Quantum-confined CsPbBr3 perovskites are promising blue emitters for ultra-high-definition displays, but their soft lattice caused by highly ionic nature has a limited stability. Here, we endow CsPbBr3 nanoplatelets (NPLs) with atomic crystal-like structural rigidity through proper surface engineering, by using strongly bound N-dodecylbenzene sulfonic acid (DBSA). A stable, rigid crystal structure, as well as uniform, orderly-arranged surface of these NPLs is achieved by optimizing intermediate reaction stage, by switching from molecular clusters to mono-octahedra, while interaction with DBSA resulted in formation of a CsxO monolayer shell capping the NPL surface. As a result, both structural and optical stability of the CsPbBr3 NPLs is enhanced by strong covalent bonding of DBSA, which inhibits undesired phase transitions and decomposition of the perovskite phase potentially caused by ligand desorption. Moreover, rather small amount of DBSA ligands at the NPL surface results in a short inter-NPL spacing in their closely-packed films, which facilitates efficient charge injection and transport. Blue photoluminescence of the produced CsPbBr3 NPLs is bright (nearly unity emission quantum yield) and peaks at 457 nm with an extremely narrow bandwidth of 3.7 nm at 80 K, while the bandwidth of the electroluminescence (peaked at 460 nm) also reaches a record-narrow value of 15 nm at room temperature. This value corresponds to the CIE coordinates of (0.141, 0.062), which meets Rec. 2020 standards for ultra-high-definition displays.
Zero-dimensional lead halide perovskite nanocrystals (NCs) exhibit size-dependent bandgap and carrier confinement compared to bulk counterparts due to the quantum confinement effect, making them essential for achieving wide-color-gamut displays, studying excitonic spin relaxation, and constructing superlattices. Despite their promising potential, they face a variety of technical bottlenecks, such as insufficient color reproducibility, limited large-scale production, low stability, and toxicity. An outline of a research roadmap is provided in the review, which highlights key challenges in developing perovskite NCs for commercial applications.
Spectrally stable pure-red perovskite quantum dots (QDs) with low lead content are essential for high-definition displays but are difficult to synthesize due to QD self-purification. Here, we make use of entropy-driven quantum-confined pure-red perovskite QDs to fabricate light-emitting diodes (LEDs) that have low toxicity and are efficient and spectrum-stable. Based on experimental data and first-principles calculations, multiple element alloying results in a 60% reduction in lead content while improving QD entropy to promote crystal stability. Entropy-driven QDs exhibit photoluminescence with 100% quantum yields and single-exponential decay lifetimes without alteration of their morphology or crystal structure. The pure-red LEDs utilizing entropy-driven QDs have spectrally stable electroluminescence, achieving a brightness of 4932 cd/m2, a maximum external quantum efficiency of over 20%, and a 15-fold longer operational lifetime than the CsPbI3 QD-based LEDs. These achievements demonstrate that entropy-driven QDs can mitigate local compositional heterogeneity and ion migration.
Colloidal perovskite nanocrystals (NCs) have risen rapidly in luminescence efficiency and color purity. However, their high performance requires careful and complex pre-treatment of precursors and precise regulation of the reaction atmosphere; otherwise, their emission will be weak and broad. To overcome these limitations, we develop a facile ligand exchange method using a new type of bidentate ligand, which is obtained by reacting cheap sulfur with tributylphosphine (S-TBP). During ligand exchange, the double bond between P and S atoms breaks and a single bond is formed between them, after which S-TBP switches into a bidentate ligand and binds to a perovskite NC at two points. With short-chain S-TBP ligands that have high spatial position resistance, both NC spacing and surface ligand density can be reduced, thereby improving carrier injection and transport. On the NC surface after ligand exchange, halogen vacancies were substantially filled, leading to a PbSP (Pb, S, and P elements) component-dominated shell that greatly decreases trap density and enhances material stability. The resulting perovskite NCs are stable and bright with a photoluminescence quantum yield of ≈96 %, and an external quantum efficiency of 22 %. Note that our ligand-exchange strategy remains effective even when scaling up, which should accelerate commercialization.
Atmosphere , Nanoparticles , Ligands , Calcium Compounds
Close attention to the interfaces of solution-processed metal halide perovskite-based light-emitting devices (LEDs) is crucial for their optimal performance. Solution processing of these devices typically leads to the formation of van der Waals interfaces with a weak connection between different functional layers, leaving great room for improvement in charge transport through strengthening of the interlayer interaction. Here, we have realized a hydrogen-bond-assisted interface that makes use of ultrasmall amine-terminated carbon dots to enhance the interaction between the hole transport layer made of PEDOT:PSS and the hybrid lead bromide perovskite emitting layer, which not only promotes the hole injection efficiency but also orients the quasi-2D perovskite crystals penetrating the vertical direction of the device without any, or very few, horizontal grain boundaries, which has a profound effect on the photophysical and transport properties of the emitting layer. As a result, LEDs based on quasi-2D perovskites show up to 24.5% external quantum efficiency, 80â¯000 cd m-2 brightness, and over 5-fold extended longevity.
Metal halide perovskite nanocrystals (NCs) attract much attention for light-emitting applications due to their exceptional optical properties. More recently, perovskite NCs have begun to be considered a promising material for nonlinear optical applications. Numerous strategies have recently been developed to improve the properties of metal halide perovskite NCs. Among them, B-site doping is one of the most promising ways to enhance their brightness and stability. However, there is a lack of study of the influence of B-site doping on the nonlinear optical properties of inorganic perovskite NCs. Here, we demonstrate that Cd2+ doping simultaneously improves both the linear (higher photoluminescence quantum yield, larger exciton binding energy, reduced trap states density, and faster radiative recombination) and nonlinear (higher two- and three-photon absorption cross-sections) optical properties of CsPbBr3 NCs. Cd2+ doping results in a two-photon absorption cross-section, reaching 2.6 × 106 Goeppert-Mayer (GM), which is among the highest reported for CsPbBr3 NCs.
Formation of a non-emissive wide bandgap CsPb2Br5 component often accompanies the synthesis of CsPbBr3 perovskites, introducing undesired energy states and impeding the charge transport. Here, we demonstrate that a small amount of a methanol additive can promote the CsBr release rate, facilitating CsPbBr3 formation and suppressing CsPb2Br5 formation. Some of the methanol ionizes into CH5O+ and CH3O-, which act as surface ligands and change the crystallization environment, inducing shape evolution from spherical nanocrystals to rectangular nanoplatelets (NPLs), leading to monodispersed and phase-pure 8 unit-cell-thick CsPbBr3 NPLs. Meanwhile, nonradiative recombination processes are inhibited as a result of NPL surface passivation. Bright CsPbBr3 NPLs with a photoluminescence quantum yield reaching 90% were employed as emitters for electroluminescent light-emitting devices.
Ruddlesden-Popper perovskites with a formula of (A')2(A) n -1B n X3 n +1 have recently gained widespread interest as candidates for the next generation of optoelectronic devices. The variations of organic cation, metal halide, and the number of layers in the structure lead to the change of crystal structures and properties for different optoelectronic applications. Herein, the different synthetic methods for 2D perovskite crystals and thin films are summarized and compared. The optoelectronic properties and the charge transfer process in the devices are also delved, in particular, for light-emitting diodes and solar cells.
Transition metal dichalcogenides have unique physicochemical properties. Herein, a low-temperature facile method is demonstrated to synthesize ultrathin tungsten disulfide nanoflakes. They are loosely stacked between layers with highly exposed edges, which provide lots of active sites for electrochemical applications. The by-product of crystalline carbon improves their conductivity, which also enhances their performance in hydrogen evolution reaction.
Lead halide perovskite nanocrystals (NCs) exhibit excellent tunable emissions covering the entire visible spectral region, but they do not emit near-infrared (NIR) light. We synthesized rare earth element doped CsPbCl3 NCs for NIR emission. The Yb3+ doped CsPbCl3 NCs emitted strong 986 nm NIR light; the Yb3+/Er3+ co-doped CsPbCl3 NCs emitted at 1533 nm. The total photoluminescence quantum yield (PL QY) of the CsPbCl3 NCs changed from 5.0% to 127.8% upon incorporating 2.0% Yb3+, a factor of 25.6 times enhancement. The material's stability was tested under continuous ultraviolet (365 nm) irradiation. The doped CsPbCl3 NCs exhibited a better stability than the undoped one. The PL intensity of the undoped CsPbCl3 NCs dropped to 20% of the initial value in 27 h, while the doped one took 85 h.
Transition-metal dichalcogenides like tungsten disulfide (WS2) are luminescent but still bear low quantum yields and hardly meet the requirement of practical applications. Here, we developed a hot-injection method to prepare highly luminescent WS2 quantum dots with tunable particle size in a noncoordinating solvent, some that are even smaller than its Bohr radius. The as-synthesized WS2 quantum dots exhibit a narrow size distribution and a high photoluminescence quantum yield of 32%, the highest record compared to the known reports. The WS2 quantum dot layer was employed to fabricate white light-emitting diodes with a maximum brightness of 507 cd/m2, adjustable color temperatures from 4100 to 10 000 K, and excellent color rendering index of 91. These results confirm the promising optoelectronic applications of WS2 quantum dots.
