Light-emitting diodes with semiconductor nanocrystals

Colloidal semiconductor nanocrystals are promising luminophores for creating a new generation of electroluminescence devices. Research on semiconductor nanocrystal based light-emitting diodes (LEDs) has made remarkable advances in just one decade: the external quantum efficiency has improved by over two orders of magnitude and highly saturated color emission is now the norm. Although the device efficiencies are still more than an order of magnitude lower than those of the purely organic LEDs there are potential advantages associated with nanocrystal-based devices, such as a spectrally pure emission color, which will certainly merit future research. Further developments of nanocrystal-based LEDs will be improving material stability, understanding and controlling chemical and physical phenomena at the interfaces, and optimizing charge injection and charge transport.     

The photosensitizing potential of compact fluorescent vs incandescent light bulbs

Recently an article about the new energy‐saving compact fluorescent light (CFL) bulbs appeared in Parade magazine [Rosenfeld, I. (2008) Parade Feb 3 , 22]. Under the heading “Bright Lights, Bad Headache?” the writer states that “new research suggests some dangers” involving these lights because they are fluorescent and “can aggravate skin rashes in people with lups, eczema, dermatitis or porphyria.” We measured the emission spectrum of a 14 W compact fluorescent bulb (with the same luminous flux as a 60 W incandescent bulb) and compared it to 60 W soft white incandescent and cool white fluorescent (CWF) bulbs. Our results clearly show that the spectral irradiance of the compact fluorescent bulb is similar to that of the CWF bulb; both exhibit sharp Hg emission lines at 365 nm (very weak), 404 nm (weak), 435 nm (moderate) and 543 nm (strong). In contrast, the emission of the incandescent bulb begins at 375 nm and then increases monotonically to above 750 nm. From their respective absorption spectra we calculated the potential photosensitization indices of protoporphyrin IX (PPIX; a prototypic porphyria skin photosensitizer) and riboflavin (a putative lens photosensitizer) vs 14 W compact fluorescent, CWF and 60 W incandescent bulbs. A higher photosensitization index would indicate a greater chance that the light/photosensitizer combination would cause photosensitization of the skin or eyes. We found that for PPIX and riboflavin the photosensitization index of the compact fluorescent bulb is less than half that of the 60 W incandescent bulb. These results suggest that substitution of a compact fluorescent bulb for an incandescent bulb of the same luminous flux should not increase the phototoxicity of skin porphyrins or lens riboflavin.     

Using an excellent near-UV-excited cyan-emitting phosphor for enhancing the color rendering index of warm-white LEDs by filling the cyan gap

White light-emitting diodes (LEDs) with high color rendering index (CRI) and low correlated color temperature (CCT) are desirable for next-generation solid-state lighting. In this work, we demonstrated an efficient near-UV-excited cyan-emitting phosphor based on Ce³⁺-doped Ca₂LuHf₂Al₃O₁₂ (CLHAO) garnet, which could be used to cover the cyan gap for fabricating high-CRI warm-white LEDs. We found that the CLHAO:Ce³⁺ samples exhibited a broad excitation band in the 300–450 nm wavelength range peaking at 400 nm, and upon 400 nm excitation they showed broad cyan emission bands in the 420–600 nm spectral region with peak positions ranging from 477 to 493 nm. The optimal CLHAO:0.02Ce³⁺ sample had CIE color coordinates of (0.160, 0.255), and its internal and external quantum efficiencies were measured to be 84.3% and 60.8%, respectively. Impressively, the luminescence intensity of CLHAO:0.02Ce³⁺ sample at 423 K still remained at 62% of the initial value at 303 K, and the chromaticity shift was calculated to be as low as 1.7 × 10^?2, revealing its high thermal stability and color stability at a higher temperature. Finally, a warm-white LED device (CCT = 3,194 K) was fabricated by combining CLHAO:0.02Ce³⁺ cyan phosphors with commercial blue/green/red tricolor phosphors, showing bright white-light emission with a high CRI of 89.4, which was superior to that of another warm-white LED device (CRI = 83.2) fabricated without CLHAO:0.02Ce³⁺ cyan phosphors. These outstanding luminescence properties of CLHAO:Ce³⁺ cyan phosphors illustrated that they offer a new feasible approach for the production of high-CRI warm-white LEDs toward high-color-quality solid-state lighting.     

Efficient and Low-voltage Phosphorescent Organic Light-emitting Devices Based on Blue Iridium Complex Host

By adopting a phosphorescent host/guest system consisting of blue iridium complex as host and a series of phosphorescent dyes as guest, efficient and low-voltage monochromic organic light-emitting devices(OLEDs) were fabricated. The devices with blue iridium host have higher power efficiency than the device with the conventional host 4,4'-N,N'-dicarbazole-biphenyl. The enhancement of the maximum power efficiency in green phosphorescent device can reach 37.2%. Dichromatic white OLED could be achieved by simply adjusting the concentration of the orange dyes. At a brightness of 1000 cd/m², the power efficiency of the white device is 8.4 lm/W with a color rendering index of 76.     

Novel high-saturated red-emitting phosphor Sr9(Mg0.5Mn0.5)K(PO4)7: Eu2+ with great quantum efficiency enhancement by La3+ codoping for white LED application

In this work, a novel whitlockite-structure red-emitting phosphor host, Sr₉(Mg_0.5Mn_0.5)K(PO₄)₇, is designed and successfully synthesized via a solid-state reaction. Upon X-ray diffractometer Rietveld refinement, it is revealed that this compound possesses compact Eu²⁺-Mn²⁺ distance (3.6809 Å) and large intra-Mn²⁺ distance (8.9905 Å), which is beneficial to the high-efficient Eu²⁺-Mn²⁺ energy transfer. By Eu²⁺ sensitization, our new phosphor exhibits a high-saturated and bright red Mn²⁺ emission at 620 nm with high color purity of 97.9%. Great emission enhancement up to 245 times than host is achieved by La³⁺ heterovalent substitution, which can be ascribed to the La³⁺-induced further structural confinement effect. Moreover, the quantum efficiency is boosted by twofold. The as-fabricated white phosphor-converted LEDs device shows bright warm white light with correlated color temperature (CCT) of 3,487 K, color-rendering index (CRI) of 92.4, and luminous efficacy of 31.59 lm/W. This work proves the feasibility of chemical unit co-substitution strategy in emission engineering of Mn²⁺-based phosphors, which can stimulate further studies on the red-emitting phosphor 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.     

Triplet Exciton Upconverting Blue Exciplex Host for Deep Blue Phosphors

A thermally activated delayed fluorescence (TADF)-type exciplex host employing a novel electron-transport type (n-type) type host managing positive polarons and stabilizing excitons was developed to elongate the device lifetime of deep blue phosphorescent organic light-emitting diodes (PhOLEDs). The bipolar n-type host was designed to prevent hole leakage and secure hole stability while being stabilized under excitons by introducing a CN-modified carbazole moiety as a weak donor. The TADF-type exciplex host-based blue PhOLEDs showed high (above 20 %) quantum efficiency with a deep blue color coordinate of (0.14, 0.16) and elongated device lifetime. The device operational lifetime of the blue PhOLEDs bearing the TADF-type exciplex host was extended by more than twice compared to that of the exciplex-free unipolar host. This work suggested a design concept of the n-type host to develop the TADF-type exciplex host for deep blue phosphors to reach a long lifespan in the deep blue PhOLEDs.     

Light-emitting diodes are better illumination sources for biological microscopy than conventional sources.

Light-emitting diodes (LEDs) can be easily and inexpensively integrated into modern light microscopes. There are numerous advantages of LEDs as illumination sources; most notably, they provide brightness and spectral control. We demonstrate that for transmitted light imaging, an LED can replace the traditional tungsten filament bulb while offering longer life; no color temperature change with intensity change; reduced emission in the infrared region, which is important for live cell imaging; and reduced cost of ownership. We show a direct substitution of the typical tungsten bulb with a commercially available LED and demonstrated the color stability by imaging a histology section over a wide range of light intensities. For fluorescent imaging, where the typical illumination sources are mercury or xenon lamps, we demonstrate that LEDs offer advantages of providing a longer lifespan, having a more constant intensity output over time, more homogeneous illumination, and significantly lower photon dose. Our LED equipped system was used to image and deconvolve dual fluorescently labeled cells, as well as image cells undergoing mitosis expressing green fluorescent protein-histone 2B complex. The timing of the stages of mitosis is well established as an indicator of cell viability.     

蓝光钙钛矿发光二极管:机遇与挑战

金属卤化钙钛矿由于具有优异的光电性能(如:高电子/空穴迁移率,高荧光量子产率,高色纯度,以及光色可调性等),成为应用于发光二极管(LED)的理想材料。近年来,钙钛矿LED的发展十分迅速,红光和绿光钙钛矿LED的外量子效率(EQE)均已超过20%。然而,蓝光(尤其是深蓝光)钙钛矿LED的EQE以及稳定性依然相对落后,这严重制约了钙钛矿LED在高性能、广色域显示领域和高显色指数白光照明领域的应用。因此,总结现阶段蓝光钙钛矿LED的发展,并剖析其机遇与挑战,对未来蓝光甚至整个钙钛矿LED领域的发展至关重要。本文将蓝光钙钛矿LED根据光色细分为天蓝光、纯蓝光、深蓝光三大部分进行总结,回顾了三种LED器件的发展历程,并详细阐述了现阶段实现他们的主要手段以及相关的基础原理,最后分析了它们各自的问题并提出了相应的解决思路。     

Effective Host Materials for Blue/White Organic Light‐Emitting Diodes by Utilizing the Twisted Conjugation Structure in 10‐Phenyl‐9,10‐Dihydroacridine Block

Two new 10‐phenyl‐9,10‐dihydroacridine derivatives attached by dibenzothiophene (DBT) and dibenzofuran (DBF) were synthesized. The influence of the substituents of these materials was studied by theoretical calculations (DFT calculation) and experimental measurements. Owing to the twisted N‐phenyl ring, both molecules possess sufficiently high triplet energies and are suitable as hosts for phosphorescent organic light‐emitting diodes. To evaluate the electroluminescent (EL) performance of these materials, FIrpic‐based blue PHOLEDs and two‐color white PHOLEDs (FIrpic and PO‐01 as the dopants) were fabricated using the common device structures. High external quantum efficiencies (EQE) of 21.1 % and 20.9 % for FIrpic‐based blue PHOLEDs were achieved by FPhAc and TPhAc, respectively. The white device based on the host FPhAc achieved a higher performance, with a maximum EQE of 24.7 % than the device with TPhAc as host material.     

Free radical bromination by the H2O2-HBr system on water

An aqueous solution of hydrogen peroxide and hydrogen bromide illuminated by a 40 W incandescent light bulb serves as a source of bromine radicals. Various substituted toluenes (H, Me, tBu, Br, COOEt, COPh, NO₂) were brominated at the benzyl position. This haloperoxidase-like system for benzylic bromination does not require the presence of metal ions or an organic solvent for efficient conversion of methyl-arenes to benzyl bromides.     

胶体量子阱发光二极管的研究进展

胶体量子阱(CQW)由于具有高色纯度、高光致发光量子效率、光色可调等优异的光电性能，近年来成为一种新型的光电材料，广泛用于制备发光二极管、激光、探测器、太阳能电池等半导体器件。其中，基于CQW的发光二极管(CQW-LED)因为具备极窄的光谱、极佳的色纯度、高效率、可溶液加工、可柔性化等优点，在显示和照明等领域展现出重要应用前景，受到学术界和工业界的广泛重视而成为研究热点。本文首先介绍了CQW-LED中的一些基本概念，包括CQW材料特性、LED器件结构、发光机理等；然后从CQW材料种类的角度出发，阐述了基于单核型、核/冠型、核/壳型、复杂异质结型、以及杂质掺杂型CQW-LED近年来的研究进展，并结合我们研究团队最近的工作详细的介绍了实现高性能CQW-LED的方法，包括对材料选取、设计策略、器件结构、器件性能、工作机理以及发光过程的分析；接着，介绍了CQW-LED的集成应用；最后探讨了CQW-LED目前面临的挑战及其未来的发展机遇。     

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.     

Immobilization of trypsin on miniature incandescent bulbs for infrared-assisted proteolysis

A novel efficient proteolysis approach was developed based on trypsin-immobilized miniature incandescent bulbs and infrared (IR) radiation. Trypsin was covalently immobilized in the chitosan coating on the outer surface of miniature incandescent bulbs with the aid of glutaraldehyde. When an illuminated enzyme-immobilized bulb was immersed in protein solution, the emitted IR radiation could trigger and accelerate heterogeneous protein digestion. The feasibility and performance of the novel proteolysis approach were demonstrated by the digestion of hemoglobin (HEM), cytochrome c (Cyt-c), lysozyme (LYS), and ovalbumin (OVA) and the digestion time was significantly reduced to 5 min. The obtained digests were identified by MALDI-TOF-MS with the sequence coverages of 91%, 77%, 80%, and 52% for HEM, Cyt-c, LYS, and OVA (200 ng μL⁻¹ each), respectively. The suitability of the prepared bulb bioreactors to complex proteins was demonstrated by digesting human serum.     

Wide‐Range Color‐Tunable Organic Phosphorescence Materials for Printable and Writable Security Inks

Organic materials with long‐lived, color‐tunable phosphorescence are potentially useful for optical recording, anti‐counterfeiting, and bioimaging. Herein, we develop a series of novel host–guest organic phosphors allowing dynamic color tuning from the cyan (502 nm) to orange red (608 nm). Guest materials are employed to tune the phosphorescent color, while the host materials interact with the guest to activate the phosphorescence emission. These organic phosphors have an ultra‐long lifetime of 0.7 s and a maximum phosphorescence efficiency of 18.2 %. Although color‐tunable inks have already been developed using visible dyes, solution‐processed security inks that are temperature dependent and display time‐resolved printed images are unprecedented. This strategy can provide a crucial step towards the next‐generation of security technologies for information handling.     

Exciton quenching in emitter blends for organic light emitting devices probed by electric field-dependent time-resolved luminescence

We investigate quenching mechanisms of excited states in emitter layers for organic light emitting diodes (LEDs). An extensive study of a strong electric field-induced modulation (over 50%) of the time-resolved luminescence in a diamine derivative (TPD): polycarbonate blend films doped with an organic complex of europium are presented as a typical example of an important class of emitters for organic monochromatic LEDs. Using this method allowed us to identify the quenched species as the excited ligand precursors of the emissive europium ion states. Manipulating the electrode materials and their electrical bias, the electric field-enhanced dissociation, and interaction with injected charge could be separated and found as principal quenching mechanisms. We show the first one to follow the three-dimensional Onsager theory of geminate recombination, and the second one raised by their interaction with the TPD-transported holes. The interaction rate constant is found to be underlain by the three-dimensional diffusion of excited ligand singlets, combining the exciton diffusion coefficient and long-range (Forster type) energy transfer parameters. The dynamic parameters of the hole-precursor excitons interactions, extracted from the experimental data, allow us to establish the criteria for identifying useful ligands and matrices in the optimized design of electrophosphorescent, linelike emitting molecules, and device structure for organic LEDs.     

量子点发光二极管中电荷累积行为

量子点发光二极管(QLED)是不需要额外光源的主动发光技术,在显示领域中的应用前景被广泛看好。寿命较短是影响QLED商业化的重要因素之一,并且其老化机理尚不清晰。在本工作中,我们通过自主搭建电荷提取装置,证实红光QLED在恒流驱动过程中,存在显著的电荷累积。累积电荷量随着驱动电流密度增加而增加,但当超过阈值电流密度(对应于开启电压)后逐渐趋于饱和。随着器件老化,亮度下降伴随着累积电荷量进一步增加。本工作对QLED老化过程中电荷累积规律的理解,能为QLED材料和界面的优化设计提供直观判据。     

High-Performance Perovskite Light-Emitting Diode with Enhanced Operational Stability Using Lithium Halide Passivation

Defect passivation has been demonstrated to be effective in improving the radiative recombination of charge carriers in perovskites, and consequently, the device performance of the resultant perovskite light-emitting diodes (LEDs). State-of-the-art useful passivation agents in perovskite LEDs are mostly organic chelating molecules that, however, simultaneously sacrifice the charge-transport properties and thermal stability of the resultant perovskite emissive layers, thereby deteriorating performance, and especially the operational stability of the devices. We demonstrate that lithium halides can efficiently passivate the defects generated by halide vacancies and reduce trap state density, thereby suppressing ion migration in perovskite films. Efficient green perovskite LEDs based on all-inorganic CsPbBr₃ perovskite with a peak external quantum efficiency of 16.2 %, as well as a high maximum brightness of 50 270 cd m⁻², are achieved. Moreover, the device shows decent stability even under a brightness of 10⁴ cd m⁻². We highlight the universal applicability of defect passivation using lithium halides, which enabled us to improve the efficiency of blue and red perovskite LEDs.     

Molecular and Device Design Strategies for Ideal Performance White Organic Light‐Emitting Diodes

The progress of white organic light‐emitting diodes (WOLEDs) via adopting fluorescent and phosphorescent organic materials have attracted commercial interest for their broad range of visible spectrum and potential of 100 % internal quantum efficiency. In this account, smart molecular designs for developing efficient phosphorescent host and good color purity blue fluorescent emitters are prepared to be discussed, especially donor‐acceptor modification to regulate their triplet states and bipolar transport properties. Rational device configuration design strategies were also introduced by cooperating with efficient conventional fluorescent and thermally activated delayed fluorescent emitting molecules to achieve full exciton utilization and simplified device structures, further suggesting perspectives of potentially low‐cost, ideal performance and promoted operational lifetime in WOLED devices.     

Modulating Photo‐ and Electroluminescence in a Stimuli‐Responsive π‐Conjugated Donor–Acceptor Molecular System

Functional organic materials that display reversible changes in fluorescence in response to external stimuli are of immense interest owing to their potential applications in sensors, probes, and security links. While earlier studies mainly focused on changes in photoluminescence (PL) color in response to external stimuli, stimuli‐responsive electroluminescence (EL) has not yet been explored for color‐tunable emitters in organic light‐emitting diodes (OLEDs). Here a stimuli‐responsive fluorophoric molecular system is reported that is capable of switching its emission color between green and orange in the solid state upon grinding, heating, and exposure to chemical vapor. A mechanistic study combining X‐ray diffraction analysis and quantum chemical calculations reveals that the tunable green/orange emissions originate from the fluorophore's alternating excited‐state conformers formed in the crystalline and amorphous phases. By taking advantage of this stimuli‐responsive fluorescence behavior, two‐color emissive OLEDs were produced using the same fluorophore in different solid phases.