Recent Progress in White Light‐Emitting Electrochemical Cells

Solid‐state white light‐emitting electrochemical cells (LECs) exhibit the following advantages: simple device structures, low operation voltage, and compatibility with inert metal electrodes. LECs have been studied extensively since the first demonstration of white LECs in 1997, due to their potential application in solid‐state lighting. This review provides an overview of recent developments in white LECs, specifically three major aspects thereof, namely, host–guest white LECs, nondoped white LECs, and device engineering of white LECs. Host–guest strategy is widely used in white LECs. Host materials are classified into ionic transition metal complexes, conjugated polymers, and small molecules. Nondoped white LECs are based on intra‐ or intermolecular interactions of emissive and multichromophore materials. New device engineering techniques, such as modifying carrier balance, color downconversion, optical filtering based on microcavity effect and localized surface plasmon resonance, light extraction enhancement, adjusting correlated color temperature of the output electroluminescence spectrum, tandem and/or hybrid devices combining LECs with organic light‐emitting diodes, and quantum‐dot light‐emitting diodes improve the device performance of white LECs by ways other than material‐oriented approaches. Considering the results of the reviewed studies, white LECs have a bright outlook.     

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.     

Small Molecules in Light‐Emitting Electrochemical Cells: Promising Light‐Emitting Materials

Light‐emitting electrochemical cells (LECs) are solid‐state lighting devices that convert electric current to light within electroluminescent organic semiconductors, and these devices have recently attracted significant attention. Introduced in 1995, LECs are considered a great breakthrough in the field of light‐emitting devices for their applications in scalable and adaptable fabrication processes aimed at producing cost‐efficient devices. Since then, LECs have evolved through the discovery of new suitable emitters, understanding the working mechanism of devices, and the development of various fabrication methods. LECs are best known for their simple architecture and easy, low‐cost fabrication techniques. The key feature of their fabrication is the use of air stable electrodes and a single active layer consisting of mobile ions that enable efficient charge injection and transport processes within LEC devices. More importantly, LEC devices can be operated at low voltages with high efficiencies, contributing to their widespread interest. This review provides a general overview of the development of LECs and discusses how small molecules can be utilized in LEC applications by overcoming the use of traditional lighting materials like polymers and ionic transition metal complexes. The achievements of each study concerning small molecule LECs are discussed.     

Recent Advances in Optical Engineering of Light‐Emitting Electrochemical Cells

Since the first demonstration of light‐emitting electrochemical cells (LECs) in 1995, much effort has been made to develop this technology for display and lighting. A common LEC generally contains a single emissive layer blended with a salt, which provides mobile ions under a bias. Ions accumulated at electrodes facilitate electrochemical doping such that operation voltage is low even when employing high‐work‐function inert electrodes. The superior properties of simple device architecture, low‐voltage operation, and compatibility with inert metal electrode render LECs suitable for cost‐effective light‐emitting sources. In addition to enormous progress in developing novel emissive materials for LECs, optical engineering has been shown to improve device performance of LECs in an alternative way. Light outcoupling enhancement technologies recycle the trapped light and increase the light output from LECs. Techniques to estimate emission zone position provide a powerful tool to study carrier balance of LECs and to optimize device performance. Spectral tailoring of the output emission from LECs based on microcavity effect and localized surface plasmon resonance of metal nanoparticles improves the intrinsic emission properties of emissive materials by optical means. These reported optical techniques are overviewed in this review.     

Light‐Emitting Electrochemical Cells Based on Color‐Tunable Inorganic Colloidal Quantum Dots

Large‐area, ultrathin light‐emitting devices currently inspire architects and interior and automotive designers all over the world. Light‐emitting electrochemical cells (LECs) and quantum dot light‐emitting diodes (QD‐LEDs) belong to the most promising next‐generation device concepts for future flexible and large‐area lighting technologies. Both concepts incorporate solution‐based fabrication techniques, which makes them attractive for low cost applications based on, for example, roll‐to‐roll fabrication or inkjet printing. However, both concepts have unique benefits that justify their appeal. LECs comprise ionic species in the active layer, which leads to the omission of additional organic charge injection and transport layers and reactive cathode materials, thus LECs impress with their simple device architecture. QD‐LEDs impress with purity and opulence of available colors: colloidal quantum dots (QDs) are semiconducting nanocrystals that show high yield light emission, which can be easily tuned over the whole visible spectrum by material composition and size. Emerging technologies that unite the potential of both concepts (LEC and QD‐LED) are covered, either by extending a typical LEC architecture with additional QDs, or by replacing the entire organic LEC emitter with QDs or perovskite nanocrystals, still keeping the easy LEC setup featured by the incorporation of mobile ions.     

Blue‐Emitting Iridium(III) Complexes for Light‐Emitting Electrochemical Cells: Advances,Challenges, and Future Prospects

Light‐emitting electrochemical cells (LECs) are one of the most promising technologies for solid‐sate lighting. Among them, LECs based on phosphorescent iridium(III) complexes have attracted significant research interest in the past 15 years, because of their high efficiency and tunable emission color across the entire visible spectrum. To fabricate white LECs for lighting, high‐performance blue LECs are the first prerequisite. Huge efforts have been devoted to improving the performances of blue LECs based on iridium(III) complexes either by developing new blue‐emitting complexes or by engineering the devices. Nevertheless, blue LECs have still shown much lower performances (brightness, efficiency, stability, etc.) compared to the red, orange‐red, yellow, and green counterpart devices. In particular, a single blue LEC with satisfactory blue‐color purity, high efficiency, and high stability is still missing. Here, the advances in blue‐emitting iridium(III) complexes for LECs and the device engineering on LECs using the complexes are reported. The challenges ahead are discussed, and future prospects are outlined.     

Recent Progress on Light‐Emitting Electrochemical Cells with Nonpolymeric Materials

Light‐emitting electrochemical cells (LECs) have emerged as some of the simplest light‐emitting devices. Indeed, numerous LECs have been produced using fluorescent polymers; however, initial LEC structures require a mixture of polymers and electrolytes, thus strictly limiting their applicability. In contrast, recent advances in device technologies and material synthesis have opened a route for LECs using nonpolymeric materials. This progress report focuses on current developments in the device concepts, mechanisms, and characteristics of LECs that allow the utilization of nonpolymeric materials. First, the three primary device types, namely, electrochemically doped, ionic‐material, and electrostatically doped LECs, are categorized, and their distinct features are described. Second, electrochemically doped LECs based on small molecules and branched molecules are introduced. Then, an overview of the rapidly growing field of ionic‐material LECs, especially ionic transition metal complexes, ionic small molecules and perovskites, and their characteristics are provided. Following these results, recent achievements in solid‐state materials, such as inorganic single crystals, quantum dots, and 2D materials, as electrostatically doped LECs are highlighted. Finally, an overview and evaluation of these LECs reveal the key directions and remaining issues that must be overcome to further functionalize LECs, which provide a versatile approach for new lighting applications comprising emergent materials.     

Fundamentals of Materials Selection for Light‐Emitting Electrochemical Cells

The in situ formation of a light‐emitting p–n or p–i–n junction in light‐emitting electrochemical cells (LECs) necessitates mixed ionic–electronic conductors in the active layer. This unique characteristic requires electronic, luminescent, and ionic ingredients that work synergistically in the LECs. The material requirements that lead to promising electroluminescent properties are discussed and the important components reported so far are surveyed. Particular attention is paid to the working mechanisms behind junction formation and stabilization to create efficient and stable electroluminescence in conjugated‐polymer‐based LECs. Keeping these fundamentals in mind explains how LEC devices have evolved from classic conjugated polymer blends into highly stable crosslinked, hybrid composite, and stretchable device architectures. To conclude, a future development strategy is proposed based on a dual approach: develop new materials specifically for LEC devices and explore novel ways to efficiently process and stabilize the p–i–n junction, which will drive improvements in both LEC external quantum efficiency and operating lifetime toward truly low‐cost solid‐state lighting applications.     

Circumventing Dedicated Electrolytes in Light‐Emitting Electrochemical Cells

Light‐emitting electrochemical cells (LECs) are devices that utilize efficient ion redistribution to produce high‐efficiency electroluminescence in a simple device architecture. Prototypical polymer LECs utilize three components in the active layer: a luminescent conducting polymer, a salt, and an electrolyte. Similarly, many small‐molecule LECs also utilize an electrolyte to disperse salts. In these systems, the electrolyte is incorporated to efficiently conduct ions and to maintain phase compatibility between all components. However, certain LEC approaches and materials systems enable device operation without a dedicated electrolyte. This review describes the general methods and materials used to circumvent the use of a dedicated electrolyte in LECs. The techniques of synthetically coupling electrolytes, incorporating ionic liquids, and introducing inorganic salts are presented in view of research efforts to date. The use of these techniques in emerging classes of light‐emitting electrochemical cells is also discussed. These approaches have yielded some of the most efficient, long‐lasting, and commercially applicable LECs to date.     

Light‐Emitting Paper

A solution‐based fabrication of flexible and light‐weight light‐emitting devices on paper substrates is reported. Two different types of paper substrates are coated with a surface‐emitting light‐emitting electrochemical cell (LEC) device: a multilayer‐coated specialty paper with an intermediate surface roughness of 0.4 μm and a low‐end and low‐cost copy paper with a large surface roughness of 5 μm. The entire device fabrication is executed using a handheld airbrush, and it is notable that all of the constituent layers are deposited from solution under ambient air. The top‐emitting paper‐LECs are highly flexible, and display a uniform light emission with a luminance of 200 cd m^?2 at a current conversion efficacy of 1.4 cd A^?1.     

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.     

Controlling the Chromaticity of Small‐Molecule Light‐Emitting Electrochemical Cells Based on TIPS‐Pentacene

This work demonstrates a novel proof‐of‐concept to implement pentacene derivatives as emitters for the third generation of light‐emitting electrochemical cells based on small‐molecules (SM‐LECs). Here, a straightforward procedure is shown to control the chromaticity of pentacene‐based lighting devices by means of a photoinduced cycloaddition process of the 6,13‐bis(triisopropylsilylethynyl) (TIPS)‐pentacene that leads to the formation of anthracene‐core dimeric species featuring a high‐energy emission. Without using the procedure, SM‐LECs featuring deep‐red emission with Commission Internationale d'Eclairage (CIE) coordinates of x = 0.69/y = 0.31 and irradiance of 0.4 μW cm^?2 are achieved. After a careful optimization of the cycloaddition process, warm white devices with CIE coordinates of x = 0.36/y = 0.38 and luminances of 10 cd m^?2 are realized. Here, the mechanism of the device is explained as a host–guest system, in which the dimeric species acts as the high‐energy band gap host and the low‐energy bandgap TIPS‐pentacene is the guest. To the best of the knowledge, this work shows the first warm white SM‐LECs. Since this work is based on the archetypal TIPS‐pentacene and the photoinduced cycloaddition process is well‐knownfor any pentacenes, this proof‐of‐concept could open a new way to use these compounds for developing white lighting sources.     

Dye Encapsulated Metal‐Organic Framework for Warm‐White LED with High Color‐Rendering Index

A strategy by encapsulating organic dyes into the pores of a luminescent metal‐organic framework (MOF) is developed to achieve white‐light‐emitting phosphor. Both the red‐light emitting dye 4‐(p‐dimethylaminostyryl)‐1‐methylpyridinium ( DSM ) and the green‐light emitting dye acriflavine ( AF ) are encapsulated into a blue‐emitting anionic MOF ZJU‐28 through an ion‐exchange process to yield the MOF?dye composite ZJU‐28?DSM/AF . The emission color of the obtained composite can be easily modulated by simply adjusting the amount and component of dyes. With careful adjustment of the relative concentration of the dyes DSM and AF , the resulting ZJU‐28?DSM/AF (0.02 wt% DSM , 0.06 wt% AF ) exhibits a broadband white emission with ideal CIE coordinates of (0.34, 0.32), high color‐rendering index value of 91, and moderate correlated color temperature value of 5327 K. Such a strategy can be easily expanded to other luminescent MOFs and dyes, thus opening a new perspective for the development of white light emitting materials.     

Cover Picture: White Electroluminescence from a Single‐Polymer System with Simultaneous Two‐Color Emission: Polyfluorene as the Blue Host and a 2,1,3‐Benzothiadiazole Derivative as the Orange Dopant (Adv. Funct. Mater. 7/2006)

New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized by Wang and co‐workers on p. 957. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue and orange emission from the corresponding emitting species. A single‐layer device has been fabricated that has performance characteristics roughly comparable to those of organic white‐light‐emitting diodes with multilayer device structures. New single‐polymer electroluminescent systems containing two individual emission species—polyfluorenes as a blue host and 2,1,3‐benzothiadiazole derivative units as an orange dopant on the main chain—have been designed and synthesized. The resulting single polymers are found to have highly efficient white electroluminescence with simultaneous blue (λ_max = 421 nm/445 nm) and orange emission (λ_max = 564 nm) from the corresponding emitting species. The influence of the photoluminescence (PL) efficiencies of both the blue and orange species on the electroluminescence (EL) efficiencies of white polymer light‐emitting diodes (PLEDs) based on the single‐polymer systems has been investigated. The introduction of the highly efficient 4,7‐bis(4‐(N‐phenyl‐N‐(4‐methylphenyl)amino)phenyl)‐2,1,3‐benzothiadiazole unit to the main chain of polyfluorene provides significant improvement in EL efficiency. For a single‐layer device fabricated in air (indium tin oxide/poly(3,4‐ethylenedioxythiophene): poly(styrene sulfonic acid/polymer/Ca/Al), pure‐white electroluminescence with Commission Internationale de l'Eclairage (CIE) coordinates of (0.35,0.32), maximum brightness of 12 300 cd m^–2, luminance efficiency of 7.30 cd A^–1, and power efficiency of 3.34 lm W^–1 can be obtained. This device is approximately two times more efficient than that utilizing a single polyfluorene containing 1,8‐naphthalimide moieties, and shows remarkable improvement over the corresponding blend systems in terms of efficiency and color stability. Thermal treatment of the single‐layer device before cathode deposition leads to the further improvement of the device performance, with CIE coordinates of (0.35,0.34), turn‐on voltage of 3.5 V, luminance efficiency of 8.99 cd A^–1, power efficiency of 5.75 lm W^–1, external quantum efficiency of 3.8 %, and maximum brightness of 12 680 cd m^–2. This performance is roughly comparable to that of white organic light‐emitting diodes (WOLEDs) with multilayer device structures and complicated fabrication processes.     

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.     

Metal Halide Perovskite Light‐Emitting Devices: Promising Technology for Next‐Generation Displays

As the requirements and expectation for displays in society are growing, higher standards of the display technology are proposed, including wider color gamut, higher color purity, and higher resolution. The recent emergence of light‐emitting halide perovskites has come with numerous advantages, such as high charge‐carrier mobility, tunable emission wavelength, narrow emission linewidth, and intrinsically high photoluminescence quantum yield. Recent advancement of perovskite‐based light‐emitting diodes (PeLEDs) as a promising technology for next‐generation displays is reviewed. Here, how the attractive optical and electrical properties of perovskite materials can be translated into high PeLED performance are discussed, and working mechanisms and optimization approaches of both perovskite materials and the respective devices are analyzed. On the material side this includes the control of size and composition of perovskites grains and nanocrystals, surface and interface passivation, doping and alloying, while on the device side this includes the interfacial engineering and energy level adjustments, and photon emission enhancement. Several challenges such as performance of blue PeLEDs, the environmental and operational stability of PeLEDs, and the toxicity issues of lead halide perovskites are discussed, and perspectives on future developments of perovskite materials and PeLEDs for the display technology are offered.     

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.     

Device Physics of White Polymer Light‐Emitting Diodes

The charge transport and recombination in white‐emitting polymer light‐ emitting diodes (PLEDs) are studied. The PLED investigated has a single emissive layer consisting of a copolymer in which a green and red dye are incorporated in a blue backbone. From single‐carrier devices the effect of the green‐ and red‐emitting dyes on the hole and electron transport is determined. The red dye acts as a deep electron trap thereby strongly reducing the electron transport. By incorporating trap‐assisted recombination for the red emission and bimolecular Langevin recombination for the blue emission, the current and light output of the white PLED can be consistently described. The color shift of single‐layer white‐emitting PLEDs can be explained by the different voltage dependencies of trap‐assisted and bimolecular recombination.     

Organic Solid Solutions: Formation and Applications in Organic Light‐Emitting Diodes

To enhance the performance of organic devices, doping and graded mixed‐layer structures, formed by co‐evaporation methods, have been extensively adopted in the formation of organic thin films. Among the criteria for selecting materials systems, much attention has been paid to the materials' energy‐band structure and carrier‐transport behavior. As a result, some other important characteristics may have been overlooked, such as material compatibility or solubility. In this paper, we propose a new doping method utilizing fused organic solid solutions (FOSSs) which are prepared via high‐pressure and high‐temperature processing. By preparing fused solid solutions of organic compounds, the stable materials systems can be selected for device fabrication. Furthermore, by using these FOSSs, doping concentration and uniformity can be precisely controlled using only one thermal source. As an example of application in organic thin films, high‐performance organic light‐emitting diodes with both single‐color and white‐light emission have been prepared using this new method. Compared to the traditional co‐evaporation method, a FOSS provides us with a more convenient way to optimize the doping system and fabricate relatively complicated organic devices.     

Progress on Light‐Emitting Electrochemical Cells toward Blue Emission,High Efficiency,and Long Lifetime

Since their emergence in the 1990s, light‐emitting electrochemical cells (LECs) have attracted much attention due to their unique properties and potential for use as an alternative technology for illuminations and displays. After decades of development, however, the performance of LECs remains far from satisfactory for practical applications, in particular for those requiring blue light. Efforts have been made to develop of highly efficient blue‐emitting materials and more advanced device structures, aiming at realizing blueshifted emission, enhancing efficiency, and extending prolonged device lifetimes. A timely review into the current state of blue LECs is deemed imperative, as a full understanding of the molecular and device design strategy and identification of the major challenges that must be addressed to realize practical applications is necessary. A specific summary of recent progress on blue LECs is provided, with the focus placed on design strategies for blue emitters for LECs and device structures with respect to color tuning, efficiency enhancement, and stability improvement. Finally, the direction of development strategies in the future is suggested.