Unveiling the Localized Exciton-Based Photoluminescence of Manganese Doped Cesium Zinc Halide Nanocrystals.

Lead-free metal halide nanocrystals (NCs) have aroused increasing attention due to their unique optoelectronic properties based on localized excitons (LEs). However, the vital influencing factors for the LEs based photoluminescence (PL) are still not well-understood due to the coupling of various intrinsic and extrinsic factors of the NCs. Herein, by engineering the phase, size, morphology, and chemical composition, we are able to decouple the intrinsic and extrinsic factors of manganese doped cesium zinc-halide NCs. We found both the intrinsic metal-halide coordination field and the extrinsic crystal defects have significant influences on the LEs' recombination and energy transfer processes, and hence determine the PL efficiency. Unlike for the free excitons (FEs) based PL, the phase as well as the crystal morphology do not play major roles for the LEs based PL. This work provides a new insight for the study of LE dynamics of metal halide NCs.

Highly Luminescent One-Dimensional Organic-Inorganic Hybrid Double-Perovskite-Inspired Materials for Single-Component Warm White-Light-Emitting Diodes.

Double perovskites (DPs) are one of the most promising candidates for developing white light-emitting diodes (WLEDs) owing to their intrinsic broadband emission from self-trapped excitons (STEs). Translation of three-dimensional (3D) DPs to one-dimensional (1D) analogues, which could break the octahedral tolerance factor limit, is so far remaining unexplored. Herein, by employing a fluorinated organic cation, we report a series of highly luminescent 1D DP-inspired materials, (DFPD)2 MI InBr6 (DFPD=4,4-difluoropiperidinium, MI =K+ and Rb+ ). Highly efficient warm-white photoluminescence quantum yield of 92 % is achieved by doping 0.3 % Sb3+ in (DFPD)2 KInBr6 . Furthermore, single-component warm-WLEDs fabricated with (DFPD)2 KInBr6 :Sb yield a luminance of 300 cd/m2 , which is one of the best-performing lead-free metal-halides WLEDs reported so far. Our study expands the scope of In-based metal-halides from 3D to 1D, which exhibit superior optical performances and broad application prospects.

All-Inorganic Lead-Free 0D Perovskites by a Doping Strategy to Achieve a PLQY Boost from <2 % to 90 .

Zero-dimensional (0D) lead-free perovskites have unique structures and optoelectronic properties. Undoped and Sb-doped all inorganic, lead-free, 0D perovskite single crystals A2 InCl5 (H2 O) (A=Rb, Cs) are presented that exhibit greatly enhanced yellow emission. To study the effect of coordination H2 O, Sb-doped A3 InCl6 (A=Rb, Cs) are also synthesized and further studied. The photoluminescence (PL) color changes from yellow to green emission. Interestingly, the photoluminescence quantum yield (PLQY) realizes a great boost from <2 % to 85-95 % through doping Sb3+ . We further explore the effect of Sb3+ dopants and the origin of bright emission by ultrafast transient absorption techniques. Furthermore, Sb-doped 0D rubidium indium chloride perovskites show excellent stability. These findings not only provide a way to design a set of new high-performance 0D lead-free perovskites, but also reveal the relationship between structure and PL properties.

Lead-Free Sodium-Indium Double Perovskite Nanocrystals through Doping Silver Cations for Bright Yellow Emission.

Lead-free halide perovskite nanocrystals (NCs) have drawn wide attention for solving the problem of lead perovskites toxicity and instability. Herein, we synthesize the direct band gap double perovskites undoped and Ag-doped Cs2 NaInCl6 NCs by variable temperature hot injection. The Cs2 NaInCl6 NCs have little photoluminescence because of dark self-trapped excitons (STEs). The dark STEs can be converted into bright STEs by doping with Ag+ to produce a bright yellow emission, with the highest photoluminescence quantum efficiency of 31.1 %. The dark STEs has been directly detected experimentally by ultrafast transient absorption (TA) techniques. The dynamics mechanism is further studied. In addition, the Ag-doped NCs show better stability than the undoped ones. This result provides a new way to enhance the optical properties of lead-free perovskites NCs for high-performance light emitters.

Lead-Free Silver-Bismuth Halide Double Perovskite Nanocrystals.

Lead-free perovskite nanocrystals (NCs) were obtained mainly by substituting a Pb2+ cation with a divalent cation or substituting three Pb2+ cations with two trivalent cations. The substitution of two Pb2+ cations with one monovalent Ag+ and one trivalent Bi3+ cations was used to synthesize Cs2 AgBiX6 (X=Cl, Br, I) double perovskite NCs. Using femtosecond transient absorption spectroscopy, the charge carrier relaxation mechanism was elucidated in the double perovskite NCs. The Cs2 AgBiBr6 NCs exhibit ultrafast hot-carrier cooling (<1 ps), which competes with the carrier trapping processes (mainly originate from the surface defects). Notably, the photoluminescence can be increased by 100 times with surfactant (oleic acid) added to passivate the defects in Cs2 AgBiCl6 NCs. These results suggest that the double perovskite NCs could be potential materials for optoelectronic applications by better controlling the surface defects.

Sb-Doped Cs3 TbCl6 Nanocrystals for Highly Efficient Narrow-Band Green Emission and X-Ray Imaging.

Metal halide nanocrystals (NCs) with high photoluminescence quantum yield (PLQY) are desirable for lighting, display, and X-ray detection. Herein, the novel lanthanide-based halide NCs are committed to designing and optimizing the optical and scintillating properties, so as to unravel the PL origin, exciton dynamics, and optoelectronic applications. Sb-doped zero-dimensional (0D) Cs3 TbCl6 NCs exhibit a green emission with a narrow full width of half maximum of 8.6 nm, and the best PLQY of 48.1% is about three times higher than that of undoped NCs. Experiments and theoretical calculations indicate that 0D crystalline and electronic structures make the exciton highly localized on [TbCl6 ]3- octahedron, which boosts the Cl- -Tb3+ charge transfer process, thus resulting in bright Tb3+ emission. More importantly, the introduction of Sb3+ not only facilitates the photon absorption transition, but also builds an effective thermally boosting energy transfer channel assisted by [SbCl6 ]3- -induced self-trapped state, which is responsible for the PL enhancement. The high luminescence efficiency and negligible self-absorption of the Cs3 TbCl6 : Sb nanoscintillator enable a more sensitive X-ray detection response compared with undoped sample. The study opens a new perspective to deeply understand the excited state dynamics of metal halide NCs, which helps to design high-performance luminescent lanthanide-based nanomaterials.

Highly Stable Cesium Molybdenum Chloride Perovskite Nanocrystals for Photothermal Semihydrogenation Applications.

Metal halide perovskite materials with excellent carrier transport properties have been regarded as a new class of catalysts with great application potential. However, their development is hampered by their instability in polar solvents and high temperatures. Herein, we report a solution-processed Cs2MoCl6 perovskite nanocrystals (NCs) capped with the Mo6+, showing high thermostability in polar solvents. Furthermore, the Pd single atoms (PdSA) can be anchored on the surface of Cs2MoCl6 NCs through the unique coordination structure of Pd-Cl sites, which exhibit excellent semihydrogenation of different alkyne derivatives with high selectivity at full conversion at room temperature. Moreover, the activity could be improved greatly under Xe lamp irradiation. Detailed experimental characterization and DFT calculations indicate the improved activity under light illumination is due to the synergistic effect of photo-to-heat conversion and photoinduced electron transfer from Cs2MoCl6 to PdSA, which facilitates the activation of the C≡C group. This work not only provides a new catalyst for high selective semihydrogenation of alkyne derivatives but also opens a new avenue for metal halides as photothermal catalysts.

Tb3+ and Bi3+ Co-Doping of Lead-Free Cs2NaInCl6 Double Perovskite Nanocrystals for Tailoring Optical Properties.

Lead halide perovskites have achieved remarkable success in various photovoltaic and optoelectronic applications, especially solar cells and light-emitting diodes (LEDs). Despite the significant advances of lead halide perovskites, lead toxicity and insufficient stability limit their commercialization. Lead-free double perovskites (DPs) are potential materials to address these issues because of their non-toxicity and high stability. By doping DP nanocrystals (NCs) with lanthanide ions (Ln3+), it is possible to make them more stable and impart their optical properties. In this work, a variable temperature hot injection method is used to synthesize lead-free Tb3+-doped Cs2NaInCl6 DP NCs, which exhibit a major narrow green photoluminescence (PL) peak at 544 nm derived from the transition of Tb3+ 5D4→7F5. With further Bi3+ co-doping, the Tb3+-Bi3+-co-doped Cs2NaInCl6 DP NCs are not only directly excited at 280 nm but are also excited at 310 nm and 342 nm. The latter have a higher PL intensity because partial Tb3+ ions are excited through more efficient energy transfer channels from the Bi3+ to the Tb3+ ions. The investigation of the underlying mechanism between the intrinsic emission of Cs2NaInCl6 NCs and the narrow green PL caused by lanthanide ion doping in this paper will facilitate the development of lead-free halide perovskite NCs.

Bright Green-Emitting All-Inorganic Terbium Halide Double Perovskite Nanocrystals for Low-Dose X-ray Imaging.

Inorganic halide double perovskite (DP) nanocrystals (NCs) have attracted great attention because of their nontoxicity, mild reaction conditions, good stability, and excellent optical and optoelectronic properties. Herein, we prepare the inorganic terbium halide DP Cs2BTbCl6 (B = Na or Ag) NCs with bright green photoluminescence (PL) emission. The Na-Tb-based DP NCs exhibit better PL properties compared with the Ag-Tb-based DP NCs, which is due to Cs2NaTbCl6 NCs having a more localized charge carrier distribution on the [TbCl6]3- octahedron. The incorporation of Sb3+ dopant in Cs2NaTbCl6 NCs can construct a more efficient energy transfer process, resulting in a doubling of PL efficiency. Furthermore, Cs2NaTbCl6: Sb3+ NCs possess excellent X-ray scintillating performance with a low-dose detection limit of 140 nGyair/s, which is nearly 5 times more sensitive than the undoped NCs. The optimized NCs show great application prospects in X-ray imaging. This work helps deepen the understanding of the luminescence mechanism, excited state dynamics, and scintillation property in Tb-based DP NCs.

Photocatalytic CO2 reduction to syngas using metallosalen covalent organic frameworks.

Metallosalen-covalent organic frameworks have recently gained attention in photocatalysis. However, their use in CO2 photoreduction is yet to be reported. Moreover, facile preparation of metallosalen-covalent organic frameworks with good crystallinity remains considerably challenging. Herein, we report a series of metallosalen-covalent organic frameworks produced via a one-step synthesis strategy that does not require vacuum evacuation. Metallosalen-covalent organic frameworks possessing controllable coordination environments of mononuclear and binuclear metal sites are obtained and act as photocatalysts for tunable syngas production from CO2. Metallosalen-covalent organic frameworks obtained via one-step synthesis exhibit higher crystallinity and catalytic activities than those obtained from two-step synthesis. The optimal framework material containing cobalt and triazine achieves a syngas production rate of 19.7 mmol g-1 h-1 (11:8 H2/CO), outperforming previously reported porous crystalline materials. This study provides a facile strategy for producing metallosalen-covalent organic frameworks of high quality and can accelerate their exploration in various applications.

Photon-Energy-Dependent Reversible Charge Transfer Dynamics of Double Perovskite Nanocrystal-Polymer Nanocomposites.

Combining steady-state photoluminescence and transient absorption (TA) spectroscopy, we have investigated the photoinduced charge transfer dynamics between lead-free Mn-doped Cs2NaIn0.75Bi0.25Cl6 double perovskite (DP) nanocrystals (NCs) and conjugated poly[2-methoxy-5-(3',7'-dimethyloctyloxy)-1,4-phenylenevinylene] (MDMO-PPV). Upon ultraviolet-A excitation, the photoinduced absorption feature of DP NCs/MDMO-PPV nanocomposites disappeared, and the stimulated emission weakened in the TA spectrum. This was due to charge transfer from the MDMO-PPV polymers to DP NCs. Upon a higher photon-energy ultraviolet-C excitation, stimulated emission and photoinduced absorption features vanished, indicating there existed a reversible charge transfer from DP NCs to MDMO-PPV polymers. Reversible charge transfer of Mn-doped DP NCs/MDMO-PPV nanocomposites was tuned by varying the excitation photon-energy. The manipulation of reversible charge transfer dynamics in the perovskite-polymer nanocomposites opens a new avenue for optical and optoelectronic applications.

Manganese-Doped, Lead-Free Double Perovskite Nanocrystals for Bright Orange-Red Emission.

Lead-free halide perovskite nanocrystals (NCs) have recently attracted attention due to their nontoxicity and stability as alternatives to lead-based perovskite NCs. Here, we report undoped and manganese-doped all-inorganic, lead-free double perovskite (DP) NCs: Cs2NaIn x Bi1-x Cl6 (0 < x < 1) and Cs2NaIn x Bi1-x Cl6:Mn (0 ≤ x ≤ 1) NCs. Undoped NCs exhibit blue emission. Through doping Mn2+ ions into Cs2NaIn x Bi1-x Cl6 NCs, we can avoid self-trapped exciton emission and realize bright orange red emission of Mn2+ dopants with the highest photoluminescence quantum efficiency of 44.6%. The photoluminescence (PL) is tunable from yellow emission to orange-red emission corresponding to a red shift from 583 to 614 nm with increasing In content. Interestingly, the PL emission of Mn-doped NCs shows a red shift from the bulk size to the nanoscale. The Mn-doped NCs show good stability in air. In addition, we further prove the process of dark self-trapped state-assisted Mn2+ emission in DP NCs by ultrafast transient absorption techniques.

Lead-Free Small-Bandgap Cs2CuSbCl6 Double Perovskite Nanocrystals.

Lead-free halide double perovskites (DPs) have attracted great attention due to their stability, nontoxicity and good photophysical property. In this work, we report a new, small-bandgap Cs2CuSbCl6 DP nanocrystals (NCs) with a bandgap of 1.66 eV, which is the smallest bandgap in reported lead-free three-dimensional DP NCs. Density functional theory calculations confirm that Cs2CuSbCl6 DP has an indirect bandgap of 1.70 eV, in good agreement with the experimental result. The photophysical property of Cs2CuSbCl6 NCs is studied by the combination of femtosecond transient absorption (TA) and nanosecond TA techniques. In addition, the Cs2CuSbCl6 NCs exhibit good stability exposed in the air. These results show that these NCs will have great potential to be used as a light-absorbing material for photovoltaic applications.