Semiconducting lead halide perovskites (LHPs) have not only become prominent thin-film absorber materials in photovoltaics but have also proven to be disruptive in the field of colloidal semiconductor nanocrystals (NCs). The most important feature of LHP NCs is their so-called defect-tolerance—the apparently benign nature of structural defects, highly abundant in these compounds, with respect to optical and electronic properties. Here, we review the important differences that exist in the chemistry and physics of LHP NCs as compared with more conventional, tetrahedrally bonded, elemental, and binary semiconductor NCs (such as silicon, germanium, cadmium selenide, gallium arsenide, and indium phosphide). We survey the prospects of LHP NCs for optoelectronic applications such as in television displays, light-emitting devices, and solar cells, emphasizing the practical hurdles that remain to be overcome.

Properties and potential optoelectronic applications of lead halide perovskite nanocrystals

Lead halide perovskites (LHPs) in the form of nanometre-sized colloidal crystals, or nanocrystals (NCs), have attracted the attention of diverse materials scientists due to their unique optical versatility, high photoluminescence quantum yields and facile synthesis. LHP NCs have a 'soft' and predominantly ionic lattice, and their optical and electronic properties are highly tolerant to structural defects and surface states. Therefore, they cannot be approached with the same experimental mindset and theoretical framework as conventional semiconductor NCs. In this Review, we discuss LHP NCs historical and current research pursuits, challenges in applications, and the related present and future mitigation strategies explored.

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Genesis, challenges and opportunities for colloidal lead halide perovskite nanocrystals

Metal halide perovskites represent a flourishing area of research, driven by both their potential application in photo-voltaics and optoelectronics, and for the fundamental science underpinning their unique optoelectronic properties. The advent of colloidal methods for the synthesis of halide perovskite nanocrystals has brought to the attention inter-esting aspects of this new type of materials, above all their defect-tolerance. This review aims to provide an updated survey of this fast-moving field, with a main focus on their colloidal synthesis. We examine the chemistry and the ca-pability of different colloidal synthetic routes to control the shape, size and optical properties of the resulting nano-crystals. We also provide an up to date overview of their post-synthesis transformations, and summarize the various so-lution processes aimed at fabricating halide perovskite-based nanocomposites. We then review the fundamental optical properties of halide perovskite nanocrystals, by focusing on their linear optical properties, on the effects of quantum confinement and, then, on the current knowledge of their exciton binding energies. We also discuss the emergence of non-linear phenomena such as multiphoton absorption, biexcitons and carrier multiplication. At last, we provide an outlook in the field, with the most cogent open questions and possible future directions.

Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications and Their Optical Properties

Metal halide perovskites represent a flourishing area of research, which is driven by both their potential application in photovoltaics and optoelectronics and by the fundamental science behind their unique optoelectronic properties. The emergence of new colloidal methods for the synthesis of halide perovskite nanocrystals, as well as the interesting characteristics of this new type of material, has attracted the attention of many researchers. This review aims to provide an up-to-date survey of this fast-moving field and will mainly focus on the different colloidal synthesis approaches that have been developed. We will examine the chemistry and the capability of different colloidal synthetic routes with regard to controlling the shape, size, and optical properties of the resulting nanocrystals. We will also provide an up-to-date overview of their postsynthesis transformations, and summarize the various solution processes that are aimed at fabricating halide perovskite-based nanocomposites. Furthermore, we...

Metal Halide Perovskite Nanocrystals: Synthesis, Post-Synthesis Modifications, and Their Optical Properties.

Beyond the unprecedented success achieved in photovoltaics (PVs), lead halide perovskites (LHPs) have shown great potential in other optoelectronic devices. Among them, nanometer-scale perovskite quantum dots (PQDs) with fascinating optical properties including high brightness, tunable emission wavelength, high color purity, and high defect tolerance have been regarded as promising alternative down-conversion materials in phosphor-converted light-emitting diodes (pc-LEDs) for lighting and next-generation of display technology. Despite the promising applications of perovskite materials in various fields, they have received strong criticism for the lack of stability. The poor stability has also attracted much attention. Within a few years, numerous strategies towards enhancing the stability have been developed. This review summarizes the mechanisms of intrinsic- and extrinsic-environment-induced decomposition of PQDs. Simultaneously, the strategies for improving the stability of PQDs are reviewed in detail, which can be classified into four types: (1) compositional engineering; (2) surface engineering; (3) matrix encapsulation; (4) device encapsulation. Finally, the challenges for applying PQDs in pc-LEDs are highlighted, and some possible solutions to improve the stability of PQDs together with suggestions for further improving the performance of pc-LEDs as well as the device lifetime are provided.

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An overview on enhancing the stability of lead halide perovskite quantum dots and their applications in phosphor-converted LEDs

Mn2+ ions doped in high-energy absorbing semiconductor host nanocrystals take away the exciton energy and result in spin-polarized d–d emission. For the last three decades this has been widely studied on group II–VI semiconductors. Recently, the doping has been extended to CsPbX3 perovskite nanocrystals. Although the optical transition follows a similar principle, in which the exciton energy is transferred to dopant Mn d-state, doping in perovskite also revealed several new fundamental aspects of doping and dopant-induced new optical properties. Here, anions which mostly tune the band gap controlled the fate of the appearance of Mn emission. Also, the doping process was observed to be different than traditional growth doping. Hence, in perovskite host nanocrystals, while some aspects of Mn doping are found to be in agreement with previous findings, some new facts also surfaced. Combining all these facts, this Perspective focuses on the journey of Mn doping from group II–VI semiconductors to lead halide pe...

Doping Mn2+ in Lead Halide Perovskite Nanocrystals: Successes and Challenges

Introducing a few atoms of impurities or dopants in semiconductor nanocrystals can drastically alter the existing properties or even introduce new properties For example, mid-gap states created by doping tremendously affect photocatalytic activities and surface controlled redox reactions, generate new emission centers, show thermometric optical switching, make FRET donors by enhancing the excited state lifetime, and also create localized surface plasmon resonance induced low energy absorption In addition, researchers have more recently started focusing their attention on doped nanocrystals as an important and alternative material for solar energy conversion to meet the current demand for renewable energy Moreover, the electrical and magnetic properties of the host are also strongly altered on doping These beneficial dopant-induced changes suggest that doped nanocrystals with proper selections of dopant-host pairs may be helpful for generating designer materials for a wide range of current technological needs How properties relate to the doping of a variety of semiconductor nanocrystals are summarized in this Review

Luminescence, Plasmonic, and Magnetic Properties of Doped Semiconductor Nanocrystals.

Doping in perovskite nanocrystals adopts different mechanistic approach in comparison to widely established doping in chalcogenide quantum dots The fast formation of perovskites makes the dopant insertions more competitive and challenging Introducing alkylamine hydrochloride (RNH3 Cl) as a promoting reagent, precise controlled doping of MnII in CsPbCl3 perovskite nanocrystals is reported Simply, by changing the amount of RNH3 Cl, the Mn incorporation and subsequent tuning in the excitonic as well as Mn d-d emission intensities are tailored Investigations suggested that RNH3 Cl acted as the chlorinating source, controlled the size, and also helps in increasing the number of particles This provided more opportunity for Mn ions to take part in reaction and occupied the appropriate lattice positions Carrying out several reactions with varying reaction parameters, the doping conditions are optimized and the role of the promoting reagent for both doped and undoped systems are compared

Chemically Tailoring the Dopant Emission in Manganese-Doped CsPbCl3 Perovskite Nanocrystals

High temperature colloidal synthesis for obtaining thermal, colloidal and phase-stable CsPbI3 nanocrystals with near-unity quantum yield is reported. While standard perovskite synthesis reactions were carried out at 160 °C (below 200 °C), increase of another ≈100 °C enabled the alkylammonium ions to passivate the surface firmly and prevented the nanocrystals from phase transformation. This did not require any inert atmosphere storage, use of heteroatoms, specially designed ligands, or the ice cooling protocol. Either at high temperature in reaction flask or in the crude mixture or purified dispersed solution; these nanocrystals were observed stable and retained the original emission. Different spectroscopic analyses were carried out and details of the surface binding of alkyl ammonium ligands in place of surface Cs in the crystal lattice were investigated. As CsPbI3 is one of the most demanding optical materials, bringing stability by proper surface functionalization without use of secondary additives would indeed help in wide spreading of their applications.

Phase-Stable CsPbI3 Nanocrystals: The Reaction Temperature Matters

For varying the size of perovskite nanocrystals, variation in the reaction temperature and tuning the ligand chain lengths are established as the key parameters for high-temperature solution-processed synthesis. These also require sharp cooling for obtaining desired dimensions and optical stability. In contrast, using preformed alkylammonium bromide salt as the precise dimension-controlling reagent, wide window size tunable CsPbBr3 nanocrystals were reported without varying the reaction temperature or changing the ligands. The size tunability even with ∼1 nm step growth regimes was achieved as a function of only the concentration of added alkylammonium bromide salt. Not only the cube shape but also the width varied in the sheet structures. Because these nanostructures lose their optical stability and crystal phase on prolonged annealing, stabilizing these in high-temperature synthesis for all-inorganic lead halide perovskites is important and remains challenging. In this aspect, this method proved to be m...

Samrat Das Adhikari

Papers

Doping Mn2+ in Lead Halide Perovskite Nanocrystals: Successes and Challenges

Luminescence, Plasmonic, and Magnetic Properties of Doped Semiconductor Nanocrystals.

Chemically Tailoring the Dopant Emission in Manganese-Doped CsPbCl3 Perovskite Nanocrystals

Phase-Stable CsPbI3 Nanocrystals: The Reaction Temperature Matters

Tuning the Size of CsPbBr3 Nanocrystals: All at One Constant Temperature