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 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.     

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.     

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.     

Exciplex Emission in Light‐Emitting Electrochemical Cells and Light Outcoupling Methods for More Efficient LEC Devices

Much effort has gone into research on light‐emitting electrochemical cells (LECs) in recent years. LECs have a simple structure and can be fabricated using low‐cost methods and materials and are seen as the next big thing in organic devices after organic light‐emitting diodes (OLEDs). In particular, expectations are high, in that LECs could be used to create a new generation of low‐cost lighting systems, making use of their surface‐emitting property. Getting such systems to the market will require the development of highly efficient white light‐emitting LECs. A variety of methods for obtaining white emission based on the light‐mixing principle have been explored. Among these, the use of exciplexes formed between donor‐type and acceptor‐type molecules is one of the more promising. Exciplex emission is broad in spectrum and can be used to produce LECs with a high color rendering index. In this progress report, the recent developments in research into LECs designed to utilize exciplex emission and present technologies used to obtain white emission are discussed. The potential for using thermally activated delayed fluorescence to improve efficiency is described. Finally, the latest developments in optical engineering techniques for LECs are also discussed.     

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 Progress in High‐Efficiency Blue‐Light‐Emitting Materials for Organic Light‐Emitting Diodes

Organic light‐emitting diodes (OLEDs) are increasingly used in displays replacing traditional flat panel displays; e.g., liquid crystal displays. Especially, the paradigm shifts in displays from rigid to flexible types accelerated the market change from liquid crystal displays to OLEDs. However, some critical issues must be resolved for expansion of OLED use, of which blue device performance is one of the most important. Therefore, recent OLED material development has focused on the design, synthesis and application of high‐efficiency and long‐life blue emitters. Well‐known blue fluorescent emitters have been modified to improve their efficiency and lifetime, and blue phosphorescent emitters are being investigated to overcome the lifetime issue. Recently, thermally activated delayed fluorescent emitters have received attention due to the potential of high‐efficiency and long‐living emitters. Therefore, it is timely to review the recent progress and future prospects of high‐efficiency blue emitters. In this feature article, we summarize recent developments in blue fluorescent, phosphorescent and thermally activated delayed fluorescent emitters, and suggest key issues for each emitter and future development strategies.     

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.     

Monothiatruxene‐Based,Solution‐Processed Green,Sky‐Blue,and Deep‐Blue Organic Light‐Emitting Diodes with Efficiencies Beyond 5% Limit

The development of blue materials with good efficiency, even at high brightness, with excellent color purity, simple processing, and high thermal stability assuring adequate device lifetime is an important remaining challenge for organic light‐emitting didoes (OLEDs) in displays and lightning applications. Furthermore, these various features are typically mutually exclusive in practice. Herein, four novel green and blue light‐emitting materials based on a monothiatruxene core are reported together with their photophysical and thermal properties, and performance in solution‐processed OLEDs. The materials show excellent thermal properties with high glass transition temperatures ranging from 171 to 336 °C and decomposition temperatures from 352 to 442 °C. High external quantum efficiencies of 3.7% for a deep‐blue emitter with CIE color co‐ordinates (0.16, 0.09) and 7% for green emitter with color co‐ordinates (0.22, 0.40) are achieved at 100 cd m^?2. The efficiencies observed are exceptionally high for fluorescent materials with photoluminescence quantum yields of 24% and 62%, respectively. The performance at higher brightness is very good with only 38% and 17% efficiency roll‐offs at 1000 cd m^?2. The results indicate that utilization of this unique molecular design is promising for efficient deep‐blue highly stable and soluble light‐emitting materials.     

Efficient Nondoped Blue Fluorescent Organic Light‐Emitting Diodes (OLEDs) with a High External Quantum Efficiency of 9.4% @ 1000 cd m−2 Based on Phenanthroimidazole−Anthracene Derivative

Organic light‐emitting diodes (OLEDs) can promise flexible, light weight, energy conservation, and many other advantages for next‐generation display and lighting applications. However, achieving efficient blue electroluminescence still remains a challenge. Though both phosphorescent and thermally activated delayed fluorescence materials can realize high‐efficiency via effective triplet utilization, they need to be doped into appropriate host materials and often suffer from certain degree of efficiency roll‐off. Therefore, developing efficient blue‐emitting materials suitable for nondoped device with little efficiency roll‐off is of great significance in terms of practical applications. Herein, a phenanthroimidazole?anthracene blue‐emitting material is reported that can attain high efficiency at high luminescence in nondoped OLEDs. The maximum external quantum efficiency (EQE) of nondoped device is 9.44% which is acquired at the luminescence of 1000 cd m^?2. The EQE is still as high as 8.09% even the luminescence reaches 10 000 cd m^?2. The maximum luminescence is ≈57 000 cd m^?2. The electroluminescence (EL) spectrum shows an emission peak of 470 nm and the Commission International de L'Eclairage (CIE) coordinates is (0.14, 0.19) at the voltage of 7 V. To the best of the knowledge, this is among the best results of nondoped blue EL devices.     

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.     

Molecularly Engineered Near‐Infrared Light‐Emitting Electrochemical Cells

The development of near‐infrared (NIR) luminescent materials has emerged as a promising research field with important applications in solid‐state lighting (SSL), night‐vision‐readable displays, and the telecommunication industry. Over the past two decades, remarkable advances in the development of light‐emitting electrochemical cells (LECs) have stunned the SSL community, which has in turn driven the quest for new classes of stable, more efficient NIR emissive molecules. In this review, an overview of the state of the art in the field of near‐infrared light‐emitting electrochemical cells (NIR‐LEC) is provided based on three families of emissive compounds developed over the past 25 years: i) transition metal complexes, ii) ionic polymers, and iii) host–guest materials. In this context, ionic and conductive emitters are particularly attractive since their emission can be tuned via molecular design, which involves varying the chemical nature and substitution pattern of their ancillary ligands. Herein, the challenges and current limitations of the latter approach are highlighted, particularly with respect to developing NIR‐LECs with high external quantum efficiencies. Finally, useful guidelines for the discovery of new, efficient emitters for tailored NIR‐LEC applications are presented, together with an outlook towards the design of new NIR‐SSL materials.     

Efficient Blue Perovskite Light‐Emitting Diodes Boosted by 2D/3D Energy Cascade Channels

Lead halide perovskite, as an emerging semiconductor, provides a fire‐new opportunity for high‐definition display and solid‐state lighting. Earthshaking improvements are implemented in green, red, and near‐infrared perovskite light‐emitting diodes (PeLEDs). However, blue PeLEDs are still far behind in performance, which restricts the development of PeLEDs in practical applications. Herein, a facile energy cascade channel strategy via one‐step self‐organized and controllable 2D/3D perovskite preparation by introducing guanidine hydrobromide (GABr) is developed that greatly improves the efficiency of blue PeLEDs. The 2D/3D perovskite structure boosts the energy cascade to induce energy transfer from the wide into the narrow bandgap domains and inhibit free charge diffusion, which increases the density of electrons and holes, and enhances the radiative recombination. Profiting from this energy cascade channels, the external quantum efficiency of blue PeLEDs, emitting at 492 nm, is considerably enhanced from 1.5% of initial blue device to 8.2%. In addition, device operating stability under ambient conditions is also improved by 2.6‐fold. The one‐step self‐organized 2D/3D hybrid perovskites induced by GABr pave a new and simple route toward high‐performance blue emission PeLEDs.     

Interfacial Nucleation Seeding for Electroluminescent Manipulation in Blue Perovskite Light-Emitting Diodes

Efficient and stable blue emission of perovskite light-emitting diodes (PeLEDs) is a requisite toward their potential applications in full-color displays and solid-state lighting. Rational manipulation over the entire electroluminescence process is promising to break the efficiency limit of blue PeLEDs. Herein, a facile device architecture is proposed to achieve efficient blue PeLEDs for simultaneously reducing the energetic loss during electron-photon conversion and boosting the light outcoupling. Effective interfacial engineering is employed to manipulate the perovskite crystallization nucleation, enabling highly compact perovskite nanocrystal assemblies and suppressing the trap-induced carrier losses by means of interfacial hydrogen bonding interactions. This strategy contributes to a high external quantum efficiency (EQE) of 12.8% for blue PeLEDs emitting at 486 nm as well as improved operational stability. Moreover, blue PeLEDs reach a peak EQE of 16.8% with the incorporation of internal outcoupling structures for waveguided light, which can be further raised to 27.5% by integrating a lens-based structure for substrate-mode light. These results verify the validity of this strategy in producing efficient and stable blue PeLEDs for practical 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.     

Synthesis of red-emitting cationic Ir (III) complex and its application in white light-emitting electrochemical cells

Construction of intramolecular π-π packing between cyclometalated and ancillary ligand have been proved to be a feasible way to design cationic Ir(III) phosphors for stable light-emitting electrochemical cells (LECs). Employing blue-green (C1) and yellow-emitting (C2) Ir(III) complexes as emitters, in which such π-π interactions between ligands occur, the stable and efficient LECs with peak current efficiency of 21.9 cd/A and 20.3 cd/A, respectively, were realized. To achieve the white electroluminescence, herein, a new red-emitting cationic Ir (III) complex (C3) using 2-(5-phenyl-2-phenyl-2H-1,2,4-triazol-3-yl)pyridine as ancillary ligand was designed and synthesized. A warm white light emitting, by doping C3 into the blue-green emitting C1, exhibits the current efficiency of 10.1 cd/A. In addition, the obtained LECs are more stable than those of previous reports due to presence of intrinsic super-cage structures in the systems. The results indicate that the efficient white LECs hold promising applications in the practical solid state lighting.     

Blue Single‐Layer Organic Light‐Emitting Diodes Using Fluorescent Materials: A Molecular Design View Point

Since the beginning of organic light‐emitting diodes (OLEDs), blue emission has attracted the most attention and many research groups worldwide have worked on the design of materials for stable and highly efficient blue OLEDs. However, almost all the high‐efficiency blue OLEDs using fluorescent materials are multilayer devices, which are constituted of a stack of organic layers to improve the injection, transport, and recombination of charges within the emissive layer. Although the technology has been mastered, it suffers from real complexity and high cost and is time‐consuming. Simplifying the multilayer structure with a single‐layer one, the simplest devices made only of electrodes and the emissive layer have appeared as an appealing strategy for this technology. However, removing the functional organic layers of an OLED stack leads to a dramatic decrease of the performance and achieving high‐efficiency blue single‐layer OLEDs requires intense research especially in terms of materials design. Herein, an exhaustive review of blue emitting fluorophores that have been incorporated in single‐layer OLEDs is reported, and the links between their electronic properties and the device performance are discussed. Thus, a structure/properties/device performance relationship map is drawn, which is of interest for the future design of organic materials.     

Light Management with Patterned Micro‐ and Nanostructure Arrays for Photocatalysis,Photovoltaics, and Optoelectronic and Optical Devices

The design and fabrication of patterned micro‐ and nanostructure arrays have been demonstrated to be a powerful strategy toward efficient light management, which is of vital importance to a variety of photon‐related applications such as photocatalysis, photovoltaics, optoelectronic devices, and optical devices. Tunable optical reflectance, scattering, transmittance, and absorption can be readily achieved by adjusting the characteristics of the primary units in the micro‐/nanoarrays and the spatial patterns of the aligned units, thus realizing controllable light–matter interactions. This review describes various light management strategies based on patterned micro‐/nanoarrays, such as scattering enhancement, antireflection, resonances, photonic crystals, and plasmonic structures. Furthermore, recent advances in the applications of patterned micro‐/nanoarrays in photoelectrochemical water splitting, solar cells, photodetectors, light emitting diodes, lasers, color display, microlens arrays, and photonic crystal sensors are summarized, with particular attention paid to the light management mechanisms and the relationship between the structure and device performance. Lastly, the prospects and existing challenges facing the development of the photon‐related applications based on patterned micro‐/nanoarrays are discussed.     

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.