Synthesis-on-substrate of quantum dot solids.

Perovskite light-emitting diodes (PeLEDs) with an external quantum efficiency exceeding 20% have been achieved in both green and red wavelengths1-5; however, the performance of blue-emitting PeLEDs lags behind6,7. Ultrasmall CsPbBr3 quantum dots are promising candidates with which to realize efficient and stable blue PeLEDs, although it has proven challenging to synthesize a monodispersed population of ultrasmall CsPbBr3 quantum dots, and difficult to retain their solution-phase properties when casting into solid films8. Here we report the direct synthesis-on-substrate of films of suitably coupled, monodispersed, ultrasmall perovskite QDs. We develop ligand structures that enable control over the quantum dots' size, monodispersity and coupling during film-based synthesis. A head group (the side with higher electrostatic potential) on the ligand provides steric hindrance that suppresses the formation of layered perovskites. The tail (the side with lower electrostatic potential) is modified using halide substitution to increase the surface binding affinity, constraining resulting grains to sizes within the quantum confinement regime. The approach achieves high monodispersity (full-width at half-maximum = 23 nm with emission centred at 478 nm) united with strong coupling. We report as a result blue PeLEDs with an external quantum efficiency of 18% at 480 nm and 10% at 465 nm, to our knowledge the highest reported among perovskite blue LEDs by a factor of 1.5 and 2, respectively6,7.

Mixed-Halide Perovskites with Halogen Bond Induced Interlayer Locking Structure for Stable Pure-Red PeLEDs.

Mixed-halide perovskites enable precise spectral tuning across the entire spectral range through composition engineering. However, mixed halide perovskites are susceptible to ion migration under continuous illumination or electric field, which significantly impedes the actual application of perovskite light-emitting diodes (PeLEDs). Here, we demonstrate a novel approach to introduce strong and homogeneous halogen bonds within the quasi-two-dimensional perovskite lattices by means of an interlayer locking structure, which effectively suppresses ion migration by increasing the corresponding activation energy. Various characterizations confirmed that intralattice halogen bonds enhance the stability of quasi-2D mixed-halide perovskite films. Here, we report that the PeLEDs exhibit an impressive 18.3% EQE with pure red emission with CIE color coordinate of (0.67, 0.33) matching Rec. 2100 standards and demonstrate an operational half-life of ∼540 min at an initial luminance of 100 cd m-2, representing one of the most stable mixed-halide pure red PeLEDs reported to date.

Universal Molecular Control Strategy for Scalable Fabrication of Perovskite Light-Emitting Diodes.

Despite the rapid progress in perovskite light-emitting diodes (PeLEDs), the electroluminescence performance of large-area perovskite devices lags far behind that of laboratory-size ones. Here, we report a 3.5 cm × 3.5 cm large-area PeLED with a record-high external quantum efficiency of 12.1% by creating an amphipathic molecular interface modifier of betaine citrate (BC) between the perovskite layer and the underlying hole transport layer (HTL). It is found that the surface wettability for various HTLs can be efficiently improved as a result of the coexistence of methyl and carboxyl groups in the BC molecules that makes favorable groups to selectively contact with the HTL surface and increases the surface free energy, which greatly facilitates the scalable process of solution-processed perovskite films. Moreover, the luminous performance of perovskite emitters is simultaneously enhanced through the coordination between C═O in the carboxyl groups and Pb dangling bonds.

Manipulating Local Lattice Distortion for Spectrally Stable and Efficient Mixed-halide Blue Perovskite LEDs.

Mixed-halide perovskites are considered the most straightforward candidate to realize blue perovskite light-emitting diodes (PeLEDs). However, they suffer severe halide migration, leading to spectral instability, which is particularly exaggerated in high chloride alloying perovskites. Here, we demonstrate energy barrier of halide migration can be tuned by manipulating the degree of local lattice distortion (LLD). Enlarging the LLD degree to a suitable level can increase the halide migration energy barrier. We herein report an "A-site" cation engineering to tune the LLD degree to an optimal level. DFT simulation and experimental data confirm that LLD manipulation suppresses the halide migration in perovskites. Conclusively, mixed-halide blue PeLEDs with a champion EQE of 14.2 % at 475 nm have been achieved. Moreover, the devices exhibit excellent operational spectral stability (T50 of 72 min), representing one of the most efficient and stable pure-blue PeLEDs reported yet.

Preliminary study for the stimulation effect of plant-based meals on pure culture Lactobacillus plantarum growth and acidification in milk fermentation.

Fermented dairy products have been recognized as the best carriers for the administration of probiotics. Because one of the potential probiotic strains, Lactobacillus plantarum, has poor proteolytic ability and weak acidifying capacity in milk fermentation, the aim of this study was to preliminarily investigate the stimulation effect of plant-based meals on L. plantarum CCFM8661 growth in milk, and subsequently develop a yogurt or yogurt drinks containing probiotic strain L. plantarum CCFM8661. Milk supplemented with different concentrations (5 to 10%, wt/wt) of oat extract and malt extract, inoculated with 2.5 × 107 cfu/mL of L. plantarum CCFM8661, and then incubated at 35°C. The pH value, titration acidity, and viable cell counts during 48-h fermentation at 35°C and 25-d storage at 4°C, were determined at different intervals. The results showed that the promotion effects of oat extract and malt extract on L. plantarum CCFM8661 growth rate in milk were much stronger than almond, walnut, sweet corn, peanut, and soybean meals. In addition, the stimulation effect of oat extract was associated with its concentration, and was much stronger than that of malt extract. Furthermore, viable counts and titration acidity of yogurt were gradually increased in the oat extract group, whereas viable counts were gradually decreased and titration acidity were slightly increased in the malt extract group during the 25-d storage at 4°C.

A-site Cation Engineering for Highly Efficient MAPbI3 Single-Crystal X-ray Detector.

Metal halide perovskites have emerged as a new generation of X-ray detector materials. However, large-sized MAPbI3 single crystals (SCs) still exhibit lower performance than MAPbBr3 SCs in X-ray detection. DFT (density functional theory) simulations suggest the problem could be overcome by alloying large-sized cations at the A site. The alloyed process could notably decrease the electron-phonon coupling strength and increase the material defect formation energy. Accordingly, centimeter-sized alloyed DMAMAPbI3 (DMA=dimethylammonium) and GAMAPbI3 (GA=guanidinium) SCs are obtained. Electrical characterizations confirm the GAMAPbI3 SCs display improved charge collection efficiency. It also exhibits a remarkable reduction of dark current, an important figure of merit for X-ray detectors. With a judiciously designed device architecture, the overall detector performance confirms GAMAPbI3 SCs as one of the most sensitive perovskite X-ray detectors to date.

Stable and Efficient Mixed-halide Perovskite LEDs.

Tailoring bandgap by mixed-halide strategy in perovskites has attracted extraordinary attention due to the flexibility of halide ion combinations and has emerged as the most direct and effective approach to precisely tune the emission wavelength throughout the entire visible light spectrum. Mixed-halide perovskites, yet, still suffered from several problems, particularly phase segregation under external stimuli because of ions migration. Understanding the essential cause and finding sound strategies, thus, remains a challenge for stable and efficient mixed-halide perovskite light-emitting diodes (PeLEDs). The review herein presents an overview of the diverse application scenarios and the profound significance associated with mixed-halide perovskites. We then summarize the challenges and potential research directions toward developing high stable and efficient mixed-halide PeLEDs. The review thus provides a systematic and timely summary for the community to deepen the understanding of mixed-halide perovskite materials and resulting PeLEDs.

Structure-Guided Approaches for Enhanced Spin-Splitting in Chiral Perovskite.

Hybrid organic-inorganic perovskites with diverse lattice structures and chemical composition provide an ideal material platform for novel functionalization, including chirality transfer. Chiral perovskites combine organic and inorganic sublattices, therefore encoding the structural asymmetry into the electronic structures and giving rise to the spin-splitting effect. From a structural chemistry perspective, the magnitude of the spin-splitting effect crucially depends on the noncovalent and electrostatic interaction within the chiral perovskite, which induces the local site and long-range bulk inversion symmetry breaking. In this regard, we systematically retrospect the structure-property relationships in chiral perovskite. Insight into the rational design of chiral perovskites based on molecular configuration, dimensionality, and chemical composition along with their effects on spin-splitting manifestation is presented. Lastly, challenges in purposeful material design and further integration into chiral perovskite-based spintronic devices are outlined. With an understanding of fundamental chemistry and physics, we believe that this Perspective will propel the application of multifunctional spintronic devices.

Uniaxial-Oriented Chiral Perovskite for Flexible Full-Stokes Polarimeter.

Full-Stokes polarization detection, with high integration and portability, offers an efficient path toward next-gen multi-information optoelectronic systems. Nevertheless, current techniques relying on optical filters create rigid and bulky configurations, limiting practicality. Here, a flexible, filter-less full-Stokes polarimeter featuring a uniaxial-oriented chiral perovskite film is first reported. It is found that, the strategic manipulation of the surfactant-mediated Marangoni effect during blade coating, is crucial for guiding an equilibrious mass transport to achieve oriented crystallization. Through this approach, the obtained uniaxial-oriented chiral perovskite films inherently possess anisotropy and chirality, and thereby with desired sensitivity to both linearly polarized light and circularly polarized light vectors. The uniaxial-oriented crystalline structure also improves photodetection, achieving a specific detectivity of 5.23 × 1013 Jones, surpassing non-oriented devices by 10×. The as-fabricated flexible polarimeters enable accurate capture of full-Stokes polarization without optical filters, exhibiting slight detection errors for the Stokes parameters: ΔS1 = 9.2%, ΔS2 = 8.6%, and ΔS3 = 6.5%, approaching the detection accuracy of optics-filter polarimeters. This proof of concept also demonstrates applications in matrix polarization imaging.

Multi-functional fluorescent probe for Hg2+, Cu2+ and ClO- based on a pyrimidin-4-yl phenothiazine derivative.

A multi-functional fluorescent probe based on PzDPM (10-ethyl-3,7-di(pyrimidin-4-yl)-10H-phenothiazine) for Hg(2+), Cu(2+) and ClO(-) has been synthesized and characterized. The probe comprises an electron-donating fluorophore core of 10-ethylphenothiazine and two Hg(2+)-specific chelating arms of pyrimidin-4-yl. The 10-ethylphenothiazine also acts as a Cu(2+)/ClO(-)-specific reactive moiety. PzDPM exhibits green fluorescence and selectively senses Hg(2+)/Cu(2+) upon coordination/reaction in acetonitrile (MeCN), and behaves as a turn-off chemosensor or ratiometric chemodosimeter, respectively. On the other hand, PzDPM is very weakly emissive in aqueous solution but acts as an excellent turn-on chemodosimeter for ClO(-) in 1 : 4 (v/v) MeCN : Tris-HCl (10 mM, pH = 7.0) with a maximum fluorescent intensity increase of over 110-fold. The probe PzDPM allows the determination of Hg(2+), Cu(2+) and ClO(-) at 10(-7) M levels with satisfactory selectivity.

Toward the Controlled Synthesis of Lead Halide Perovskite Nanocrystals.

Lead halide perovskite nanocrystals (LHP NCs) have rapidly emerged as one of the most promising materials for optical sources, photovoltaics, and sensor fields. The controlled synthesis of LHP NCs with high monodispersity and precise size tunability has been a subject of intensive research in recent years. However, due to their ionic nature, LHP NCs are usually formed instantaneously, and the corresponding nucleation and growth are difficult to monitor and regulated. In this Perspective, we summarize the representative attempts to achieve controlled synthesis of LHP NCs. We first highlight the burst nucleation and rapid growth characteristics of conventional synthesis methods. Afterward, we introduce the scheme of changing the LHP NCs into kinetically dominant, continuously size-tunable synthesis via nucleation-growth decoupling. We also summarize methods to eliminate undesired ripening effects and achieve homogeneous size distribution through rational ligand selection and solvent engineering. We hope this Perspective will facilitate the development of controlled LHP NCs synthesis protocols and advance the understanding of crystal growth fundamentals of perovskite materials.

Open-circuit voltage loss in perovskite quantum dot solar cells.

Perovskite quantum dots are a competitive candidate for next-generation solar cells owing to their superior phase stability and multiple exciton generation effects. However, given the voltage loss in perovskite quantum dot solar cells (PQDSCs) is mainly caused by various surface and interfacial defects and the energy band mismatch in the devices, tremendous achievements have been made to mitigate the Voc loss of PQDSCs. Herein, we elucidate the potential threats that hinder the high Voc of PQDSCs. Then, we summarize recent progress in minimizing open-circuit voltage (Voc) loss, including defect manipulation and device optimization, based on band-alignment engineering. Finally, we attempt to shed light on the methodologies used to further improve the performance of PQDSCs.

Unraveling Size-Dependent Ion-Migration for Stable Mixed-Halide Perovskite Light-Emitting Diodes.

Mixed-halide perovskites show tunable emission wavelength across the visible-light range, with optimum control of the light color. However, color stability remains limited due to the notorious halide segregation under illumination or an electric field. Here, a versatile path toward high-quality mixed-halide perovskites with high emission properties and resistance to halide segregation is presented. Through systematic in and ex situ characterizations, key features for this advancement are proposed: a slowed and controllable crystallization process can promote achievement of halide homogeneity, which in turn ensures thermodynamic stability; meanwhile, downsizing perovskite nanoparticle to nanometer-scale dimensions can enhance their resistance to external stimuli, strengthening the phase stability. Leveraging this strategy, devices are developed based on CsPbCl1.5 Br1.5 perovskite that achieves a champion external quantum efficiency (EQE) of 9.8% at 464 nm, making it one of the most efficient deep-blue mixed-halide perovskite light-emitting diodes (PeLEDs) to date. Particularly, the device demonstrates excellent spectral stability, maintaining a constant emission profile and position for over 60 min of continuous operation. The versatility of this approach with CsPbBr1.5 I1.5 PeLEDs is further showcased, achieving an impressive EQE of 12.7% at 576 nm.

Energy-Funneling Process in Quasi-2D Perovskite Light-Emitting Diodes.

Quasi-two-dimensional (quasi-2D) perovskites, demonstrating excellent radiative efficiency and facile processability, have been considered as next-generation materials for light-emitting applications. Quasi-2D perovskites with a unique energy-funneling process offer an approach to achieve not only high photoluminescence quantum yields at low excitation but also tunable emission induced by dielectric and quantum confinement. In this Perspective, we highlight the mechanism of the energy-funneling process and discuss the salient position of it in quasi-2D perovskite materials for light-emitting applications; we then present the significance of component and molecular engineering strategies for the energy-funneling process to meet the requirements of stable emission and display technologies. Considering present achievements, we also provide promising directions for future advancements of quasi-2D perovskite materials. We hope this Perspective can provide a new viewpoint for researchers to encourage the commercial progress of quasi-2D perovskites for light-emitting applications.

High-performance quasi-2D perovskite light-emitting diodes: from materials to devices.

Quasi-two-dimensional (quasi-2D) perovskites have attracted extraordinary attention due to their superior semiconducting properties and have emerged as one of the most promising materials for next-generation light-emitting diodes (LEDs). The outstanding optical properties originate from their structural characteristics. In particular, the inherent quantum-well structure endows them with a large exciton binding energy due to the strong dielectric- and quantum-confinement effects; the corresponding energy transfer among different n-value species thus results in high photoluminescence quantum yields (PLQYs), particularly at low excitation intensities. The review herein presents an overview of the inherent properties of quasi-2D perovskite materials, the corresponding energy transfer and spectral tunability methodologies for thin films, as well as their application in high-performance LEDs. We then summarize the challenges and potential research directions towards developing high-performance and stable quasi-2D PeLEDs. The review thus provides a systematic and timely summary for the community to deepen the understanding of quasi-2D perovskite materials and resulting LED devices.

Reducing the impact of Auger recombination in quasi-2D perovskite light-emitting diodes.

Rapid Auger recombination represents an important challenge faced by quasi-2D perovskites, which induces resulting perovskite light-emitting diodes' (PeLEDs) efficiency roll-off. In principle, Auger recombination rate is proportional to materials' exciton binding energy (Eb). Thus, Auger recombination can be suppressed by reducing the corresponding materials' Eb. Here, a polar molecule, p-fluorophenethylammonium, is employed to generate quasi-2D perovskites with reduced Eb. Recombination kinetics reveal the Auger recombination rate does decrease to one-order-of magnitude lower compared to its PEA+ analogues. After effective passivation, nonradiative recombination is greatly suppressed, which enables resulting films to exhibit outstanding photoluminescence quantum yields in a broad range of excitation density. We herein demonstrate the very efficient PeLEDs with a peak external quantum efficiency of 20.36%. More importantly, devices exhibit a record luminance of 82,480 cd m-2 due to the suppressed efficiency roll-off, which represent one of the brightest visible PeLEDs yet.

High-performance large-area quasi-2D perovskite light-emitting diodes.

Serious performance decline arose for perovskite light-emitting diodes (PeLEDs) once the active area was enlarged. Here we investigate the failure mechanism of the widespread active film fabrication method; and ascribe severe phase-segregation to be the reason. We thereby introduce L-Norvaline to construct a COO--coordinated intermediate phase with low formation enthalpy. The new intermediate phase changes the crystallization pathway, thereby suppressing the phase-segregation. Accordingly, high-quality large-area quasi-2D films with desirable properties are obtained. Based on this, we further rationally adjusted films' recombination kinetics. We reported a series of highly-efficient green quasi-2D PeLEDs with active areas of 9.0 cm2. The peak EQE of 16.4% is achieved in = 3, represent the most efficient large-area PeLEDs yet. Meanwhile, high brightness device with luminance up to 9.1 × 104 cd m-2 has achieved in = 10 film.

Smoothing the energy transfer pathway in quasi-2D perovskite films using methanesulfonate leads to highly efficient light-emitting devices.

Quasi-two-dimensional (quasi-2D) Ruddlesden-Popper (RP) perovskites such as BA2Csn-1PbnBr3n+1 (BA = butylammonium, n > 1) are promising emitters, but their electroluminescence performance is limited by a severe non-radiative recombination during the energy transfer process. Here, we make use of methanesulfonate (MeS) that can interact with the spacer BA cations via strong hydrogen bonding interaction to reconstruct the quasi-2D perovskite structure, which increases the energy acceptor-to-donor ratio and enhances the energy transfer in perovskite films, thus improving the light emission efficiency. MeS additives also lower the defect density in RP perovskites, which is due to the elimination of uncoordinated Pb2+ by the electron-rich Lewis base MeS and the weakened adsorbate blocking effect. As a result, green light-emitting diodes fabricated using these quasi-2D RP perovskite films reach current efficiency of 63 cd A-1 and 20.5% external quantum efficiency, which are the best reported performance for devices based on quasi-2D perovskites so far.

Structured Perovskite Light Absorbers for Efficient and Stable Photovoltaics.

Organic-inorganic hybrid lead-halide perovskite materials (ABX3 ) have attracted widespread attention in the field of photovoltaics owing to their impressive optical and electrical properties. However, obstacles still exist in the commercialization of perovskite photovoltaics, such as poor stability, hysteresis, and human toxicity. A-site cation engineering is considered to be a powerful tool to tune perovskite structures and the resulting optoelectronic properties. Based on the selection and combination of A-site cations, three types of perovskite structures, i.e., 3D perovskite, reduced-dimensional (2D/quasi-2D) perovskite, and 2D/3D hybrid perovskite can be formed. Herein, the remarkable breakthroughs resulting from these three perovskite structures are summarized, and their corresponding properties and characteristics, as well as their intrinsic disadvantages, are highlighted. By summarizing recent research progress, a new viewpoint for improving the performance and stability of perovskite photovoltaics is provided.

Direct Observation of Competition between Amplified Spontaneous Emission and Auger Recombination in Quasi-Two-Dimensional Perovskites.

Quasi-two-dimensional (quasi-2D) Ruddlesden-Popper perovskites (RPPs) have been reported recently as laser media. The carrier dynamics of lasing in quasi-2D RPP films is still controversial. This work presents the amplified spontaneous emission (ASE) at room temperature based on the solution-processed quasi-2D (PEA)2Csn-1PbnBr3n+1 (⟨n⟩ = 3-5) thin films. Transient absorption spectroscopy was conducted to demonstrate the accumulation of excitons and population inversion for ASE caused by the energy transfer process along cascade quantum wells. The competition between the ASE and Auger recombination processes was observed via systematic and quantitative studies on the carrier dynamics. It is found that the contribution of Auger recombination is reduced by decreasing the temperature or adjusting the domain distribution of the quasi-2D RPP films, in order to achieve lower thresholds. This work re-emphasizes the importance of Auger recombination control for achieving low-threshold electrically or continuous-wave driven lasers and deepens the fundamental understanding of charge carrier dynamics of lasing in quasi-2D perovskite films.