Ligand Engineering Enables Efficient Pure Red Tin-Based Perovskite Light-Emitting Diodes.

With increasing ecological and environmental concerns, tin (Sn)-based perovskite light-emitting diodes (PeLEDs) are competitive candidates for future displays because of their environmental friendliness, excellent photoelectric properties, and low-cost solution-processed fabrication. Nonetheless, their electroluminescence (EL) performance still lags behind that of lead (Pb)-based PeLEDs due to the fast crystallization rate of Sn-based perovskite films and undesired oxidation from Sn2+ to Sn4+ , leading to poor film morphology and coverage, as well as high density defects. Here, we propose a ligand engineering strategy to construct high-quality phenethylammonium tin iodide (PEA2 SnI4 ) perovskite films by using L-glutathione reduced (GSH) as surface ligands toward efficient pure red PEA2 SnI4 -based PeLEDs. We show that the hydrogen-bond and coordinate interactions between GSH and PEA2 SnI4 effectively reduce the crystallization rate of the perovskites and suppress the oxidation of Sn2+ and formation of defects. The improved pure red perovskite films not only show excellent uniformity, density, and coverage but also exhibit enhanced optical properties and stability. Finally, state-of-the-art pure red PeLEDs achieve a record external quantum efficiency of 9.32 % in the field of PEA2 SnI4 -based devices. This work demonstrates that ligand engineering represents a feasible route to enhance the EL performance of Sn-based PeLEDs.

Weakening Ligand-Liquid Affinity to Suppress the Desorption of Surface-Passivated Ligands from Perovskite Nanocrystals.

The interfacial migration of surface-bound ligands highly affects the colloidal stability and optical quality of semiconductor nanocrystals, of which the underlying mechanism is not fully understood. Herein, colloidal CsPbBr3 perovskite nanocrystals (PNCs) with fragile dynamic equilibrium of ligands are taken as the examples to reveal the important role of balancing ligand-solid/solvent affinity in suppressing the desorption of ligands. As a micellar surfactant, glycyrrhizic acid (GA) with bulky hydrophobic and hydrophilic groups exhibits a relatively smaller diffusion coefficient (∼440 µm2/s in methanol) and weaker ligand-liquid affinity than that of conventional alkyl amine and carboxy ligands. Consequently, hydrophilic GA-passivated PNCs (PNCs-GA) show excellent colloidal stability in various polar solvents with dielectric constant ranging from 2.2 to 32.6 and efficient photoluminescence with a quantum yield of 85.3%. Due to the suppressed desorption of GA, the morphological and optical properties of PNCs-GA are well maintained after five rounds purification and two months long-term storage. At last, hydrophilic PNCs-GA are successfully patterned through inkjet- and screen-printing technology. These findings offer deep insights into the interfacial chemistry of colloidal NCs and provide a universal strategy for preparing high-quality hydrophilic PNCs.

Water-Soluble Quantum Dots for Inkjet Printing Color Conversion Films with Simultaneous High Efficiency and Stability.

Water-soluble quantum dots (QDs) are necessary to prepare patterned pixels or films for high-resolution displays with less environmental burden but are very limited by the trade-off between photoluminescence and stability of QDs. In this work, we proposed synthesizing water-soluble QDs with simultaneous excellent luminescence properties and high stability by coating the amphiphilic poly(maleic anhydride-alt-1-octadecene)-ethanol amine (PMAO-EA) polymer on the surface of silane-treated QDs. These coated QDs show a photoluminescence quantum yield (PLQY) as high as 94%, and they have good photoluminescence stability against light irradiation and thermal attacks, owing to the suppression of the nonradiative recombination by the polymer layer and the isolation of oxygen and water by the silica layer. The water-soluble QDs, mixed with ethylene glycol, enable inkjet printing of QD color conversion films (QD-CCFs) with an average diameter of 68 µm for each pixel and a high PLQY of 91%. The QD-CCFs are demonstrated to fabricate red-emitting mini-LEDs by combining with blue mini-LED chips, which have an external quantum efficiency as high as 25.86% and a luminance of 2.44 × 107 cd/m2. We believe that the proposed strategy is applicable to other water-soluble QDs and paves an avenue for inkjet printing environmentally friendly QD-CCFs for mini/micro-LED displays.

Perovskite Light-Emitting Diodes with an External Quantum Efficiency Exceeding 30.

Perovskite light-emitting diodes (PeLEDs) are strong candidates for next-generation display and lighting technologies due to their high color purity and low-cost solution-processed fabrication. However, PeLEDs are not superior to commercial organic light-emitting diodes (OLEDs) in efficiency, as some key parameters affecting their efficiency, such as the charge carrier transport and light outcoupling efficiency, are usually overlooked and not well optimized. Here, ultrahigh-efficiency green PeLEDs are reported with quantum efficiencies surpassing a milestone of 30% by regulating the charge carrier transport and near-field light distribution to reduce electron leakage and achieve a high light outcoupling efficiency of 41.82%. Ni0.9 Mg0.1 Ox films are applied with a high refractive index and increased hole carrier mobility as the hole injection layer to balance the charge carrier injection and insert the polyethylene glycol layer between the hole transport layer and the perovskite emissive layer to block the electron leakage and reduce the photon loss. Therefore, with the modified structure, the state-of-the-art green PeLEDs achieve a world record external quantum efficiency of 30.84% (average =  29.05 ± 0.77%) at a luminance of 6514 cd m-2 . This study provides an interesting idea to construct super high-efficiency PeLEDs by balancing the electron-hole recombination and enhancing the light outcoupling.

Constructing Perovskite/Polymer Core/Shell Nanocrystals with Simultaneous High Efficiency and Stability for Mini-LED Backlights.

Lead halide perovskite nanocrystals (NCs) have been the star material in lighting and displays owing to their excellent photoelectrical properties, but they have not simultaneously realized high photoluminescence quantum yield (PLQY) and high stability. To solve this problem, we propose a perovskite/linear low-density polyethylene (perovskite/LLDPE) core/shell NC by the synergistic role of the pressure effect and steric effect. Green CsPbBr3/LLDPE core/shell NCs with near-unity PLQY and nonblinking behavior were synthesized through an in situ hot-injection process. The mechanism of the improved photoluminescence (PL) properties is the enhanced pressure effect resulting in increased radiative recombination and interaction between the ligand and perovskite crystals, as confirmed by the PL spectra and finite element calculations. Meanwhile, the NCs show high stability under ambient conditions (with a PLQY of 92.5% after 166 days) and against 365 nm UV light (maintaining 61.74% of the initial PL intensity after continuous radiation for 1000 min). This strategy also works well in the blue and red perovskite/LLDPE NCs and red InP/ZnSeS/ZnS/LLDPE NCs. Finally, white-emitting Mini-LEDs were fabricated by combining the green CsPbBr3/LLDPE and red CsPbBr1.2I1.8/LLDPE core/shell NCs with blue Mini-LED chips. The white-emitting Mini-LEDs exhibit super wide color gamut (∼129% of the National Television Standards Committee or 97% of the Rec. 2020 standards).

Passivation Layer of Potassium Iodide Yielding High Efficiency and Stable Deep Red Perovskite Light-Emitting Diodes.

Perovskite light-emitting diodes (PeLEDs) are promising candidates used for superthin emissive displays with high resolution, high brightness, and wide color gamut, but the CsPbI3 nanocrystal (NC) based ones usually have an external quantum efficiency (EQE) of less than 20%, which needs further enhancement to minimize the gap between their counterparts. Herein, we propose to improve optical properties of the CsPbI3:Sr emissive layer (EML) by inserting an additional potassium iodide (KI) passivation layer between the hole transport layer and EML to increase the film quality, photoluminescence quantum yield, and thermal stability of the EML. The KI layer can also increase the carrier mobility to balance the charge injection in PeLEDs, leading to a reduction in Auger recombination and Joule heating. An interesting deep-red-emitting PeLED (λem = 687 nm) with a record EQE of 21.8% and a lifetime T50 of 69 min is obtained by applying the additional KI passivation layer. Moreover, a flexible PeLED consisting of the KI layer is also demonstrated to have a record EQE of 12.7%. These results indicate that the use of a functional KI layer is a feasible way to develop high-performance electroluminescent devices.

In Situ Growth of High-Quality CsPbBr3 Quantum Dots with Unusual Morphology inside a Transparent Glass with a Heterogeneous Crystallization Environment for Wide Gamut Displays.

All-inorganic CsPbBr3 perovskite quantum dots (QDs) are considered to be one of the most promising green candidates for the new-generation backlight displays. The pending barriers to their applications, however, lie in their mismatching of the target window of green light, scalable production, susceptibility to the leaching of lead ions, and instability in harsh environments (such as moisture, light, and heat). Herein, high-quality CsPbBr3 QDs with globoid shapes and cuboid shapes were in situ crystallized/grown inside a well-designed glass to produce nanocomposites with peak emission at 526 nm, which not only exhibited photoluminescence quantum yields of 53 and 86% upon 455 and 365 nm excitation, respectively, but also have been imparted of high stability when they were submerged in water and exposed to heat and light. These characteristics, along with their lead self-sequestration capability and easy-to-scale preparation, can enable breakthrough applications for CsPbBr3 QDs in the field of wide color gamut backlit display. A high-performance backlight white LEDs was fabricated using the CsPbBr3 QDs@glass powder and K2SiF6:Mn4+ red phosphor, which shows a color gamut of ∼126% of the NTSC or 94% of the Rec. 2020 standards.

In Situ Inkjet Printing Patterned Lead Halide Perovskite Quantum Dot Color Conversion Films by Using Cheap and Eco-Friendly Aqueous Inks.

Inkjet-printed perovskite quantum dot (PQD) color conversion films (CCFs) have great potentials for mini/micro-LED displays because of their ultrahigh color purity, tunable emissions, high efficiency, and high-resolution. However, current PQD inks mainly use expensive, toxic, and flammable organic substances as solvents. In this work, water is proposed to be used as the solvent for inkjet printing PQD/polymer CCFs. The green-emitting patterned MAPbBr3 /polyvinyl alcohol (PVA) films are in situ prepared by using halides and the PVA-based aqueous ink. The as-printed CCFs exhibit a high-resolution dot matrix of 90 µm with a bright green emission (λem  = 526 nm), a high photoluminescence quantum yield of 85%, and a narrow full width at half maximum of 22 nm. They have both air- and photo-stabilities under ambient conditions, and each pixel of CCFs is relatively uniform in morphology and fluorescence when the substrate temperature is 80 °C. The patterned blue-emitting MAPbClx Br3-x /PVA and red-emitting Cs0.3 MA0.7 PbBrx I3-x /PVA can also be printed by aqueous inks. These results indicate that the designed aqueous inks are promising for in situ inkjet printing high resolution and reliability PQD CCFs for mini/micro-LED displays.

Inkjet-Printed Quantum Dot Color Conversion Films for High-Resolution and Full-Color Micro Light-Emitting Diode Displays.

Micro light-emitting diodes (µLEDs) have been considered an excellent candidate for next-generation display technology because of their promising optical properties, outstanding power efficiency, fast response time, high reliability, etc. However, the µLED displays based on individual red-green-blue (RGB) primary chips suffer from severe issues in mass production, such as difficulty in mass transfer, high cost, and low reproducibility. To overcome these issues, an alternative approach has been proposed to achieve full-color µLEDs by assembling ultraviolet- or blue-µLEDs with QD color conversion films (CCFs). In this Perspective, we give a general introduction of QD-based µLEDs and provide an overview of the preparation of fine patterned QD CCFs by inkjet printing. We then discuss advances in II-VI core/shell QD-based µLEDs. This is followed by representative progress on preliminary exploration of lead halide perovskite QD CCFs, which have great potential for use in high-resolution and full-color µLEDs displays. Finally, we address the remaining challenges for further improvement of QD-based µLEDs.

Chemical Transformation of Lead Halide Perovskite into Insoluble, Less Cytotoxic, and Brightly Luminescent CsPbBr3/CsPb2Br5 Composite Nanocrystals for Cell Imaging.

Lead halide perovskite nanocrystals (NCs) have been widely investigated owing to their potential applications as optoelectronic devices. However, these materials suffer from poor water stability, which make them impossible to be applied in biomedicine. Here, insoluble CsPbBr3/CsPb2Br5 composite NCs were successfully synthesized via simple water-assisted chemical transformation of perovskite NCs. Water plays two key roles in this synthesis: (i) stripping CsBr from CsPbBr3/Cs4PbBr6 and (ii) modifying the coordination number of Pb2+ (six in CsPbBr3 and Cs4PbBr6 vs eight in CsPb2Br5). The as-prepared CsPbBr3/CsPb2Br5 composite NCs not only retain the photoluminescence quantum yield (up to 80%) and a narrow full width to half-maximum of 16 nm, but also present excellent water stability and low cytotoxicity. With these properties, the CsPbBr3/CsPb2Br5 composite NCs were demonstrated as efficient fluorescent probes in live HeLa cells. We believe that our finding not only provides a new method to prepare insoluble, narrow-band, and brightly luminescent CsPbBr3/CsPb2Br5 composite NCs, but also extend the potential applications of lead halides in biomedicine.

Controllable and facile synthesis of CsPbBr3-Cs4PbBr6 perovskite composites in pure polar solvent.

Here, we present a single atomic supersaturated recrystallization method to synthesize the green-emitting CsPbBr3-Cs4PbBr6 perovskite composites in solid state with the highest PLQY of 40.8% in pure polar solvent. The component, morphology, and optical properties of the microcrystals can be tuned by varying growth time, the content of ammonium bromide, and bromine source. The developed method provides a new route to large-scale synthesize high quality perovskite composites emitters for light-emitting diodes.

Synthesis of Eu2+/Eu3+ Co-Doped Gallium oxide nanocrystals as a full colour converter for white light emitting diodes.

Eu2+ and Eu3+ co-doped Ga2O3 nanocrystals (Ga2O3:Eu NCs) were synthesized in an organic phase at a low reaction temperature of 300 °C. The surface of Ga2O3:Eu NCs was passivated by oleylamine (OAm) and acetylacetone (acac). The coexistence of Eu2+ and Eu3+ as well as passivation by acac and OAm enable Ga2O3 to be excited in the broad spectral range of 200-500 nm. The broadened absorption band is attributed to the strong acac → Ln(III) ligand to the metal charge transfer transition at ∼370 nm, Eu(III) f-f allowed 7F0 → 5L6 transition at 395 nm, and 7F0 → 5D2 transition at 465 nm, as well as the efficient electronic transition of Eu(II) 4f → 5d at ∼400 nm. Under near-ultraviolet excitation, white light emission can be achieved by combining orange-red light from f-f electronic transition of Eu(III) with blue-green-yellow light from Ga2O3 oxygen defects levels. Furthermore, the resultant Ga2O3:Eu NCs with optimized quantum yield of 14.5% were coated onto 395 nm near-ultraviolet chips to fabricate a white light emitting diode. It exhibits a luminous efficiency of 34 lm/W, CIE colour coordinate of (0.2964, 0.2831) and high colour rendering index of 80.

Highly Stable K2SiF6:Mn4+@K2SiF6 Composite Phosphor with Narrow Red Emission for White LEDs.

Poor water resistance and nongreen synthesis remain great challenges for commercial narrow red-emitting phosphor A2MF6:Mn4+ (A = alkali metal ion; M = Si, Ge, Ti) for solid-state lighting and display. We develop here a simple and green growth route to synthesize homogeneous red-emitting composite phosphor K2SiF6:Mn4+@K2SiF6 (KSFM@KSF) with excellent water resistance and high efficiency without the usage of toxic and volatile hydrogen fluoride solution. After immersing into water for 6 h, the as-obtained water-resistant products maintain 76% of the original emission intensity, whereas the emission intensity of non-water-resistant ones steeply drops down to 11%. A remarkable result is that after having kept at 85% humidity and at 85 °C for 504 h (21 days), the emission intensity of the as-obtained water-resistant products is at 80-90%, from its initial value, which is 2-3 times higher than 30-40% for the non-water-resistant products. The surface deactivation-enabled growth mechanism for these phosphors was proposed and investigated in detail. We found that nontoxic H3PO4/H2O2 aqueous solution promotes the releasing and decomposition of the surface [MnF6]2- ions and the transformation of the KSFM surface to KSF, which finally contributes to the homogeneous KSFM@KSF composite structure. This composite structure strategy was also successfully used to treat KSFM phosphor prepared by other methods. We believe that the results obtained in the present paper will open the pathway for the large-scale environmentally friendly synthesis of the excellent antimoisture narrow red-emitting A2MF6:Mn4+ phosphor to be used for white light-emitting diode applications.

Monodisperse and brightly luminescent CsPbBr3/Cs4PbBr6 perovskite composite nanocrystals.

The microscale composite structure strategy of embedding CsPbBr3 nanocrystals (NCs) in the microscale Cs4PbBr6 matrix (CPB113/CPB416) has successfully demonstrated its ability to resolve the fluorescence quenching of perovskite NCs in the solid agglomeration state due to the loss of quantum confinement. Unfortunately, the controllable synthesis of monodisperse nanoscale composites with bright emission in the solid state remains a great challenge. Here, we present for the first time a novel supersaturated recrystallization process to controllably synthesize monodisperse CPB113/CPB416 composite NCs with bright emission in the solid form, where CsPbBr3 NCs were uniformly embedded in the nano hexagonal Cs4PbBr6 matrix. The existence of 2-methylimidazole (MeIm) not only can control the composition rate of CsPbBr3 to Cs4PbBr6, the size and dispersity of CsPbBr3 in the composite NCs but can also help controllably obtain the monodisperse and hexagonal Cs4PbBr6 matrix. The as-prepared composite structure can effectively prevent CsPbBr3 fluorescence quenching and make the composite NCs have a high photoluminescence quantum yield (PLQY) of 83%. In addition, we obtained tunable blue to red emitting composite NCs by varying the halide salts.

Cs4PbBr6/CsPbBr3 Perovskite Composites with Near-Unity Luminescence Quantum Yield: Large-Scale Synthesis, Luminescence and Formation Mechanism, and White Light-Emitting Diode Application.

All-inorganic perovskites have emerged as a new class of phosphor materials owing to their outstanding optical properties. Zero-dimensional inorganic perovskites, in particular the Cs4PbBr6-related systems, are inspiring intensive research owing to the high photoluminescence quantum yield (PLQY) and good stability. However, synthesizing such perovskites with high PLQYs through an environment-friendly, cost-effective, scalable, and high-yield approach remains challenging, and their luminescence mechanisms has been elusive. Here, we report a simple, scalable, room-temperature self-assembly strategy for the synthesis of Cs4PbBr6/CsPbBr3 perovskite composites with near-unity PLQY (95%), high product yield (71%), and good stability using low-cost, low-toxicity chemicals as precursors. A broad range of experimental and theoretical characterizations suggest that the high-efficiency PL originates from CsPbBr3 nanocrystals well passivated by the zero-dimensional Cs4PbBr6 matrix that forms based on a dissolution-crystallization process. These findings underscore the importance in accurately identifying the phase purity of zero-dimensional perovskites by synchrotron X-ray technique to gain deep insights into the structure-property relationship. Additionally, we demonstrate that green-emitting Cs4PbBr6/CsPbBr3, combined with red-emitting K2SiF6:Mn4+, can be used for the construction of WLEDs. Our work may pave the way for the use of such composite perovskites as highly luminescent emitters in various applications such as lighting, displays, and other optoelectronic and photonic devices.

Highly stable CsPbBr3 quantum dots coated with alkyl phosphate for white light-emitting diodes.

Inorganic halide perovskite quantum dots (QDs) suffer from problems related to poor water stability and poor thermal stability. Here we developed a simple strategy to synthesize alkyl phosphate (TDPA) coated CsPbBr3 QDs by using 1-tetradecylphosphonic acid both as the ligand for the CsPbBr3 QDs and as the precursor for the formation of alkyl phosphate. These QDs not only retain a high photoluminescence quantum yield (PLQY, 68%) and narrow band emission (FHWM ∼ 22 nm) but also exhibit high stability against water and heat. The relative PL intensity of the QDs was maintained at 75% or 59% after being dispersed in water for 5 h or heated to 375 K (100 °C), respectively. Finally, white light-emitting diodes (WLEDs) with a high luminous efficiency of 63 lm W-1 and a wide color gamut (122% of NTSC) were fabricated by using green-emitting CsPbBr3/TDPA QDs and red-emitting K2SiF6:Mn4+ phosphors as color converters. The luminous efficiency of the WLEDs remained at 90% after working under a relative humidity (RH) of 60% for 15 h, thereby showing promise for use as backlight devices in LCDs.

Facile Synthesis of Cadmium-Free Zn-In-S:Ag/ZnS Nanocrystals for Bio-Imaging.

High quality cadmium-free Zn-In-S:Ag doped-nanocrystals (d-NCs) were synthesized via a simple one-step noninjection route using silver nitrate, indium acetate, zinc acetate, oleylamine, S powder and 1-dodecanethiol as starting materials in an organic phase. The size and optical properties can be effectively tailored by controlling the reaction time, reaction temperature, Ag(+) dopant concentration, and the molar ratio of In to Zn. The photoluminescence wavelength of as-prepared Zn-In-S:Ag NCs covered a broad visible range from 458 nm to 603 nm. After being passivated by protective ZnS shell, the photoluminescence quantum yield (PLQY) of Zn-In-S:Ag(+) /ZnS was greatly improved to 43.5%. More importantly, the initial high PLQY of the obtained core/shell d-NCs in organic media can be preserved when being transferred into the aqueous media via ligand exchange. Finally, high quality Zn-In-S:Ag(+) /ZnS d-NCs in aqueous phase were applied as bio-imaging agents for identifying living KB cells.

Single-step noninjection synthesis of highly luminescent water soluble Cu+ doped CdS quantum dots: application as bio-imaging agents.

Novel highly luminescent Cu(+) doped CdS quantum dots (QDs) were directly synthesized in aqueous phase through a facile single-step noninjection method. Due to their bright red fluorescence, ultrasmall size, and good biocompatibility, as-prepared CdS:Cu(+) QDs have potential as probes in bio-imaging.