Doped Lead Halide White Phosphors for Very High Efficiency and Ultra‐High Color Rendering

Near‐UV‐pumped white‐light‐emitting diodes with ultra‐high color rendering and decreased blue‐light emission is highly desirable. However, discovering a single‐phase white light emitter with such characteristics remains challenging. Herein, we demonstrate that Mn doping as low as 0.027 % in the hybrid post‐perovskite type (TDMP)PbBr₄ (TDMP=trans‐2,5‐dimethylpiperaziniium) enables to achieve a bright pure white emission replicating the spectrum of the sun's rays. Thus, a white phosphor exhibiting an emission with CIE coordinates (0.330, 0.365), a high photoluminescence quantum yield of 60 % (new record for white light emission of hybrid lead halides), and an ultra‐high color rendering index (CRI=96, R9=91.8), corresponding to the record value for a single phase emitter was obtained. The investigation of the photoluminescence properties revealed how free excitons, self‐trapped excitons, and low amount of Mn dopants are coupled to give rise to such pure white emission.     

Zero‐Dimensional Hybrid Cd‐Based Perovskites with Broadband Bluish White‐Light Emissions

Recently, low‐dimensional organic‐inorganic hybrid metal halide perovskites acting as single‐component white‐light emitting materials have attracted extensive attention, but most studies concentrate on hybrid lead perovskites. Herein, we present two isomorphic zero‐dimensional (0D) hybrid cadmium perovskites, (HMEDA)CdX₄ (HMEDA=hexamethylenediamine, X=Cl ( 1 ), Br ( 2 )), which contain isolated [CdX₄]^2? anions separated by [HMEDA]²⁺ cations. Under UV light excitation, both compounds display broadband bluish white‐light emission (515 nm for 1 and 445 nm for 2 ) covering the entire visible light spectrum with sufficient photophysical stabilities. Remarkably, compound 2 shows a high color rendering index (CRI) of 83 enabling it as a promising candidate for single‐component WLED applications. Based on the temperature‐dependent, powder‐dependent and time‐resolved PL measurements as well as other detailed studies, the broadband light emissions are attributed to self‐trapped excitons stemming from the strong electron‐phonon coupling.     

Improving Broadband White-Light Emission Performances of 2D Perovskites by Subtly Regulating Organic Cations

Recently, 2D organic–inorganic hybrid lead halide perovskites have attracted intensive attention in solid-state luminescence fields such as single-component white-light emitters, and rational optimization of the photoluminescence (PL) performance through accurate structural-design strategies is still significant. Herein, by carefully choosing homologous aliphatic amines as templates, isotypical perovskites [DMEDA]PbCl₄ ( 1 , DMEDA=N,N-dimethylethylenediamine) and [DMPDA]PbCl₄ ( 2 , DMPDA=N,N-dimethyl-1,3-diaminopropane) having tunable and stable broadband bluish white emission properties were rationally designed. The subtle regulation of organic cations leads to a higher degree of distortion of the 2D [PbCl₄]²⁻ layers and enhanced photoluminescence quantum efficiencies (<1 % for 1 and 4.9 % for 2 ). The broadband light emissions could be ascribed to self-trapped excitons on the basis of structural characterization, time-resolved PL, temperature-dependent PL emission, and theoretical calculations. This work gives a new guidance to rationally optimize the PL properties of low-dimensional halide perovskites and affords a platform to probe the structure–property relationship.     

Acridan‐Grafted Poly(biphenyl germanium) with High Triplet Energy,Low Polarizability,and an External Heavy‐Atom Effect for Highly Efficient Sky‐Blue TADF Electroluminescence

We propose the novel σ–π conjugated polymer poly(biphenyl germanium) grafted with two electron‐donating acridan moieties on the Ge atom for use as the host material in a polymer light‐emitting diode (PLED) with the sky‐blue‐emitting thermally activated delayed fluorescence (TADF) material DMAC‐TRZ as the guest. Its high triplet energy (E_T) of 2.86 eV is significantly higher than those of conventional π–π conjugated polymers (E_T=2.65 eV as the limit) and this guest emitter (E_T=2.77 eV). The TADF emitter emits bluer emission than in other host materials owing to the low orientation polarizability of the germanium‐based polymer host. The Ge atom also provides an external heavy‐atom effect, which increases the rate of reverse intersystem crossing in this TADF guest, so that more triplet excitons are harvested for light emission. The sky‐blue TADF electroluminescence with this host/guest pair gave a record‐high external quantum efficiency of 24.1 % at maximum and 22.8 % at 500 cd m^?2.     

Acridan‐Grafted Poly(biphenyl germanium) with High Triplet Energy,Low Polarizability,and an External Heavy‐Atom Effect for Highly Efficient Sky‐Blue TADF Electroluminescence

We propose the novel σ–π conjugated polymer poly(biphenyl germanium) grafted with two electron‐donating acridan moieties on the Ge atom for use as the host material in a polymer light‐emitting diode (PLED) with the sky‐blue‐emitting thermally activated delayed fluorescence (TADF) material DMAC‐TRZ as the guest. Its high triplet energy (E_T) of 2.86 eV is significantly higher than those of conventional π–π conjugated polymers (E_T=2.65 eV as the limit) and this guest emitter (E_T=2.77 eV). The TADF emitter emits bluer emission than in other host materials owing to the low orientation polarizability of the germanium‐based polymer host. The Ge atom also provides an external heavy‐atom effect, which increases the rate of reverse intersystem crossing in this TADF guest, so that more triplet excitons are harvested for light emission. The sky‐blue TADF electroluminescence with this host/guest pair gave a record‐high external quantum efficiency of 24.1 % at maximum and 22.8 % at 500 cd m^?2.     

Merging Boron and Carbonyl based MR-TADF Emitter Designs to Achieve High Performance Pure Blue OLEDs**

Multiresonant thermally activated delayed fluorescence (MR-TADF) compounds are attractive as emitters for organic light-emitting diodes (OLEDs) as they can simultaneously harvest both singlet and triplet excitons to produce light in the device and show very narrow emission spectra, which translates to excellent color purity. Here, we report the first example of an MR-TADF emitter (DOBDiKTa) that fuses together fragments from the two major classes of MR-TADF compounds, those containing boron (DOBNA) and those containing carbonyl groups (DiKTa) as acceptor fragments in the MR-TADF skeleton. The resulting molecular design, this compound shows desirable narrowband pure blue emission and efficient TADF character. The co-host OLED with DOBDiKTa as the emitter showed a maximum external quantum efficiency (EQE_max) of 17.4 %, an efficiency roll-off of 32 % at 100 cd m⁻², and Commission Internationale de l’Éclairage (CIE) coordinates of (0.14, 0.12). Compared to DOBNA and DiKTa, DOBDiKTa shows higher device efficiency with reduced efficiency roll-off while maintaining a high color purity, which demonstrates the promise of the proposed molecular design.     

Ca[B8O11(OH)4] : Eu2+ – A Highly Efficient Deep Blue-Emitting Phosphor Prepared by Low-Temperature Self-reduction

Highly efficient inorganic phosphors are crucial for solid-state lighting. In this paper, a new method of low-temperature self-reduction was used for preparing a highly efficient deep blue-emitting phosphor of Ca[B₈O₁₁(OH)₄] : Eu²⁺ (CBH : Eu²⁺). The crystal structure, morphology, chemical state, and photoluminescence (PL) properties of the CBH : Eu²⁺ phosphor have been investigated. By using the screened hybrid function (HSE06), the band gap (E_g) of CBH was calculated to be 7.48 eV, which is a necessary condition for achieving high quantum yield phosphors. The experiment results show that almost all the added raw materials of Eu³⁺ can be reduced to Eu²⁺ in CBH crystal under a non-reducing atmosphere. The CBH : Eu²⁺ phosphor shows a broad excitation spectrum centered at 277 and 327 nm in the range of 220 to 400 nm, and a narrow-band emission spectrum centered at 428 nm in the range of 400 to 500 nm, with a full width at half maximum (fwhm) of 42.35 nm. Under UV radiation, the CBH : 2 %Eu²⁺ exhibits high photoluminescence quantum yield (PLQY=95.0 %), high external quantum efficiency (EQE=31.1 %), and ultra-high color purity (97.6 %). The PL intensity of CBH : 2 %Eu²⁺ remains 62.6 % of the initial intensity at 150 °C. Finally, the white light-emitting diodes (WLED) fabricated by CBH : 2 %Eu²⁺, excited by a 365 nm chip, presents outstanding performances with a luminous efficacy (LE) of 13.9 lm/W, a color rendering index (CRI) of 89.4, and a correlated color temperature (CCT) of 5825 K. The above results show that CBH : Eu²⁺ can be used as a promising blue phosphor for WLED. This new method of low-temperature self-reduction can be applied to design and prepare other new types of highly efficient phosphors.     

Hydrogen Peroxide Assisted Synthesis of Highly Luminescent Sulfur Quantum Dots

An H₂O₂‐assisted top‐down approach is used to synthesize brightly luminescent, color‐tunable sulfur quantum dots (SQDs), with a photoluminescence quantum yield of up to 23 %. The formation of SQDs involves dissolution of bulk sulfur powder into small particles in an alkaline environment in the presence of polyethylene glycol, followed by H₂O₂‐assisted etching of polysulfide species, which has the advantage of the passivation of surface states. This synthetic strategy allows us to simultaneously control the final size of SQDs, to tune their emission color, and to improve their emission quantum yield by eliminating surface traps. Down‐conversion white light emitting diodes were also fabricated using blue emissive SQDs and orange emissive copper nanoclusters, with CIE color coordinates of (0.33, 0.32) and a high color rendering index of 91. The water‐soluble, highly luminescent SQDs are promising luminescent materials that can be produced from abundant precursor materials.     

Highly Effective Hybrid Copper(I) Iodide Cluster Emitter with Negative Thermal Quenched Phosphorescence for X-Ray Imaging

The low efficiency triplet emission of hybrid copper(I) iodide clusters is a critical obstacle to their further practical optoelectronic application. Herein, we present an efficient hybrid copper(I) iodide cluster emitter (DBA)₄Cu₄I₄ , where the cooperation of excited state structure reorganization and the metallophilicity interaction enables ultra-bright triplet yellow-orange emission with a photoluminescence quantum yield over 94.9 %, and the phonon-assisted de-trapping process of exciton induces the negative thermal quenching effect at 80–300 K. We also investigate the potential of this emitter for X-ray imaging. The (DBA)₄Cu₄I₄ wafer demonstrates a light yield higher than 10⁴ photons MeV⁻¹ and a high spatial resolution of ≈5.0 lp mm⁻¹, showing great potential in practical X-ray imaging applications. Our new copper(I) iodide cluster emitter can serve as a model for investigating the thermodynamic mechanism of photoluminescence in hybrid copper(I) halide phosphorescence materials.     

Crystal rigidifying strategy toward hybrid cadmium halide to achieve highly efficient and narrowband blue light emission

Highly efficient and narrowband blue light-emitting performance is extremely crucial for the optoelectronic applications of organic-inorganic hybrid perovskites. However, the not yet viable approach has been shown to simultaneously improve photoluminescence quantum yield (PLQY) and narrow linewidth of blue light emission. Herein, a new crystal rigidifying strategy is proposed as a viable dual-optimization avenue. Specifically, we perform a post-synthetic technique on hybrid cadmium halides and successfully convert zero-dimensional (0D) DMP-0-CdBr₄ to one-dimensional (1D) DMP-1-CdBr₃, accompanied by luminescent transformation from sky-blue (470 nm) to deep-blue (432 nm) emissions. The structural evolution from discrete block to infinite chain significantly enhances the crystal rigidity, which results in narrower emission linewidth (89 to 50 nm) and increased color purity (74.5% to 96.7%). Synchronously, the PLQY also realizes a notable enhancement from 14.0% to 52.3%. Systematical characterizations demonstrate that enhanced crystal rigidity simultaneously weakens the electron-phonon interaction and slows down nonradiative decay, which narrows the emission linewidth and boosts the PLQY. The highly efficient light-emitting performance enables them as excellent down-conversion blue phosphors to fabricate solid-state LED giving bright warm white light with high color rendering index of 95.4. This work paves a novel structural optimization way to rationally design or fine-tune high-performance blue-light emitting halides.     

Novel Composites of Graphitic‐phase Nitrogen Carbon/Lanthanide Coordination Polymers as White Light‐emitting Phosphor

Lanthanide coordination polymers (Ln‐CPs) are excellent candidates for designing white light materials due to their adjustable fluorescent characteristic by decorating organic ligands, changing metal centers and including guests. However, low quantum yield, weak blue emission, high prices and supply risks have hindered the application and developments of the pure Ln‐CPs materials. Herein, we have designed a new white color composite material capable of white light‐emission upon excitation at 338 nm, which fabricated by compositing a graphitic‐phase nitrogen carbon (g‐C₃N₄) treated with nitric acid and lanthanide‐based complexes, with the photoluminescencequantum yield (QY) in solid state reaching 11.7 %. WLEDs constructed by depositing the (g‐C₃N₄)_0.783/Eu_0.133/Tb_0.083‐dbpt [dbpt = 3‐(3,5‐dicarboxylphenyl)‐5‐(pyrazinyl)‐1H‐1,2,4‐triazole] composites on a commercial UV LED chip feature a CIE chromaticity coordinate at (0.33, 0.33), high color rendering index (CRI) of 94.6. Compared to conventional white light‐emission Ln‐CPs materials of La_0.928Eu_0.045Tb_0.027‐dbpt and La_0.896Eu_0.104‐dbpt reveals that (g‐C₃N₄)_0.783/Eu_0.133/Tb_0.083‐dbpt composites have higher QY and CRI values.     

High red,green, and blue color purity electroluminescence from MEH‐PPV and polyalkyfluorenes‐based bright white polymer light emitting displays

A series of white polymer light emitting displays (PLEDs) based on a polymer blend of polyalkylfluorenes and poly(2‐methoxy‐5,2′‐ethyl‐hexyloxy‐1,4‐phenylene vinylene) (MEH‐PPV) was developed. MEH‐PPV or red light emitting alkyfluorene copolymer (PFR) was blended with blue light emitting alkyfluorene copolymer (PFB), and MEH‐PPV was blended with both green light emitting alkyfluorene copolymer (PFG) and PFB to generate white light emission PLEDs. Low turn on voltage (2.7 V), high brightness (12,149 nits), high efficiency (4.0 cd/A, 4.0 lm/W), and good color purity (Commission Internationale de L'Eclairage (CIE_x,y) co‐ordinates (0.32, 0.34)) were obtained for the white PLEDs based on the PFB and MEH‐PPV polymer blend. Exciplex formation in the interface between PFR and PFB induced a new green emission peak for these two components based white PLEDs. As a result, strong white emission (4078 nits) was obtained by mixing the red, green, and blue (RGB) three primary colors. High color purity of blue (CIE, x = 0.14, y = 0.08), green (CIE, x = 0.32, y = 0.64) and red (CIE, x = 0.67, y = 0.33) emissions was achieved for white PLEDs combining with dielectric interference color‐filters. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 330–341, 2007     

Solid‐State Carbon Dots with Efficient Cyan Emission towards White Light‐Emitting Diodes

Efficient cyan‐emitting solid carbon dots (CDs) were synthesized via a one‐pot hydrothermal method. The obtained solid CDs show a broad absorption from 270–460 nm with a maximum around 400 nm, and emit intense cyan light around 500 nm with an internal photoluminescence quantum efficiency of 34.1 % under 400 nm excitation. The emission maximum of the solid CDs remains unchanged under 320–400 nm excitations. Compared with dilute aqueous of CDs (2.5 mg mL^?1), the emission of solid CDs shows an obvious red‐shift of 50 nm. The red‐shift is caused by resonant energy transfer due to larger spectral overlap and smaller interparticle distance, together with a new surface state caused by aggregation in solid CDs. A lamp with white LEDs was fabricated by dropping a mixture of solid CDs, CaAlSiN₃:Eu²⁺ and silicon resin on the top of a near‐ultraviolet LED chip. Under an operating current of 20 mA, the as‐fabricated white LED generates a high‐quality, warm white light with a color rendering index of 86.1, a color temperature of 4340 K, and a luminescence efficiency of 31.3 lm W^?1.     

Fixed‐Component Lanthanide‐Hybrid‐Fabricated Full‐Color Photoluminescent Films as Vapoluminescent Sensors

Full‐color lanthanide (Ln) photoluminescent materials have attracted considerable interest owing to their potential applications in display systems and lighting technologies. Herein, full‐color photoluminescent films have been designed and fabricated facilely with a fixed‐component Ln‐based (Ln=Tb and Eu) polymer hybrid doped with a proton‐sensitive amide‐type β‐diketonated photosensitizer, N‐(2‐pyridinyl)benzoylacetamide (HPBA). The tunable photoluminescence emissions of the films are achieved by changing the amounts of OH^? in the hybrid rather than varying the relative concentrations of the lanthanide ions and photosensitizers, thus representing a new paradigm for full‐color displays. The emission color can also be finely tuned through the variation of the excitation wavelength, and white‐light emission can be achieved when the given film is excited at the visible region (405 nm). The photophysical properties and the mechanisms of the intra‐ and intermolecular energy transfer before and after deprotonation have been investigated in detail. Meanwhile, the films might find application as vapoluminescent sensors due to their good stability, sensitivity, reversibility, and quick response when triggered by a base–acid vapor.     

Facile Synthesis of Highly Emissive All-Inorganic Manganese Bromide Compounds with Perovskite-Related Structures for White LEDs

Lead-free all-inorganic halide materials with different Mn²⁺-based crystal structures (Cs₃MnBr₅ and CsMnBr₃) were obtained using a convenient synthetic method. Cs₃MnBr₅ had a bright green emission (522 nm), with a unique single-exponential lifetime (τ_avg = 236 µs) and a high photoluminescence quantum yield (82 ± 5%). A red emission was observed in the case of the CsMnBr₃ structure with a two-exponential fluorescence decay curve, and the lifetime was 1.418 µs (93%) and 18.328 µs (7%), respectively. By a judicious tuning of the synthetic conditions, a mixed phase of Cs₃MnBr₅/CsMnBr₃ was also produced that emitted white light, covering almost the entire visible spectrum. White-light-emitting diodes (WLEDs) with color coordinates (0.4269, 0.4955), a color temperature of (3773 K), and a color rendering index (68) were then fabricated using the as-prepared powder of mixed phases of Cs₃MnBr₅/CsMnBr₃ with a commercial UV LED chip (365 nm).     

White‐Light Emission from a Semi‐Conductive Borate‐Stannate

In response to ever‐increasing application requirements in lighting and displays, a tremendous emphasis is being placed on single‐component white‐light emission. Single‐component inorganic borates doped with rare earth metal ions have shown prominent achievements in white‐light emission. The first environmentally friendly defect‐induced white‐light emitting crystalline inorganic borate, Ba₂[Sn(OH)₆][B(OH)₄]₂, has been prepared. Additionally, it is the first borate‐stannate without a Sn?O?B linkage. Notably, Ba₂[Sn(OH)₆][B(OH)₄]₂ shows Commission Internationale de l'Eclairage (CIE) chromaticity coordinates of (0.42, 0.38), an ultrahigh color rendering index (CRI) of 94.1, and an appropriate correlated color temperature (CCT) of 3083 K. Such a promising material will provide a new approach in the development of white‐light emitting applications.     

Obtain full visible spectrum light-emitting diode illumination via bismuth-activated cyan phosphors

Developing highly efficient cyan-emitting fluorescent materials is essential to bridge the cyan gap in phosphor-converted white light-emitting diodes for full-spectrum white illumination. Here, a Bi-doped cyan phosphor has been reported to solve this gap. The phase purity, photoluminescence emission/excitation spectra, concentration quenching, lifetime decay curves, and temperature-dependent photoluminescence emission spectra were systematically investigated. SrLaGaO₄:Bi³⁺ exhibits a broad excitation band (250–400 nm), which matches with the emission of a commercial near-ultraviolet light-emitting diode chip. The cyan light peaked at 475 nm is observed, which is attributed to the ³P₁→¹S₀ transition of Bi³⁺. The thermal quenching experiment was performed, and the activation energy was calculated as 0.36 eV. Finally, full-spectrum white light-emitting diode devices were fabricated using SrLaGaO₄:Bi³⁺ phosphors, commercial blue BaMgAl₁₀O₁₇:Eu²⁺ phosphor, green (Ba, Sr)₂SiO₄:Eu²⁺ phosphor, and red CaAlSiN₃:Eu²⁺ phosphor, which displayed an International Commission on an illumination coordinate of (0.3732, 0.3850), a correlated color temperature of 4290 K, and a color rendering index of 93.2 at a drive current of 20 mA. This result indicates that SrLaGaO₄:Bi³⁺ plays an essential role in bridging the cyan gap, providing new inspiration for applying cyan-emitting phosphors in full-spectrum white lighting.     

Twisted penta‐Carbazole/Benzophenone Hybrid Compound as Multifunctional Organic Host,Dopant or Non‐doped Emitter for Highly Efficient Solution‐Processed Delayed Fluorescence OLEDs

A new multi‐functional penta‐carbazole/benzophenone hybrid compound 5CzBP was designed and synthesized through a simple one‐step catalyst‐free C—N coupling reaction by using 2,3,4,5,6‐pentafluorobenzophenone and carbazole as starting materials. 5CzBP is very soluble in tetrahydrofuran (THF), which brings an environmentally friendly device fabrication for solution‐processed OLEDs instead of most widely used chlorinated solvents when 5CzBP is employed as the bulk‐phase of organic host or non‐doped emitter in the emissive layer. 5CzBP exhibits thermally activated delayed fluorescence (TADF) characteristic with relatively high triplet energy of 2.60 eV and a low ΔE_ST of 0.01 eV. By using the new TADF material as organic host for another green TADF emitter, maximum external quantum efficiency (EQE) of 12.5% has been achieved in simple solution‐processed OLED device. Besides, a maximum EQE of 8.9% and 5.7% was further obtained in TADF devices based on 5CzBP as dopant and non‐doped emitter, respectively. The simultaneously acting as efficient TADF host and non‐doped TADF emitter provides the potential guidance of the future simple single‐layer two‐color white OLEDs based on low‐cost pure organic TADF materials.     

New Phosphors for White LEDs

White light-emitting diodes (WLEDs) have matched the emission efficiency of florescent lights and will rapidly spread as light source for homes and offices in the next 5 to 10 years. WLEDs provide a light element having a semiconductor light emitting layer (blue or UV LEDs) and photoluminescence phosphors. GaN-based highly efficient blue InGaN LEDs combined with phosphors can produce white light. These solid-state LED lamps have a number of advantages over conventional incandescent bulbs and halogen lamps, such as high efficiency to convert electrical energy into light, reliability, and long operating lifetime (about 100,000 hours). For the purpose of development of high energy-efficient white light sources, we need to produce highly efficient new phosphors, which can absorb excitation energy from blue or UV LEDs and generate emissions.In this paper, we investigate the development of blue or UV LEDs by the appropriate combination of new phosphors which can lead us to obtain high brightness white light. The criteria of choosing the best phosphors, for blue (380-450 nm) and UV (360-400 nm) LEDs, strongly depends on the absorption and emission of the phosphors. Moreover, the balance light between the light emission from blue LEDs and the yellow YAG:Ce,Gd phosphor is important to obtain white light with high color temperature. The phosphors with high efficiency which can be excited by UV LEDs are important to obtain the white light with high color rendering index.     

One‐pot synthesis of carbon dots@ZrO2 nanoparticles with tunable solid‐state fluorescence

In recent years, fluorescent carbon dots (CDs) have been developed and showed potential applications in biomedical imaging and light‐emitting diodes (LEDs) for their excellent fluorescent properties. However, it still remains a challenge to incorporate fluorescent CDs into the host matrix in situ to overcome their serious self‐quenching. Herein, a one‐pot hydrothermal method is used to prepare nano‐zirconia with CDs (CDs@ZrO₂) nanoparticles. During the reaction, CDs and nano‐zirconia are generated simultaneously and connected with silane coupling agent. The CDs@ZrO₂ nanoparticles exhibit tunable emission wavelength from 450 to 535 nm emission by regulating the content of citric acid in the feed. The quantum yield of the CDs@ZrO₂ is up to 23.8%. Furthermore, the CDs@ZrO₂ nanoparticles with regulable fluorescence emission can be used for the fluorescent material to prepare white LEDs. The prepared LED has significant white light emission with color coordinates of (0.30, 0.37) and its color rendering index (CRI) is 67.1. In summary, we have developed the solid‐state CDs@ZrO₂ nanoparticles with tunable emission by a valuable strategy, that is, one‐pot method, for white LEDs.