Facile low-temperature solid-state synthesis of efficient blue-emitting Cs3Cu2I5 powder phosphors for solid-state lighting

The discovery of new environmentally friendly luminescent materials with high photoluminescence quantum yield and long-term stability is critical for future solid-state lighting and displays applications. Although lead halide perovskite materials with excellent optical properties have been extensively investigated in recent years because they hold tremendous promise in optoelectronic devices, the toxicity of lead and poor air-stability still hinder their commercial applications. Moreover, while substantial work has been done on three-dimensional (3D) perovskite halides, the zero-dimensional (0D) halide emitters with bright luminescence remain elusive. Herein we report a facile solid-state reaction method to prepare an efficient lead-free all-inorganic halide material with 0D structure, Cs₃Cu₂I₅, with photoluminescence quantum yield up to 80%. Under ultraviolet excitation at 313 nm, the Cs₃Cu₂I₅ powder phosphors show a strong blue photoluminescence emission with peak at 445 nm and CIE color coordinates of (0.1486, 0.0873). Notably, Cs₃Cu₂I₅ exhibits good color stability at high temperatures and outstanding stability towards air exposure exceeding one month (30 days). These findings not only open up a door for the development of promising highly emissive low-dimensional halide materials for lighting and displays, but also offer a new scalable approach for the potential mass production of halide emitters.     

Efficient Thermally Activated Delayed Fluorescence from All-Inorganic Cesium Zirconium Halide Perovskite Nanocrystals

Thermally activated delayed fluorescence (TADF) is generally observed in solid-state organic molecules or metal-organic complexes. However, TADF in all-inorganic colloidal nanocrystals (NCs) is rare. Herein, we report the first colloidal synthesis of an air-stable all-inorganic lead-free Cs₂ZrCl₆ perovskite NCs. The Cs₂ZrCl₆ NCs exhibit long-lived triplet excited state (138.2 μs), and feature high photoluminescence (PL) quantum efficiency (QY=60.37 %) due to TADF mechanism. The emission color can be easily tuned from blue to green by synthesizing the mixed-halide Cs₂ZrBr_xCl_6−x (0≤x≤1.5) NCs. Femtosecond transient absorption and temperature dependent PL measurements are performed to clarify the emission mechanism. In addition, Bi³⁺ ions are successfully doped into Cs₂ZrCl₆ NCs, which further extends the PL properties. This work not only develops a new lead-free halide perovskite NCs for potential optoelectronic applications, but also offers unique strategies for developing new inorganic phosphors.     

Colloidal Synthesis and Optical Properties of All‐Inorganic Low‐Dimensional Cesium Copper Halide Nanocrystals

Low‐dimensional metal halides have recently attracted extensive attention owing to their unique structure and photoelectric properties. Herein, we report the colloidal synthesis of all‐inorganic low‐dimensional cesium copper halide nanocrystals (NCs) by adopting a hot‐injection approach. Using the same reactants and ligands, but different reaction temperatures, both 1D CsCu₂I₃ nanorods and 0D Cs₃Cu₂I₅ NCs can be prepared. Density functional theory indicates that the reduced dimensionality in 1D CsCu₂I₃ compared to 0D Cs₃Cu₂I₅ makes the excitons more localized, which accounts for the strong emission of 0D Cs₃Cu₂I₅ NCs. Subsequent optical characterization reveals that the highly luminescent, strongly Stokes‐shifted broadband emission of 0D Cs₃Cu₂I₅ NCs arises from the self‐trapped excitons. Our findings not only present a method to control the synthesis of low‐dimensional cesium copper halide nanocrystals but also highlight the potential of 0D Cs₃Cu₂I₅ NCs in optoelectronics.     

Three-Dimensional Cuprous Lead Bromide Framework with Highly Efficient and Stable Blue Photoluminescence Emission

Considering the instability and low photoluminescence quantum yield (PLQY) of blue-emitting perovskites, it is still challenging and attractive to construct single crystalline hybrid lead halides with highly stable and efficient blue light emission. Herein, by rationally introducing d¹⁰ transition metal into single lead halide as new structural building unit and optical emitting center, we prepared a bimetallic halide of [(NH₄)₂]CuPbBr₅ with new type of three-dimensional (3D) anionic framework. [(NH₄)₂]CuPbBr₅ exhibits strong band-edge blue emission (441 nm) with a high PLQY of 32 % upon excitation with UV light. Detailed photophysical studies indicate [(NH₄)₂]CuPbBr₅ also displays broadband red light emissions derived from self-trapped states. Furthermore, the 3D framework features high structural and optical stabilities at extreme environments during at least three years. To our best knowledge, this work represents the first 3D non-perovskite bimetallic halide with highly efficient and stable blue light emission.     

Three‐Dimensional Cuprous Lead Bromide Framework with Highly Efficient and Stable Blue Photoluminescence Emission

Considering the instability and low photoluminescence quantum yield (PLQY) of blue‐emitting perovskites, it is still challenging and attractive to construct single crystalline hybrid lead halides with highly stable and efficient blue light emission. Herein, by rationally introducing d¹⁰ transition metal into single lead halide as new structural building unit and optical emitting center, we prepared a bimetallic halide of [(NH₄)₂]CuPbBr₅ with new type of three‐dimensional (3D) anionic framework. [(NH₄)₂]CuPbBr₅ exhibits strong band‐edge blue emission (441 nm) with a high PLQY of 32 % upon excitation with UV light. Detailed photophysical studies indicate [(NH₄)₂]CuPbBr₅ also displays broadband red light emissions derived from self‐trapped states. Furthermore, the 3D framework features high structural and optical stabilities at extreme environments during at least three years. To our best knowledge, this work represents the first 3D non‐perovskite bimetallic halide with highly efficient and stable blue light emission.     

Doped Zero-Dimensional Cesium Zinc Halides for High-Efficiency Blue Light Emission

All-inorganic zero-dimensional (0D) metal halides have recently received increasing attention due to their excellent photoluminescence (PL) performance and high stability. Herein, we present the successful doping of copper(I) into 0D Cs₂ZnBr₄. The incorporating of Cu⁺ cations enables the originally weakly luminescent Cs₂ZnBr₄ to exhibit an efficient blue emission centered at around 465 nm, with a high photoluminescence quantum yield (PLQY) of 65.3 %. Detailed spectral characterizations, including ultrafast transient absorption (TA) techniques, were carried out to investigate the effect of Cu⁺ dopants and the origin of blue emission in Cs₂ZnBr₄:Cu. To further study the role of the A-site cation and halogen, A₂ZnCl₄:Cu (A=Cs, Rb) were also synthesized and found to generate intense sky-blue emission (PLQY≈73.1 %). This work represents an effective strategy for the development of environmentally friendly, low-cost and high-efficiency blue-emitting 0D all-inorganic metal halides.     

SrCO3:Tb3+ hollow microspheres fabricated via solvothermal process and their optical properties

Well-dispersed SrCO₃:Tb³⁺ hollow microspheres have been synthesized in the water-ethanol-ethylene glycol solvent system using oleic acid (OA) as an additive without further annealing treatment. X-ray diffraction (XRD), fourier transform-infrared spectroscopy (FT–IR), and field emission scanning electron microscopy (FE-SEM), as well as photoluminescence spectroscopy (PL) were used to characterize the resulting samples. The dosage of OA and the reaction time play key roles in the formation of the final samples. The possible formation mechanism for SrCO₃:Tb³⁺ hollow microsphere is proposed. The SrCO₃:Tb³⁺ phosphors show strong photoluminescence with green emission ⁵D₄–⁷F₅ (544 nm) as the most prominent group under ultraviolet excitation, which have potential applications in field emission displays. The present synthesis process may be extended to fabricate other inorganic materials with special morphologies and functions.     

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 Cs₂NaInCl₆ NCs by variable temperature hot injection. The Cs₂NaInCl₆ 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.     

Room-Temperature Synthesized Cd-Doped Cs3Cu2I5: Stable and Excitation-Wavelength Dependent Dual-Color Emission for Advanced Anti-Counterfeiting

With the development of intellectual properties, concern about advanced anti-counterfeiting is accumulating, which conventional single-modal luminescence can no longer satisfy. As one of rapidly developing 0D materials, copper-based perovskite shows great potential to realize multiple luminescent centers for complex emissions. In this work, Cd was doped into Cs₃Cu₂I₅ and showed resultant emission at 560 nm which surprisingly showed a red-shifted excitation peak from that of intrinsic self-trapped emission, resulting in excitation-wavelength dependent emission. When the excitation wavelength increased from 290 nm to 330 nm, the emission of Cd-doped Cs₃Cu₂I₅ changed from deep blue to cold white and finally yellow. Afterwards, Cd-doped Cs₃Cu₂I₅ was mixed with polystyrene to prepare anti-counterfeiting ink for silk-screen printing. Meanwhile, Cd-doped Cs₃Cu₂I₅ maintains outstanding stability after doping, no matter under ambient, continuous UV radiation or high-temperature environment. The intensity can be almost totally recovered after heating-and-cooling cycles. This study lays groundwork for future research into multiple luminescent center manipulation in 0D materials.     

GdAlO_3:Er~(3+),Yb~(3+)荧光粉的制备与上转换发光性能

采用共沉淀、溶胶-凝胶和固相反应法制备了GdAlO3:Er3+,Yb3+荧光粉.借助X射线衍射、扫描电子显微镜、傅里叶变换红外光谱、N2-吸附、吸收光谱和荧光光谱等手段研究了不同方法制备的GdAlO3:Er3+,Yb3+荧光粉结构、形貌、表面基团和光吸收及上转换发光性能.结果表明:用共沉淀法比固相反应法和溶胶-凝胶法可以在更温和的条件下制得纯相GdAlO3:Er3+,Yb3+荧光粉,用共沉淀法和溶胶-凝胶法制备的GdAlO3:Er3+,Yb3+荧光粉颗粒都在纳米尺寸,溶胶-凝胶法制得的样品存在相对严重的颗粒团聚现象,而用固相反应法制备的荧光粉为微米级颗粒.GdAlO3:Er3+,Yb3+荧光粉在980 nm激发的上转换发射光谱包含波长为524和546 nm的绿光与659 nm的红光,且三种方法制备的样品绿光发射强度都显著高于红光.不同方法制备的荧光粉上转换发光强度和红光/绿光强度比相差较大,共沉淀法制备的样品上转换发光强度要显著高于固相法以及溶胶-凝胶法制备的样品,而溶胶-凝胶法制备的样品发光中红光/绿光相对强度比最高.红外光谱显示,不同方法制备的GdAlO3:Er3+,Yb3+荧光粉表面OH-、CO32-及CO2官能团含量不同,溶胶-凝胶法制备的样品要明显高些.基于红外光谱、不同Er3+和Yb3+离子掺杂浓度及不同激光功率上转换发光的结果,对Er3+和Yb3+之间的能量传递过程及不同方法制备荧光粉的上转换发光性能进行了讨论.     

Bi3+‐Er3+ and Bi3+‐Yb3+ Codoped Cs2AgInCl6 Double Perovskite Near‐Infrared Emitters

Bi³⁺ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi³⁺ and lanthanide ions. Codoping of Bi³⁺ and Ln³⁺ (Ln=Er and Yb) in Cs₂AgInCl₆ double perovskite is presented. Bi³⁺‐Er³⁺ codoped Cs₂AgInCl₆ shows Er³⁺ f‐electron emission at 1540 nm (suitable for low‐loss optical communication). Bi³⁺ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi³⁺‐Er³⁺ codoped Cs₂AgInCl₆ shows ca. 45 times higher emission intensity compared to the Er³⁺ doped Cs₂AgInCl₆. Similar results are also observed in Bi³⁺‐Yb³⁺ codoped sample emitting at 994 nm. A combination of temperature‐dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.     

Bi3+-Er3+ and Bi3+-Yb3+ Codoped Cs2AgInCl6 Double Perovskite Near-Infrared Emitters

Bi³⁺ and lanthanide ions have been codoped in metal oxides as optical sensitizers and emitters. But such codoping is not known in typical semiconductors such as Si, GaAs, and CdSe. Metal halide perovskite with coordination number 6 provides an opportunity to codope Bi³⁺ and lanthanide ions. Codoping of Bi³⁺ and Ln³⁺ (Ln=Er and Yb) in Cs₂AgInCl₆ double perovskite is presented. Bi³⁺-Er³⁺ codoped Cs₂AgInCl₆ shows Er³⁺ f-electron emission at 1540 nm (suitable for low-loss optical communication). Bi³⁺ codoping decreases the excitation (absorption) energy, such that the samples can be excited with ca. 370 nm light. At that excitation, Bi³⁺-Er³⁺ codoped Cs₂AgInCl₆ shows ca. 45 times higher emission intensity compared to the Er³⁺ doped Cs₂AgInCl₆. Similar results are also observed in Bi³⁺-Yb³⁺ codoped sample emitting at 994 nm. A combination of temperature-dependent (5.7 K to 423 K) photoluminescence and calculations is used to understand the optical sensitization and emission processes.     

Preparation,characterization and luminescent properties of spherical CaTiO3:Pr3+ phosphors by spray pyrolysis

In this paper, spherical Pr³⁺-doped CaTiO₃ phosphor particles were fabricated through a two-step spray pyrolysis process, using citric acid and polyethylene glycol (PEG) as additives. X-ray diffraction (XRD), scanning electron microscopy (SEM), High-resolution transmission electron microscopy (HRTEM), thermogravimetric and differential thermal analysis (TG–DTA), X-ray photoelectron spectra (XPS), photoluminescence (PL), cathodoluminescence (CL) spectroscopy, and lifetime measurements were employed to characterize these samples. The results reveal that the as-prepared CaTiO₃:Pr³⁺ phosphors are spherical with submicron particle size. The particles show a strong red emission corresponding to ¹D₂–³H₄ (612 nm) of Pr³⁺ under the ultraviolet excitation (325 nm) and low voltage electron beams (1–5 kV). Furthermore, the morphology, PL and CL intensities of the CaTiO₃:Pr³⁺ phosphors can be tuned by altering the concentration of PEG, annealing temperature, and acceleration voltage. These phosphors show potential applications in the field of field emission displays (FEDs).     

Lead‐Free,Air‐Stable All‐Inorganic Cesium Bismuth Halide Perovskite Nanocrystals

Lead‐based perovskite nanocrystals (NCs) have outstanding optical properties and cheap synthesis conferring them a tremendous potential in the field of optoelectronic devices. However, two critical problems are still unresolved and hindering their commercial applications: one is the fact of being lead‐based and the other is the poor stability. Lead‐free all‐inorganic perovskite Cs₃Bi₂X₉ (X=Cl, Br, I) NCs are synthesized with emission wavelength ranging from 400 to 560 nm synthesized by a facile room temperature reaction. The ligand‐free Cs₃Bi₂Br₉ NCs exhibit blue emission with photoluminescence quantum efficiency (PLQE) about 0.2 %. The PLQE can be increased to 4.5 % when extra surfactant (oleic acid) is added during the synthesis processes. This improvement stems from passivation of the fast trapping process (2–20 ps). Notably, the trap states can also be passivated under humid conditions, and the NCs exhibited high stability towards air exposure exceeding 30 days.     

Lead‐Free,Air‐Stable All‐Inorganic Cesium Bismuth Halide Perovskite Nanocrystals

Lead‐based perovskite nanocrystals (NCs) have outstanding optical properties and cheap synthesis conferring them a tremendous potential in the field of optoelectronic devices. However, two critical problems are still unresolved and hindering their commercial applications: one is the fact of being lead‐based and the other is the poor stability. Lead‐free all‐inorganic perovskite Cs₃Bi₂X₉ (X=Cl, Br, I) NCs are synthesized with emission wavelength ranging from 400 to 560 nm synthesized by a facile room temperature reaction. The ligand‐free Cs₃Bi₂Br₉ NCs exhibit blue emission with photoluminescence quantum efficiency (PLQE) about 0.2 %. The PLQE can be increased to 4.5 % when extra surfactant (oleic acid) is added during the synthesis processes. This improvement stems from passivation of the fast trapping process (2–20 ps). Notably, the trap states can also be passivated under humid conditions, and the NCs exhibited high stability towards air exposure exceeding 30 days.     

A new stepped tetranuclear copper(II) complex: synthesis,crystal structure and photoluminescence properties

Binuclear and tetranuclear copper(II) complexes are of interest because of their structural, magnetic and photoluminescence properties. Of the several important configurations of tetranuclear copper(II) complexes, there are limited reports on the crystal structures and solid‐state photoluminescence properties of `stepped' tetranuclear copper(II) complexes. A new Cu^II complex, namely bis{μ₃‐3‐[(4‐methoxy‐2‐oxidobenzylidene)amino]propanolato}bis{μ₂‐3‐[(4‐methoxy‐2‐oxidobenzylidene)amino]propanolato}tetracopper(II), [Cu₄(C₁₁H₁₃NO₃)₄], has been synthesized and characterized using elemental analysis, FT–IR, solid‐state UV–Vis spectroscopy and single‐crystal X‐ray diffraction. The crystal structure determination shows that the complex is a stepped tetranuclear structure consisting of two dinuclear [Cu₂(L )₂] units {L is 3‐[(4‐methoxy‐2‐oxidobenzylidene)amino]propanolate}. The two terminal Cu^II atoms are four‐coordinated in square‐planar environments, while the two central Cu^II atoms are five‐coordinated in square‐pyramidal environments. The solid‐state photoluminescence properties of both the complex and 3‐[(2‐hydroxy‐4‐methoxybenzylidene)amino]propanol (H₂L ) have been investigated at room temperature in the visible region. When the complex and H₂L are excited under UV light at 349 nm, the complex displays a strong blue emission at 469 nm and H₂L displays a green emission at 515 nm.     

Mn4+-, Tb3+,4+-, and Er3+-activated red phosphors in the MgAl2Si2O8 system

Mn⁴⁺ doped and Tb^3+,4+, Er³⁺ co-doped MgAl₂Si₂O₈-based phosphors were prepared by conventional solid-state synthesis at 1,300 °C. They were characterized by thermogravimetry, differential thermal analysis, X-ray powder diffraction, photoluminescence, and scanning electron microscopy. The luminescence mechanism of the phosphors, which showed broad red emission bands in the range of 600–715 nm and had different maximum intensities when activated by UV illumination, was discussed. Such a red emission can be attributed to the intrinsic ²E → ⁴A₂ transitions of Mn⁴⁺.     

Antimony-Based Halide Perovskite Nanoparticles as Lead-Free Photocatalysts for Controlled Radical Polymerization

Metal halide perovskites have emerged as versatile photocatalysts to convert solar energy for chemical processes. Perovskite photocatalyzed polymerization draws special attention due to its straightforward synthesis process and the ability to create advanced perovskite-polymer nanocomposites. Herein, this work employs Cs₃Sb₂Br₉ perovskite nanoparticles (NPs) as a lead-free photocatalyst for light-controlled atom transfer radical polymerization (ATRP). Cs₃Sb₂Br₉ NPs exhibit high reduction potential and interact with electronegative bromide initiator with Lewis acid Sb sites, enabling efficient photoinduced reduction of initiators and controlled polymerization under blue light irradiation. Methacrylate monomers with various functional groups are successfully polymerized, and the resulting polymer showcased a dispersity (Đ) as small as 1.27. The living nature of polymerization is confirmed by high chain end fidelity and kinetic studies. Moreover, Cs₃Sb₂Br₉ NPs serve as heterogeneous photocatalysts, demonstrating recyclability and reusability for up to four cycles. This work presents a promising approach to overcome the limitations of lead-based perovskites in photoinduced controlled radical polymerization, offering a sustainable and efficient alternative for the synthesis of well-defined polymeric materials.     

Wide-coverage and Efficient NIR Emission from Single-component Nanophosphors through Shaping Multiple Metal-halide Packages

Wide-coverage near infrared (NIR) phosphor-converted LEDs possess promising potential for practical applications, but little is developed towards the efficient and wide-coverage NIR phosphors. Here, we report the single-component lanthanide (Ln³⁺) ions doped Cs₂M(In_0.95Sb_0.05)Cl₆ (M=alkali metal) nanocrystals (NCs), exhibiting emission from 850 to 1650 nm with high photoluminescence quantum yield of 20.3 %, which is accomplished by shaping the multiple metal halide octahedra of double perovskite via the simple alkali metal substitution. From Judd-Ofelt theoretical calculation and spectroscopic investigations, the shaping of metal halide octahedra in Cs₂M(In_1−xSb_x)Cl₆ NCs can break the forbidden of f-f transition of Ln³⁺, thus increasing their radiative transition rates and simultaneously boosting the energy transfer efficiency from host to Ln³⁺. Finally, the wide-coverage NIR LEDs based on Sm³⁺, Nd³⁺, Er³⁺-tridoped Cs₂K_0.5Rb_0.5(In_0.95Sb_0.05)Cl₆ NCs are fabricated and employed in the multiplex gas sensing and night-vision application.     

Optical Spectroscopy and Excited-State Dynamics of Eu3+-Doped Bismuth Borate Glasses Containing CuO

Bismuth borate glasses containing phosphors and luminescent rare-earths are of interest for applications in light-emitting devices. Herein, the influence of CuO impurities on red-emitting Eu³⁺-doped bismuth borate glasses of the 25Bi₂O₃-15BaO-10Li₂O-50B₂O₃ type was investigated by various spectroscopic methods. The glasses were prepared by the melt-quench technique and characterized by X-ray diffraction (XRD), Fourier transform-infrared (FT-IR) spectroscopy, UV/Vis optical absorption (OA), and photoluminescence (PL) spectroscopy including decay kinetics assessment. The XRD data confirmed the amorphous nature of the glasses whereas FT-IR spectra indicated the basic structural features of trigonal BO₃ units and BO₄ tetrahedra. The OA analysis showed that addition of CuO up to 0.5 mol% results in significant growth of the visible Cu²⁺ absorption band around 715 nm, with slight decrease in the optical band gap energies assessed through Tauc plots. A drastic PL quenching of Eu³⁺ ions emission was evidenced concurring with the detrimental effect of Cu²⁺. The assessment of the Eu³⁺ emission decay curves revealed significant lifetime decrease of the ⁵D₀ emitting state with increasing CuO concentration. An analysis of quenching constants was finally performed comparing results from integrated PL data with the emission decay rates. It is argued that the bismuth borate glass system supports an effective Eu³⁺→Cu²⁺ energy transfer (more so than phosphates) in connection with a strong spectral overlap between Eu³⁺ emission and Cu²⁺ absorption.