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.

Ligands in Lead Halide Perovskite Nanocrystals: From Synthesis to Optoelectronic Applications.

Ligands are indispensable for perovskite nanocrystals (NCs) throughout the whole lifetime, as they not only play key roles in the controllable synthesis of NCs with different sizes and shapes, but also act as capping shell that affects optical properties and electrical coupling of NCs. Establishing a systematic understanding of the relationship between ligands and perovskite NCs is significant to enable many potential applications of NCs. This review mainly focuses on the influence of ligands on perovskite NCs. First of all, the ligands-dominated size and shape control of NCs is discussed. Whereafter, the surface defects of NCs and the bonding between ligands and perovskite NCs are classified, and corresponding post-treatment of surface defects via ligands is also summarized. Furthermore, advances in engineering the ligands towards the high performance of optoelectronic devices based on perovskite NCs, including photodetector, solar cell, light emitting diode (LED), and laser, and finally to potential challenges are also discussed.

Graphdiyne-Based Single-Atom Catalysts with Different Coordination Environments.

As a special carbon material, graphdiyne (GDY) features the superiorities of incomplete charge transfer effect on the atomic level, tunable electronic structure and anchoring metal atoms directly with organometallic coordination bonds M (metal)-C (alkynyl carbon in GDY), providing it an ideal platform to construct single-atom catalysts (ACs). The coordination environment of single atoms anchored on GDY plays a key role in their catalytic performance. The mini-review highlights state-of-the-art progress in the rational design of GDY-based ACs and their applications, and mainly reveals the relationship between the coordination engineering of the GDY-based ACs and corresponding catalytic performance. Finally, some prospects concerning the future development of GDY-based ACs in energy conversion are also discussed.

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.

Constructing Cu-C Bonds in a Graphdiyne-Regulated Cu Single-Atom Electrocatalyst for CO2 Reduction to CH4.

Regulating intermediates through elaborate catalyst design to control the reaction direction is crucial for promoting the selectivity of electrocatalytic CO2 -to-CH4 . M-C (M=metal) bonds are particularly important for tuning the multi-electron reaction; however, its construction in nanomaterials is challenging. Here, via rational design of in situ anchoring of Cu SAs (single atoms) on the unique platform graphdiyne, we firstly realize the construction of a chemical bond Cu-C (GDY). In situ Raman spectroelectrochemistry and DFT calculations confirm that due to the fabrication of the Cu-C bond, during CO2 reduction, the formation of *OCHO intermediates is dominant rather than *COOH on Cu atoms, facilitating the formation of CH4 . Therefore, we find that constructing the Cu-C bond in Cu SAs/GDY can supply an efficient charge transfer channel, but most importantly control the reaction intermediates and guide a more facile reaction pathway to CH4 , thereby significantly boosting its catalytic performance. This work provides new insights on enhancing the selectivity for CO2 RR at the atomic level.

Pore size effect of graphyne supports on CO2 electrocatalytic activity of Cu single atoms.

The instinctive chemical inertia of CO2 impedes its electrochemical reduction by high energy input. Single atom catalysts (SACs) on supports are considered as a class of excellent electrocatalysts with high activity, selectivity and atomic efficiency for CO2 electrochemical reduction. Supports for single atoms are believed to greatly impact the electrocatalytic activity of SACs. However, further research on the relationship between the structure of supports for SACs and CO2 electroreduction is still needed. Herein, density functional theory (DFT) calculations are performed to investigate the role of supports in tuning the CO2 electrocatalytic activity of SACs. Graphynes with different pore sizes (graphyne, graphdiyne, graphyne-3 and graphyne-4) are taken into account to unveil the effect of their skeleton structure on the anchored Cu single atoms. We found that support skeletons could greatly impact the coordination configuration of metal atoms and the steric repulsion of support skeletons to intermediates. These two factors jointly result in different electrocatalytic performances of SACs. The comparative analysis proves that the graphynes with large pores are appropriate supports for Cu adatoms for CO2 electroreduction due to the low-coordinated Cu atoms and weak-steric-repulsion carbon skeleton. Such SACs exhibit much enhanced activity and selectivity as compared with the Cu(111) surface and monoatomic Cu on nitrogen-doped graphene. This work provides a new insight into the rational design of supports for SACs.

A Chiral Reduced-Dimension Perovskite for an Efficient Flexible Circularly Polarized Light Photodetector.

Chiral quasi-2D perovskite single crystals (SCs) were investigated for their circular polarized light (CPL) detecting capability. Quasi-2D chiral perovskites, [(R)-ß-MPA]2 MAPb2 I7 ((R)-ß-MPA=(R)-(+)-ß-methylphenethylamine, MA=methylammonium), have intrinsic chirality and the capability to distinguish different polarization states of CPL photons. Corresponding quasi-2D SCs CPL photodetector exhibit excellent detection performance. In particular, our device responsivity is almost one order of magnitude higher than the reported 2D perovskite CPL detectors to date. The crystallization dynamics of the film were modulated to facilitate its carrier transport. Parallel oriented perovskite films with a homogeneous energy landscape is crucial to maximize the carrier collection efficiency. The photodetector also exhibits superior mechanical flexibility and durability, representing a promising candidate for sensitive and robust CPL photodetectors.

Electron-phonon interaction in efficient perovskite blue emitters.

Low-dimensional perovskites have-in view of their high radiative recombination rates-shown great promise in achieving high luminescence brightness and colour saturation. Here we investigate the effect of electron-phonon interactions on the luminescence of single crystals of two-dimensional perovskites, showing that reducing these interactions can lead to bright blue emission in two-dimensional perovskites. Resonance Raman spectra and deformation potential analysis show that strong electron-phonon interactions result in fast non-radiative decay, and that this lowers the photoluminescence quantum yield (PLQY). Neutron scattering, solid-state NMR measurements of spin-lattice relaxation, density functional theory simulations and experimental atomic displacement measurements reveal that molecular motion is slowest, and rigidity greatest, in the brightest emitter. By varying the molecular configuration of the ligands, we show that a PLQY up to 79% and linewidth of 20 nm can be reached by controlling crystal rigidity and electron-phonon interactions. Designing crystal structures with electron-phonon interactions in mind offers a previously underexplored avenue to improve optoelectronic materials' performance.

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.

Fast Postmoisture Treatment of Luminescent Perovskite Films for Efficient Light-Emitting Diodes.

Despite the recent advances in the performance of perovskite light-emitting diodes (PeLEDs), the effects of water on the perovskite emissive layer and its electroluminescence are still unclear, even though it has been previously demonstrated that moisture has a significant impact on the quality of perovskite films in the fabrication process of perovskite solar cells and is a prerequisite for obtaining high-performance PeLEDs. Here, the effects of postmoisture on the luminescent CH3 NH3 PbBr3 (MAPbBr3 ) perovskite films are systematically investigated. It is found that postmoisture treatment can efficiently control the morphology and growth of perovskite films and only a fast moisture exposure at a 60% high relative humidity results in significantly improved crystallinity, carrier lifetime, and photoluminescence quantum yield of perovskite films. With the optimized moisture-treated perovskite films, a high-performance PeLED is fabricated, exhibiting a maximum current efficiency of 20.4 cd A-1 , which is an almost 20-fold enhancement when compared with perovskite films without moisture treatment. The results provide valuable insights into the moisture-assisted growth of luminescent perovskite films and will aid in the development of high-performance perovskite light-emitting devices.

Tailoring the Energy Landscape in Quasi-2D Halide Perovskites Enables Efficient Green-Light Emission.

Organo-metal halide perovskites are a promising platform for optoelectronic applications in view of their excellent charge-transport and bandgap tunability. However, their low photoluminescence quantum efficiencies, especially in low-excitation regimes, limit their efficiency for light emission. Consequently, perovskite light-emitting devices are operated under high injection, a regime under which the materials have so far been unstable. Here we show that, by concentrating photoexcited states into a small subpopulation of radiative domains, one can achieve a high quantum yield, even at low excitation intensities. We tailor the composition of quasi-2D perovskites to direct the energy transfer into the lowest-bandgap minority phase and to do so faster than it is lost to nonradiative centers. The new material exhibits 60% photoluminescence quantum yield at excitation intensities as low as 1.8 mW/cm2, yielding a ratio of quantum yield to excitation intensity of 0.3 cm2/mW; this represents a decrease of 2 orders of magnitude in the excitation power required to reach high efficiency compared with the best prior reports. Using this strategy, we report light-emitting diodes with external quantum efficiencies of 7.4% and a high luminescence of 8400 cd/m2.

Ligand-Stabilized Reduced-Dimensionality Perovskites.

Metal halide perovskites have rapidly advanced thin-film photovoltaic performance; as a result, the materials' observed instabilities urgently require a solution. Using density functional theory (DFT), we show that a low energy of formation, exacerbated in the presence of humidity, explains the propensity of perovskites to decompose back into their precursors. We find, also using DFT, that intercalation of phenylethylammonium between perovskite layers introduces quantitatively appreciable van der Waals interactions. These drive an increased formation energy and should therefore improve material stability. Here we report reduced-dimensionality (quasi-2D) perovskite films that exhibit improved stability while retaining the high performance of conventional three-dimensional perovskites. Continuous tuning of the dimensionality, as assessed using photophysical studies, is achieved by the choice of stoichiometry in materials synthesis. We achieve the first certified hysteresis-free solar power conversion in a planar perovskite solar cell, obtaining a 15.3% certified PCE, and observe greatly improved performance longevity.

Jointly tuned plasmonic-excitonic photovoltaics using nanoshells.

Recent advances in spectrally tuned, solution-processed plasmonic nanoparticles have provided unprecedented control over light's propagation and absorption via engineering at the nanoscale. Simultaneous parallel progress in colloidal quantum dot photovoltaics offers the potential for low-cost, large-area solar power; however, these devices suffer from poor quantum efficiency in the more weakly absorbed infrared portion of the sun's spectrum. Here, we report a plasmonic-excitonic solar cell that combines two classes of solution-processed infrared materials that we tune jointly. We show through experiment and theory that a plasmonic-excitonic design using gold nanoshells with optimized single particle scattering-to-absorption cross-section ratios leads to a strong enhancement in near-field absorption and a resultant 35% enhancement in photocurrent in the performance-limiting near-infrared spectral region.

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.

Eliminating Halogen Vacancies Enables Efficient MACL-Assisted Formamidine Perovskite Solar Cells.

Methylammonium chloride (MACl) additive is almost irreplaceable in high-performance formamidine perovskite photovoltaics. Nevertheless, Some of the problems that can arise from adding MACl are rarely mentioned. Herein, it is proposed for the first time that the addition of MACl would cause the non-stoichiometric ratio in the perovskite film, resulting in the halogen vacancy. It is demonstrated that the non-synchronous volatilization of methylamine cations and chloride ions leads to the formation of halogen vacancy defects. To solve this problem, the NH4 HCOO is introduced into the perovskite precursor solution to passivate the halogen vacancy. The HCOO- ions have a strong force with lead ions and can fill the halogen vacancy defects. Consequently, the champion devices' power conversion efficiency (PCE) can be improved from 21.23% to 23.72% with negligible hysteresis. And the unencapsulated device can still retain >90% of the initial PCE even operating in N2 atmosphere for over 1200 h. This work illustrates another halogen defect source in the MACl-assisted formamidine perovskite photovoltaics and provides a new route to obtain high-performance perovskite solar cells.

Strain Regulation of Mixed-Halide Perovskites Enables High-Performance Wide-Bandgap Photovoltaics.

Wide-bandgap mixed-halogen perovskite materials are widely used as top cells in tandem solar cells. However, serious open-circuit voltage (Voc) loss restricts the power conversion efficiency (PCE) of wide-bandgap perovskite solar cells (PSCs). Herein, it is shown that the resulting methylammonium vacancies induce lattice distortion in methylammonium chloride-assisted perovskite film, resulting in an inhomogeneous halogen distribution and low Voc. Thus, a lattice strain regulation strategy is reported to fabricate high-performance wide-bandgap PSCs. Rubidium (Rb) cations are introduced to fill the A-site vacancy caused by the methylammonium volatilization, which alleviates shrinkage strain of the perovskite crystal. The reduced lattice distortion and increased halide ion migration barrier result in a homogeneous mixed-halide perovskite film. Due to improved carrier transport and suppressed nonradiative recombination, the Rb-treated wide-bandgap PSC (1.68 eV) achieves an excellent PCE of 21.72%, accompanied by a high Voc of 1.22 V. The resulting device maintains more than 90% of its initial PCE after 1500 h under 1-sun illumination conditions.

Structural Modification Strategies, Interfacial Charge-Carrier Dynamics, and Solar Energy Conversion Applications of Organic-Inorganic Halide Perovskite Photocatalysts.

Over the past few decades, organic-inorganic halide perovskites (OIHPs) as novel photocatalyst materials have attracted intensive attention for an impressive variety of photocatalytic applications due to their excellent photophysical (chemical) properties. Regarding practical application and future commercialization, the air-water stability and photocatalytic performance of OIHPs need to be further improved. Accordingly, studying modification strategies and interfacial interaction mechanisms is crucial. In this review, the current progress in the development and photocatalytic fundamentals of OIHPs is summarized. Furthermore, the structural modification strategies of OIHPs, including dimensionality control, heterojunction design, encapsulation techniques, and so on for the enhancement of charge-carrier transfer and the enlargement of long-term stability, are elucidated. Subsequently, the interfacial mechanisms and charge-carrier dynamics of OIHPs during the photocatalytic process are systematically specified and classified via diverse photophysical and electrochemical characterization methods, such as time-resolved photoluminescence measurements, ultrafast transient absorption spectroscopy, electrochemical impedance spectroscopy measurements, transient photocurrent densities, and so forth. Eventually, various photocatalytic applications of OIHPs, including hydrogen evolution, CO2 reduction, pollutant degradation, and photocatalytic conversion of organic matter.