Fabrication of red-emitting perovskite LEDs by stabilizing their octahedral structure.

Light-emitting diodes (LEDs) based on metal halide perovskites (PeLEDs) with high colour quality and facile solution processing are promising candidates for full-colour and high-definition displays1-4. Despite the great success achieved in green PeLEDs with lead bromide perovskites5, it is still challenging to realize pure-red (620-650 nm) LEDs using iodine-based counterparts, as they are constrained by the low intrinsic bandgap6. Here we report efficient and colour-stable PeLEDs across the entire pure-red region, with a peak external quantum efficiency reaching 28.7% at 638 nm, enabled by incorporating a double-end anchored ligand molecule into pure-iodine perovskites. We demonstrate that a key function of the organic intercalating cation is to stabilize the lead iodine octahedron through coordination with exposed lead ions and enhanced hydrogen bonding with iodine. The molecule synergistically facilitates spectral modulation, promotes charge transfer between perovskite quantum wells and reduces iodine migration under electrical bias. We realize continuously tunable emission wavelengths for iodine-based perovskite films with suppressed energy loss due to the decrease in bond energy of lead iodine in ionic perovskites as the bandgap increases. Importantly, the resultant devices show outstanding spectral stability and a half-lifetime of more than 7,600 min at an initial luminance of 100 cd m-2.

Tautomeric mixture coordination enables efficient lead-free perovskite LEDs.

Lead halide perovskite light-emitting diodes (PeLEDs) have demonstrated remarkable optoelectronic performance1-3. However, there are potential toxicity issues with lead4,5 and removing lead from the best-performing PeLEDs-without compromising their high external quantum efficiencies-remains a challenge. Here we report a tautomeric-mixture-coordination-induced electron localization strategy to stabilize the lead-free tin perovskite TEA2SnI4 (TEAI is 2-thiopheneethylammonium iodide) by incorporating cyanuric acid. We demonstrate that a crucial function of the coordination is to amplify the electronic effects, even for those Sn atoms that aren't strongly bonded with cyanuric acid owing to the formation of hydrogen-bonded tautomeric dimer and trimer superstructures on the perovskite surface. This electron localization weakens adverse effects from Anderson localization and improves ordering in the crystal structure of TEA2SnI4. These factors result in a two-orders-of-magnitude reduction in the non-radiative recombination capture coefficient and an approximately twofold enhancement in the exciton binding energy. Our lead-free PeLED has an external quantum efficiency of up to 20.29%, representing a performance comparable to that of state-of-the-art lead-containing PeLEDs6-12. We anticipate that these findings will provide insights into the stabilization of Sn(II) perovskites and further the development of lead-free perovskite applications.

Deep-Blue Electroluminescence of Perovskites with Reduced Dimensionality Achieved by Manipulating Adsorption-Energy Differences.

The lagging development of deep-blue perovskite light-emitting diodes (PeLEDs) heavily impedes their practical applications in full-color display due to the absence of spectrally stable emitters and the mismatch of carrier injection capacity. Herein, we report highly efficient deep-blue PeLEDs through a new chemical strategy that addresses the dilemma for simultaneously constant electroluminescence (EL) spectra and high-purify phase in reduced-dimensional perovskites. The success lies in the control of adsorption-energy differences between phenylbutylamine (PBA) and ethylamine (EA) interacting with perovskites, which facilitates narrow n-value distribution. This approach leads to an increased exciton binding energy and enhanced surface potential, hence improving radiative recombination. As a result, an external quantum efficiency of 4.62 % is achieved in PeLEDs with a stable EL peak at 457 nm, demonstrating the best reported result for deep-blue PeLEDs so far.

Growing MASnI3perovskite single-crystal films by inverse temperature crystallization.

Perovskite single-crystal films are promising candidates for high-performance perovskite optoelectronic devices due to their optoelectrical properties. However, there are few reports of single-crystal films of tin based perovskites. Here, for the first time, we realize the controllable growth and preparation of lead-free tin perovskite MASnI3single crystals via inverse temperature crystallization (ITC) strategy with γ-butyrolactone (GBL) as solvent. The solubility characteristics of MASnI3in GBL are clarified by quantitative analytical method. Highly repeatability experiments are further demonstrated using this unique solubility and ITC properties. Sequentially, using space limiting method, tin perovskite MASnI3single-crystal thin films are fabricated with micron-scale thickness, which is highly desired for efficient tin perovskite solar cells. Our MASnI3single-crystal thin films show typical single-crystalline features including strongly optical absorbance with sharp absorption edges, pure-phase x-ray diffraction patterns, and absence of Sn(IV) x-ray photoelectron spectroscopy. We believe that our findings will further broaden the application prospects of tin perovskite MASnI3single crystals and cause a new upsurge in exploring the field of lead-free perovskite single-crystal growth.

Two-step synthesis of hole structure bastnasite (RECO3F RE = Ce, La, Pr, Nd) sub-microcrystals with tunable luminescence properties.

A two-step synthetic route using RE(OH)CO3 colloid spheres as the sacrificial template was designed to prepare monodisperse, pure bastnasite (RECO3F: RE = Ce, La, Pr, Nd) with a hole structure for the first time. A variety of morphologies, including jujube core-like, stacked nanoblocks, and stacked nanosheets were obtained through changing the ratio of reactants. The phase, structure, shapes, and photoluminescence properties of samples were characterized by X-ray diffraction (XRD), field-emission scanning electron microscopy (FE-SEM), transmission electron microscopy (TEM) and photoluminescence (PL) spectroscopy. The CeCO3F:Ln3+ (Ln = Tb, Eu, Dy) phosphors give green, yellow and blue emission, respectively, due to the f-f transitions of Ln3+ ions. Furthermore, the energy transfer from Ce3+ to Dy3+ and Tb3+ was described in detail.

A novel color-tunable phosphor, Na5Gd9F32:Ln3+ (Ln = Eu, Tb, Dy, Sm, Ho) sub-microcrystals: structure, luminescence and energy transfer properties.

Ln3+-Doped fluorides are economical and highly efficient luminescent materials, which play a crucial role in LEDs, biolabeling, and sensors. Therefore, Na5Gd9F32:Ln3+ sub-microspheres with tunable multicolor emissions were successfully synthesized via a simple water bath method employing colloidal Gd(OH)CO3 spheres as precursors. Samples were characterized by XRD, SEM, TEM, EDS and PL. It was found that the hydrolysis of BF4- ions had a dynamic effect on the retention of the morphology of the product owing to the mild reaction environment caused by the low hydrolysis rate of BF4- ions. Upon excitation by ultraviolet light, the Na5Gd9F32:Ln3+ (Ln = Eu, Tb, Dy, Sm, Ho) phosphors underwent characteristic f-f transitions and gave rise to red, green, green, yellow, and pale green emissions, respectively. Moreover, various emission colors could be obtained by using different excitation wavelengths and adjusting the Eu3+/Tb3+ molar ratio owing to energy transfer between Tb3+ and Eu3+ ions in the Na5Gd9F32 host. The energy transfer mechanism was demonstrated to be a dipole-dipole interaction. The multicolor luminescent phosphors with a certain dopant concentration based on a single host and excitation wavelength may have potential applications in the field of lighting displays.

Facile synthesis and color-tunable properties of monodisperse ß-NaYF4:Ln3+ (Ln = Eu, Tb, Tm, Sm, Ho) microtubes.

In this study, monodisperse and uniform ß-NaYF4 hexagonal microtubes were successfully synthesized via a simple hydrothermal method without any organic surfactants, employing Y(OH)CO3 colloid spheres as precursors. The possible formation mechanism was studied on the basis of a series of time-dependent control experiments and its intrinsic crystal structure. The integrated emission intensity of ß-NaYF4:0.05Tb3+ is almost 1.78 times stronger than that of α-NaYF4:0.05Tb3+. In addition, the photoluminescence properties of ß-NaYF4:Ln3+ (Ln = Eu, Tb, Tm, Sm, Ho) were studied in detail, and it was found that the photoluminescence color of ß-NaYF4:0.03Tm3+ phosphor was close to the standard blue light (0.14, 0.08). Moreover, by co-doping the Tb3+ and Eu3+ ions into the ß-NaYF4 host, multicolor tunable emissions were obtained due to the efficient energy transfer from Tb3+ to Eu3+ at 368 nm excitation. These merits demonstrate that this material may find potential application in color display fields.

Fabrication of CeO2 nanoparticles decorated three-dimensional flower-like BiOI composites to build p-n heterojunction with highly enhanced visible-light photocatalytic performance.

Three-dimensional (3D) flower-like CeO2/BiOI heterostructures with different Ce/Bi molar ratio were successfully synthesized via a hydrothermal method using polyvinylpyrrolidone (PVP) as surfactant. The X-ray diffraction (XRD), scanning electron microscope (SEM), transmission electron microscopy (TEM) and high-resolution transmission electron microscopy (HRTEM) results indicate that the CeO2 nanoparticles were successfully loaded on the surface of the flower-like BiOI. The photodegradation experiment demonstrated that the photocatalytic efficiency of CeO2/BiOI samples were higher than that of pure BiOI and CeO2, and CeO2/BiOI heterostructure showed the best photocatalytic performance when the amount of CeO2 located at BiOI up to 15%. The result also exhibits that CeO2/BiOI catalysts possess higher photocatalytic efficiency for Rhodamine B (RhB) and methylene orange (MO) degradation, while it has a slight influence for phenol elimination. Meanwhile, the repeated photocatalytic degradation of RhB experiment reveals excellent photostability. A possible mechanism of photocatalysis was also explored and proposed. Furthermore, loading CeO2 on the surface of BiOI can accelerate the separation rate of photogenerated electron-hole pairs, which is analyzed by photoluminescence (PL) spectroscopy, photocurrent experiments (PC) and electrochemical impedance spectroscopy (EIS). These results exhibit that BiOI can be modified by CeO2 and there exists synergistic effect between CeO2 and BiOI. The present work provides a new means to synthesize heterostructured photocatalyst for environmental remediation.