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              Intrinsic white-light emission from layered hybrid perovskites.

              We report on the second family of layered perovskite white-light emitters with improved photoluminescence quantum efficiencies (PLQEs). Upon near-ultraviolet excitation, two new Pb-Cl and Pb-Br perovskites emit broadband "cold" and "warm" white light, respectively, with high color rendition. Emission from large, single crystals indicates an origin from the bulk material and not surface defect sites. The Pb-Br perovskite has a PLQE of 9%, which is undiminished after 3 months of continuous irradiation. Our mechanistic studies indicate that the emission has contributions from strong electron-phonon coupling in a deformable lattice and from a distribution of intrinsic trap states. These hybrids provide a tunable platform for combining the facile processability of organic materials with the structural definition of crystalline, inorganic solids.
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                Author and article information

                Journal
                J Phys Chem Lett
                J Phys Chem Lett
                jz
                jpclcd
                The Journal of Physical Chemistry Letters
                American Chemical Society
                1948-7185
                13 April 2018
                03 May 2018
                : 9
                : 9
                : 2326-2337
                Affiliations
                []Nanochemistry Department, Istituto Italiano di Tecnologia , Via Morego 30, 16163 Genova, Italy
                []Dipartimento di Chimica e Chimica Industriale, Università degli Studi di Genova , Via Dodecaneso 31, 16146 Genova, Italy
                Author notes
                [* ]E-mail: ahmed.abdelhady@ 123456iit.it (A.L.A.).
                [* ]E-mail: liberato.manna@ 123456iit.it (L.M.).
                Article
                10.1021/acs.jpclett.8b00572
                5937914
                29652149
                79aa0c01-05e4-4bd9-92af-54bf447d73a8
                Copyright © 2018 American Chemical Society

                This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes.

                History
                : 22 February 2018
                : 13 April 2018
                Categories
                Perspective
                Custom metadata
                jz8b00572
                jz-2018-00572n

                Physical chemistry
                Physical chemistry

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