Metal-halide perovskites have rapidly emerged as one of the most promising materials of the 21st century, with many exciting properties and great potential for a broad range of applications, from photovoltaics to optoelectronics and photocatalysis. The ease with which metal-halide perovskites can be synthesized in the form of brightly luminescent colloidal nanocrystals, as well as their tunable and intriguing optical and electronic properties, has attracted researchers from different disciplines of science and technology. In the last few years, there has been a significant progress in the shape-controlled synthesis of perovskite nanocrystals and understanding of their properties and applications. In this comprehensive review, researchers having expertise in different fields (chemistry, physics, and device engineering) of metal-halide perovskite nanocrystals have joined together to provide a state of the art overview and future prospects of metal-halide perovskite nanocrystal research.

State of the Art and Prospects for Halide Perovskite Nanocrystals.

Highly efficient blue-emitting three-dimensional (3D) lead-free halide perovskites with excellent stability have attracted worldwide attention. Herein, a doping route was adopted to incorporate Sb3+ ions into the Cs2NaInCl6 for decorating the electronic band structure. Due to the moderate electron-phonon coupling, the Sb3+-doped Cs2NaInCl6 double perovskites showed a narrow and relatively unusual blue emission of self-trapped excitons (STEs). Density functional theory (DFT) calculation indicated that the doped Sb3+ ions could break the parity-forbidden transition rule and modulate the density of state (DOS) population effectively to boost the PLQY of STEs drastically. The optimized Sb3+:Cs2NaInCl6 exhibited a PLQY of up to 75.89% and excellent stability under the consecutive illumination of 365 nm UV light for 1000 h. This kind of highly efficient lead-free Sb3+-doped Cs2NaInCl6 double perovskites may overcome the bottlenecks of severe toxicity and insufficient stability and therefore have an extensive application in the scarce blue photonic and optoelectronic fields.

Highly Efficient Blue Emission from Self-Trapped Excitons in Stable Sb3+-Doped Cs2NaInCl6 Double Perovskites.

The past decade has witnessed tremendous advances in synthesis of metal halide perovskites and their use for a rich variety of optoelectronics applications. Metal halide perovskite has the general formula ABX3, where A is a monovalent cation (which can be either organic (e.g., CH3NH3+ (MA), CH(NH2)2+ (FA)) or inorganic (e.g., Cs+)), B is a divalent metal cation (usually Pb2+), and X is a halogen anion (Cl-, Br-, I-). Particularly, the photoluminescence (PL) properties of metal halide perovskites have garnered much attention due to the recent rapid development of perovskite nanocrystals. The introduction of capping ligands enables the synthesis of colloidal perovskite nanocrystals which offer new insight into dimension-dependent physical properties compared to their bulk counterparts. It is notable that doping and ion substitution represent effective strategies for tailoring the optoelectronic properties (e.g., absorption band gap, PL emission, and quantum yield (QY)) and stabilities of perovskite nanocrystals. The doping and ion substitution processes can be performed during or after the synthesis of colloidal nanocrystals by incorporating new A', B', or X' site ions into the A, B, or X sites of ABX3 perovskites. Interestingly, both isovalent and heterovalent doping and ion substitution can be conducted on colloidal perovskite nanocrystals. In this review, the general background of perovskite nanocrystals synthesis is first introduced. The effects of A-site, B-site, and X-site ionic doping and substitution on the optoelectronic properties and stabilities of colloidal metal halide perovskite nanocrystals are then detailed. Finally, possible applications and future research directions of doped and ion-substituted colloidal perovskite nanocrystals are also discussed.

Doping and ion substitution in colloidal metal halide perovskite nanocrystals.

The incorporation of impurity ions or doping is a promising method for controlling the electronic and optical properties and the structural stability of halide perovskite nanocrystals (NCs). Herein, we establish relationships between rare-earth ions doping and intrinsic emission of lead-free double perovskite Cs2 AgInCl6 NCs to impart and tune the optical performances in the visible light region. Tb3+ ions were incorporated into Cs2 AgInCl6 NCs and occupied In3+ sites as verified by both crystallographic analyses and first-principles calculations. Trace amounts of Bi doping endowed the characteristic emission (5 D4 →7 F6-3 ) of Tb3+ ions with a new excitation peak at 368 nm rather than the single characteristic excitation at 290 nm of Tb3+ . By controlling Tb3+ ions concentration, the emission colors of Bi-doped Cs2 Ag(In1-x Tbx )Cl6 NCs could be continuously tuned from green to orange, through the efficient energy-transfer channel from self-trapped excitons to Tb3+ ions. Our study provides the salient features of the material design of lead-free perovskite NCs and to expand their luminescence applications.

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Incorporating Rare‐Earth Terbium(III) Ions into Cs 2 AgInCl 6 :Bi Nanocrystals toward Tunable Photoluminescence

Improving Lead-Free Double Perovskite Cs2NaBiCl6 Nanocrystal Optical Properties via Ion Doping

Lead-free double perovskite materials, A2M(I)M′(III)X6, have recently attracted attention as environment-friendly alternatives to lead-based perovskites, APbX3, because of both rich fundamental sci...

Band Gap Engineering in Cs2(NaxAg1-x)BiCl6 Double Perovskite Nanocrystals.

Lead-free halide double perovskites (DPs) have emerged as a stable and greener alternative to very toxic lead-based perovskites owing to their outstanding photophysical properties. Here, a series o...

Raman Singh Lamba

Papers

Band Gap Engineering in Cs2(NaxAg1-x)BiCl6 Double Perovskite Nanocrystals.

Lead-Free Alloyed Double-Perovskite Nanocrystals of Cs2(NaxAg1–x)BiBr6 with Tunable Band Gap