Construction of White‐Light‐Emitting Silk Protein Hybrid Films by Molecular Recognized Assembly among Hierarchical Structures

The fabrication of bio‐hybrid functional films is demonstrated by applying a materials assembly technique. Based on the hierarchical structures of silk fibroin materials, functional molecular/materials, i.e., quantum dots (QDs), can be fixed to amino acid groups in silk fibroin films. It follows that white‐light‐emitting QD silk hybrid films are obtained by hydrogen bond molecular recognition to the –COO^– groups functionalized to blue luminescent ZnSe (5.2 nm) and yellow luminescent CdTe (4.1 nm) QDs in a molar ratio of 30:1 of ZnSe to CdTe QDs. Simultaneously, a systematic blue shift in the emission peak is observed from the QD solution to QDs silk fibroin films. The significant blue shift hints the appearance of the strong interaction between QDs and silk fibroins, which causes strong white‐light‐emitting uniform silk films. The molecular recognized interactions are confirmed by high resolution transmission electron microscopy, field scanning electron microscope, and attenuated total internal reflectance Fourier transform infrared spectroscopy. The QD silk films show unique advantages, including simple preparation, tunable white‐light emission, easy manipulation, and low fabrication costs, which make it a promising candidate for multicomponent optodevices.     

Organic Light‐Emitting Diodes with a White‐Emitting Molecule: Emission Mechanism and Device Characteristics

The unique and unprecedented electroluminescence behavior of the white‐emitting molecule 3‐(1‐(4‐(4‐(2‐(2‐hydroxyphenyl)‐4,5‐diphenyl‐1H‐imidazol‐1‐yl)phenoxy)phenyl)‐4,5‐diphenyl‐1H‐imidazol‐2‐yl)naphthalen‐2‐ol (W1), fluorescence emission from which is controlled by the excited‐state intramolecular proton transfer (ESIPT) is investigated. W1 is composed of covalently linked blue‐ and yellow‐color emitting ESIPT moieties between which energy transfer is entirely frustrated. It is demonstrated that different emission colors (blue, yellow, and white) can be generated from the identical emitter W1 in organic light‐emitting diode (OLED) devices. Charge trapping mechanism is proposed to explain such a unique color‐tuned emission from W1. Finally, the device structure to create a color‐stable, color reproducible, and simple‐structured white organic light‐emitting diode (WOLED) using W1 is investigated. The maximum luminance efficiency, power efficiency, and luminance of the WOLED were 3.10 cd A^?1, 2.20 lm W^?1, 1 092 cd m^?2, respectively. The WOLED shows white‐light emission with the Commission Internationale de l′Eclairage (CIE) chromaticity coordinates (0.343, 0.291) at a current level of 10 mA cm^?2. The emission color is high stability, with a change of the CIE chromaticity coordinates as small as (0.028, 0.028) when the current level is varied from 10 to 100 mA cm^?2.     

Microwave‐Assisted Preparation of White Fluorescent Graphene Quantum Dots as a Novel Phosphor for Enhanced White‐Light‐Emitting Diodes

Graphene quantum dots (GQDs) with white fluorescence are synthesized by a microwave‐assisted hydrothermal method using graphite as the precursor. A solution‐processed white‐light‐emitting diode (WLED) is fabricated using the as‐prepared white fluorescent GQDs (white‐light‐emitting graphene quantum dots, WGQDs) doped 4,4‐bis(carbazol‐9‐yl)biphenyl as the emissive layer. White‐light emission is obtained from the WLED with 10 wt% doping concentration of WGQDs, which shows a luminance of 200 cd m^?2 at the applied voltage of 11–14 V. Importantly, an external quantum efficiency of 0.2% is achieved, which is the highest among all the reported WLED based on GQDs or carbon dots. The results demonstrate that WGQDs as a novel phosphor may open up a new avenue to develop the environmentally friendly WLEDs for practical application in solid‐state lighting.     

Protein/Polymer‐Based Dual‐Responsive Gold Nanoparticles with pH‐Dependent Thermal Sensitivity

This article presents the synthesis and physicochemical behavior of dual‐responsive plasmonic nanoparticles with reversible optical properties based on protein‐coated gold nanoparticles grafted with thermosensitive polymer brushes by means of surface‐initiated atom transfer radical polymerization (SI‐ATRP) that exhibit pH‐dependent thermo‐responsive behavior. Spherical gold NPs of two different sizes (15 nm and 60 nm) and with different stabilizing agents (citrate and cetyltrimethylammonium bromide (CTAB), respectively) were first capped with bovine serum albumin (BSA). The resulting BSA‐capped NPs (Au@BSA NPs) exhibited not only extremely high colloidal stability under physiological conditions, but also a reversible U‐shaped pH‐responsive behavior, similar to pure BSA. The ?‐amine of the L‐lysine in the protein coating was then used to covalently bind an ATRP‐initiator, allowing for the SI‐ATRP of thermosensitive polymer brushes of oligo(ethylene glycol) methacrylates with an LCST of 42 °C in pure water and around 37 °C under physiological conditions. Such protein coated nanoparticles grafted with thermosensitive polymers exhibit a smart pH‐dependent thermosensitive behavior.     

High‐Performance All‐Polymer White‐Light‐Emitting Diodes Using Polyfluorene Containing Phosphonate Groups as an Efficient Electron‐Injection Layer

We report an efficient non‐doped all‐polymer polymer white‐light‐emitting diode (PWLED) with a fluorescent three‐color, white single polymer as an emissive layer, an ethanol‐soluble phosphonate‐functionalized polyfluorene (PF‐EP) as an electron‐injection/electron‐transport layer, and LiF/Al as a cathode, respectively. The all‐polymer PWLED achieves a peak external quantum efficiency of 6.7%, a forward viewing luminous efficiency of 15.4 cd A^?1 and a power efficiency of 11.4 lm W^?1, respectively, at a brightness of 347 cd m^?2 with Commission Internationale d’Eclairage coordinates of (0.37, 0.42) and color rendering index of 85, which is the best results among the non‐doped PWLEDs. Moreover, this kind of PWLED not only shows excellent color stability, but also achieves high brightness at low voltages. The brightness reaches 1000, 10000, and 46830 cd m^?2 at voltages of 4.5, 5.4, and 7.5 V, respectively. The significant enhancement of white‐single‐polymer‐based PWLEDs with PF‐EP/LiF/Al to replace for the commonly used Ca/Al cathode is attributed to the more efficient electron injection at PF‐EP/LiF/Al interfaces, and the coordinated protecting effect of PF‐EP from diffusion of Al atoms into the emissive layer and exciton‐quenching near cathode interfaces. The developed highly efficient non‐doped all‐polymer PWLEDs are well suitable for solution‐processing technology and provide a huge potential of low‐cost large‐area manufacturing for PWLEDs.     

Hydrogen‐Bonding‐Assisted Intermolecular Charge Transfer: A New Strategy to Design Single‐Component White‐Light‐Emitting Materials

This study reveals the mechanism of the dual‐emission properties for asymmetrical diphenylsulfone and diphenylketone derivatives. A series of asymmetrical diphenylketone and diphenylsulfone derivatives with dual‐emission properties are designed and synthesized. By single crystal structure analyses, various photophysical studies, and 2D ¹H–¹H NOSEY NMR studies, the lower energy emission bands in the dual‐emission spectra are successfully assigned to hydrogen‐bonding‐assisted intermolecular charge transfer emission. The emission properties of these compounds can easily be tuned in both solid state and solution state by destroying or strengthening the intermolecular hydrogen bonding. In addition, thermally activated delayed fluorescence characteristics for the intermolecular charge transfer emissions are also observed. The control of the intermolecular and intramolecular charge transfers serves as the basis for the generation of the white‐light emission. For compound CPzPO, nearly pure white‐light emission with CIE coordinates of (0.31, 0.32) is easily achieved by precipitation from dichloromethane and hexane mixed solvent system. These results clearly give an insight into the dual‐emission properties and provide a rational strategy for the design and synthesis of single‐component white‐light‐emitting materials and mechanoresponsive light‐emitting materials.     

Organic Light‐Emitting Diodes: Organic Light‐Emitting Diodes with a White‐Emitting Molecule: Emission Mechanism and Device Characteristics (Adv. Funct. Mater. 4/2011)

The unique and unprecedented electroluminescence behavior of the white‐emitting molecule 3‐(1‐(4‐(4‐(2‐(2‐hydroxyphenyl)‐4,5‐diphenyl‐1H‐imidazol‐1‐yl)phenoxy)phenyl)‐4,5‐diphenyl‐1H‐imidazol‐2‐yl)naphthalen‐2‐ol (W1), fluorescence emission from which is controlled by the excited‐state intramolecular proton transfer (ESIPT) is investigated. W1 is composed of covalently linked blue‐ and yellow‐color emitting ESIPT moieties between which energy transfer is entirely frustrated. It is demonstrated that different emission colors (blue, yellow, and white) can be generated from the identical emitter W1 in organic light‐emitting diode (OLED) devices. Charge trapping mechanism is proposed to explain such a unique color‐tuned emission from W1. Finally, the device structure to create a color‐stable, color reproducible, and simple‐structured white organic light‐emitting diode (WOLED) using W1 is investigated. The maximum luminance efficiency, power efficiency, and luminance of the WOLED were 3.10 cd A^?1, 2.20 lm W^?1, 1 092 cd m^?2, respectively. The WOLED shows white‐light emission with the Commission Internationale de l′Eclairage (CIE) chromaticity coordinates (0.343, 0.291) at a current level of 10 mA cm^?2. The emission color is high stability, with a change of the CIE chromaticity coordinates as small as (0.028, 0.028) when the current level is varied from 10 to 100 mA cm^?2.     

The Fabrication and Characterization of Single‐Component Polymeric White‐Light‐Emitting Diodes

By using Ni⁰‐mediated polymerization, we have systematically synthesized a series of fluorene‐based copolymers composed of blue‐, green‐, and red‐light‐emitting comonomers with a view to producing polymers with white‐light emission. 2,7‐Dibromo‐9,9‐dihexylfluorene, {4‐(2‐[2,5‐dibromo‐4‐{2‐(4‐diphenylamino‐phenyl)‐vinyl}‐phenyl]‐vinyl)‐phenyl}‐diphenylamine (DTPA), and 2‐{2‐(2‐[4‐{bis(4‐bromo‐phenyl)amino}‐phenyl]‐vinyl)‐6‐tert‐butyl‐pyran‐4‐ylidene}‐malononitrile (TPDCM) were used as the blue‐, green‐, and red‐light‐emitting comonomers, respectively. It was found that the emission spectra of the resulting copolymers could easily be tuned by varying their DTPA and TPDCM content. Thus with the appropriate red/green/blue (RGB) unit ratio, we were able to obtain white‐light emission from these copolymers. A white‐light‐emitting diode using the polyfluorene copolymer containing 3 % green‐emitting DTPA and 2 % red‐emitting TPDCM (PG3R2) with a structure of indium tin oxide/poly(3,4‐ethylenedioxythiophene):poly(styrene sulfonic acid)/PG3R2/Ca/Al was found to exhibit a maximum brightness of 820 cd m^–2 at 11 V with Commission Internationale de L'Eclairage (CIE) coordinates of (0.33,0.35), which are close to the standard CIE coordinates for white‐light emission (0.33,0.33).     

Extremely Efficient White Organic Light‐Emitting Diodes for General Lighting

Highly power‐efficient white organic light‐emitting diodes (OLEDs) are still challenging to make for applications in high‐quality displays and general lighting due to optical confinement and energy loss during electron‐photon conversion. Here, an efficient white OLED structure is shown that combines deterministic aperiodic nanostructures for broadband quasi‐omnidirectional light extraction and a multilayer energy cascade structure for energy‐efficient photon generation. The external quantum efficiency and power efficiency are raised to 54.6% and 123.4 lm W^?1 at 1000 cd m^?2. An extremely small roll‐off in efficiency at high luminance is also obtained, yielding a striking value of 106.5 lm W^?1 at 5000 cd m^?2. In addition to a substantial increase in efficiency, this device structure simultaneously offers the superiority of angular color stability over the visible wavelength range compared to conventional OLEDs. It is anticipated that these findings could open up new opportunities to promote white OLEDs for commercial applications.     

Tuning the Emitting Color of Organic Light‐Emitting Diodes Through Photochemically Induced Transformations: Towards Single‐Layer,Patterned, Full‐Color Displays and White‐Lighting Applications

Photochemically induced emission tuning for the definition of pixels emitting the three primary colors, red, green, blue (RGB), in a single conducting polymeric layer is investigated. The approach proposed is based on an acid‐induced emission shift of the (1‐[4‐(dimethylamino)phenyl]‐6‐phenylhexatriene) (DMA‐DPH) green emitter and acid‐induced quenching of the red fluorescent emitter (4‐dimethylamino‐4′‐nitrostilbene) (DANS). The two emitters are dispersed in the wide bandgap conducting polymer poly(9‐vinylcarbazole) (PVK), along with a photoacid generator (PAG). In the unexposed film areas, red emission is observed because of efficient energy transfer from PVK and DMA‐DPH to DANS. Exposure of selected areas of the film at different doses results in quenching of the red emitter's fluorescence and the formation of green, blue, or even other color‐emitting pixels, depending on the exposure dose and the relative concentrations of the different compounds in the film. Organic light‐emitting diodes having the PVK polymer containing the appropriate amounts of DMA‐DPH, DANS, and PAG as the emitting layer are fabricated and electroluminescence spectra are recorded. The time stability of induced emission spectrum changes and the color stability during device operation are also examined, and the first encouraging results are obtained.     

Toward Highly Efficient Solid‐State White Light‐Emitting Electrochemical Cells: Blue‐Green to Red Emitting Cationic Iridium Complexes with Imidazole‐Type Ancillary Ligands

Using imidazole‐type ancillary ligands, a new class of cationic iridium complexes ( 1 – 6 ) is prepared, and photophysical and electrochemical studies and theoretical calculations are performed. Compared with the widely used bpy (2,2′‐bipyridine)‐type ancillary ligands, imidazole‐type ancillary ligands can be prepared and modified with ease, and are capable of blueshifting the emission spectra of cationic iridium complexes. By tuning the conjugation length of the ancillary ligands, blue‐green to red emitting cationic iridium complexes are obtained. Single‐layer light‐emitting electrochemical cells (LECs) based on cationic iridium complexes show blue‐green to red electroluminescence. High efficiencies of 8.4, 18.6, and 13.2 cd A^?1 are achieved for the blue‐green‐emitting, yellow‐emitting, and orange‐emitting devices, respectively. By doping the red‐emitting complex into the blue‐green LEC, white LECs are realized, which give warm‐white light with Commission Internationale de L'Eclairage (CIE) coordinates of (0.42, 0.44) and color‐rendering indexes (CRI) of up to 81. The peak external quantum efficiency, current efficiency, and power efficiency of the white LECs reach 5.2%, 11.2 cd A^?1, and 10 lm W^?1, respectively, which are the highest for white LECs reported so far, and indicate the great potential for the use of these cationic iridium complexes in white LECs.     

Highly Efficient Pure‐White‐Light‐Emitting Diodes from a Single Polymer: Polyfluorene with Naphthalimide Moieties

Light‐emitting diodes exhibiting efficient pure‐white‐light electroluminescence have been successfully developed by using a single polymer: polyfluorene derivatives with 1,8‐naphthalimide chromophores chemically doped onto the polyfluorene backbones. By adjusting the emission wavelength of the 1,8‐naphthalimide components and optimizing the relative content of 1,8‐naphthalimide derivatives in the resulting polymers, white‐light electroluminescence from a single polymer, as opposed to a polymer blend, has been obtained in a device with a configuration of indium tin oxide/poly(3,4‐ethylenedioxythiophene)(50 nm)/polymer(80 nm)/Ca(10 nm)/Al(100 nm). The device exhibits Commission Internationale de l'Eclairage coordinates of (0.32,0.36), a maximum brightness of 11 900 cd m^–2, a current efficiency of 3.8 cd A^–1, a power efficiency of 2.0 lm W^–1, an external quantum efficiency of 1.50 %, and quite stable color coordinates at different driving voltages, even at high luminances of over 5000 cd m^–2.     

Red,Green, and Blue Light‐Emitting Polyfluorenes Containing a Dibenzothiophene‐S,S‐Dioxide Unit and Efficient High‐Color‐Rendering‐Index White‐Light‐Emitting Diodes Made Therefrom

A series of blue (B), green (G) and red (R) light‐emitting, 9,9‐bis(4‐(2‐ethyl‐hexyloxy)phenyl)fluorene (PPF) based polymers containing a dibenzothiophene‐S,S‐dioxide (SO) unit (PPF‐SO polymer), with an additional benzothiadiazole (BT) unit (PPF‐SO‐BT polymer) or a 4,7‐di(4‐hexylthien‐2‐yl)‐benzothiadiazole (DHTBT) unit (PPF‐SO‐DHTBT polymer) are synthesized. These polymers exhibit high fluorescence yields and good thermal stability. Light‐emitting diodes (LEDs) using PPF‐SO25, PPF‐SO15‐BT1, and PPF‐SO15‐DHTBT1 as emission polymers have maximum efficiencies LE_max = 7.0, 17.6 and 6.1 cd A^?1 with CIE coordinates (0.15, 0.17), (0.37, 0.56) and (0.62, 0.36), respectively. 1D distributed feedback lasers using PPF‐SO30 as the gain medium are demonstrated, with a wavelength tuning range 467 to 487 nm and low pump energy thresholds (≥18 nJ). Blending different ratios of B (PPF‐SO), G (PPF‐SO‐BT) and R (PPF‐SO‐DHTBT) polymers allows highly efficient white polymer light‐emitting diodes (WPLEDs) to be realized. The optimized devices have an attractive color temperature close to 4700 K and an excellent color rendering index (CRI) ≥90. They are relatively stable, with the emission color remaining almost unchanged when the current densities increase from 20 to 260 mA cm^?2. The use of these polymers enables WPLEDs with a superior trade‐off between device efficiency, CRI, and color stability.     

Conjugated Polyelectrolyte Hybridized ZnO Nanoparticles as a Cathode Interfacial Layer for Efficient Polymer Light‐Emitting Diodes

Alkoxy side‐chain tethered polyfluorene conjugated polyelectrolyte (CPE), poly[(9,9‐bis((8‐(3‐methyl‐1‐imidazolium)octyl)‐2,7‐fluorene)‐alt‐(9,9‐bis(2‐(2‐methoxyethoxy)ethyl)‐fluorene)] dibromide (F8imFO₄), is utilized to obtain CPE‐hybridized ZnO nanoparticles (NPs) (CPE:ZnO hybrid NPs). The surface defects of ZnO NPs are passivated through coordination interactions with the oxygen atoms of alkoxy side‐chains and the bromide anions of ionic pendent groups from F8imFO₄ to the oxygen vacancies of ZnO NPs, and thereby the fluorescence quenching at the interface of yellow‐emitting poly(p‐phenylene vinylene)/CPE:ZnO hybrid NPs is significantly reduced at the CPE concentration of 4.5 wt%. Yellow‐emitting polymer light‐emitting diodes (PLEDs) with CPE(4.5 wt%):ZnO hybrid NPs as a cathode interfacial layer show the highest device efficiencies of 11.7 cd A^?1 at 5.2 V and 8.6 lm W^?1 at 3.8 V compared to the ZnO NP only (4.8 cd A^?1 at 7 V and 2.2 lm W^?1 at 6.6 V) or CPE only (7.3 cd A^?1 at 5.2 V and 4.9 lm W^?1 at 4.2 V) devices. The results suggest here that the CPE:ZnO hybrid NPs has a great potential to improve the device performance of organic electronics.     

Investigation of Optical and Structural Stability of Localized Surface Plasmon Mediated Light‐Emitting Diodes by Ag and Ag/SiO2 Nanoparticles

Localized surface plasmon (LSP) effects due to Ag and Ag/SiO₂ nanoparticles (NPs) deposited on GaN/InGaN multiquantum well (MQW) light‐emitting diode (LED) structures are studied. The colloidal NPs are synthesized by a sol‐gel method and drop‐cased on the LED structures. The surface density of NPs its controlled by the concentration of the NP solution. Theoretical modeling is performed for the emission spectrum and the electric field distribution of LSP resonance for Ag/SiO₂ NPs. Enhanced photoluminescence (PL) efficiency is observed in the LED structures and the amount of PL enhancement increases with increasing the surface density of Ag and Ag/SiO₂ NPs. These effects are attributed to resonance coupling between the MQW and LSP in the NPs. It is also shown that the PL enhancement attainable with Ag NPs and Ag/SiO₂ NPs is comparable, but the latter displays a much higher stability with respect to long‐term storage and annealing due to a barrier for NP agglomeration, Ag oxidation, and impurity diffusion provided by the SiO₂ shell.     

Advances and Challenges in White Light‐Emitting Electrochemical Cells

Since the birth of light‐emitting electrochemical cells (LECs) in 1995, white LECs (WLECs) still represent a milestone. To date, over 50 contributions have been reported, presenting record WLECs with brightness of up to 10 000 cd m^?2, efficiencies of >10 cd A^?1, and excellent color rendering index >90 in different contributions. This is achieved following three main strategies focused on modifying: i) the design of the emitters, that is, emissive aggregates, multiemissive mechanism, multifluorophoric emitters; ii) the active layer composition, that is, host–guest, multilayers, exciplex‐ and electroplex‐like emitting species systems; and iii) the device architecture, that is, tandem, photoactive filters, and microcavity/interfacial dipole effects. Herein, all of them are comprehensively discussed with respect to the above strategies in the frame of the type of emitters employed. Overall, this work highlights both the advances and challenges of the WLEC field.     

Simplified Bilayer White Phosphorescent Organic Light‐Emitting Diodes

We report on highly efficient blue, orange, and white phosphorescent organic light‐emitting diodes consisting only two organic layers. Hole transporting 4, 4,’ 4”‐tris (N‐carbazolyl)triphenylamine (TcTa) and electron transporting 2‐(diphenylphosphoryl) spirofluorene (SPPO1) are used as an emitting host for orange light‐emitting bis(3‐benzothiazol‐2‐yl‐9‐ethyl‐9H‐carbazolato) (acetoacetonate) iridium ((btc)2(acac)Ir) and blue light‐emitting iridium(III)bis(4,6‐difluorophenyl‐pyridinato‐N,C2’) picolinate (FIrpic) dopant, respectively. Combining these two orange and blue light‐emitting layers, we successfully demonstrate highly efficient white PHOLEDs while maintaining Commission internationale de l'éclairage coordinates of (, ). Accordingly, we achieve a maximum external quantum, current, and power efficiencies of 12.9%, 30.3 cd/A, and 30.0 lm/W without out‐coupling enhancement.     

White‐Light‐Emitting Diodes Based on Iridium Complexes via Efficient Energy Transfer from a Conjugated Polymer

Efficient white‐light‐emitting diodes (WLEDs) have been developed using a polyfluorene‐type blue‐emitting conjugated polymer doped with green and red phosphorescent dyes. The emission spectrum of the conjugated polymer, which has a very high luminescent efficiency, shows a large spectral overlap with the absorbance of green and red iridium complexes. Also, efficient energy transfer from the conjugated polymer to the iridium complexes is observed. Poly(N‐vinyl carbazole) is used to improve the miscibility between conjugated polymer and iridium complexes because of their poor chemical compatibility and phase separation. A white emission spectrum is easily obtained by varying the contents of the three materials and controlling the phase morphology. Moreover, these WLEDs show a voltage‐independent electroluminescence owing to the threshold and driving voltage of the three materials being similar as a result of energy transfer.