Optimizing carrier balance of a red quantum-dot light-emitting electrochemical cell with a carrier injection layer of cationic Ir(III) complex

Solid-state light-emitting electrochemical cells (LECs) with promising features of solution processability, low-voltage operation and compatibility with inert cathode metals have shown great potential in display and lighting applications in recent years. Among the reported emissive materials for LECs, ionic transition metal complexes (iTMCs) have relatively higher electroluminescence (EL) efficiencies due to their phosphorescent property. However, the red iTMCs generally exhibit moderate color saturation and low emission efficiency, limiting their display applications. To improve color saturation and device efficiency of red LECs, efficient quantum dots (QDs) with narrow emission bandwidth are good alternative emissive materials. In this work, efficient and saturated red QD LECs employing iTMC carrier injection layers to provide in situ electrochemical doping are demonstrated. The thicknesses of iTMC and red-QD layers are systematically adjusted to achieve the best carrier balance. In the optimized device, the iTMC carrier injection layer facilitates hole injection into the red-QD layer while electrons are injected from the cathode into the red-QD layer directly since the electron injection barrier is low. The Commission Internationale de I'Eclairage (CIE) coordinates of the EL spectra approach the red standard point of National Television System Committee (NTSC). High external quantum efficiency and current efficiency reaching 9.7% and 16.1 cd A⁻¹, respectively. These results confirm superior carrier balance in such a simple iTMC/QD bilayer device structure. Furthermore, compared with iTMC LECs, less degree of device efficiency roll-off upon increasing device current is observed in QD LECs since a shorter excited-state lifetime of fluorescent QDs reduces the probability of collision exciton quenching. Saturated and efficient red EL with mitigated efficiency roll-off from red-QD LECs employing iTMC carrier injection layers confirms that they are good candidates of saturated light sources for displays.     

Extracting evolution of recombination zone position in sandwiched solid-state light-emitting electrochemical cells by employing microcavity effect

Techniques of probing for time-dependent evolution of recombination zone position in sandwiched light-emitting electrochemical cells (LECs) would be highly desired since they can provide direct experimental evidence to confirm altered carrier balance when device parameters are adjusted. However, direct imaging of recombination zones in thin emissive layers of sandwiched LECs could not be obtained easily. In this work, we propose an alternative way to extract evolution of recombination zone position in sandwiched LECs by utilizing microcavity effect. Recombination zone positions can be estimated by fitting the measured electroluminescence spectra to simulated output spectra based on microcavity effect and properly adjusted emissive zone positions. With this tool, effects of modified carrier transport and carrier injection on performance of LECs are studied and significantly altered carrier balance can be measured, revealing that microcavity effect is useful in tracing evolution of recombination zone position in sandwiched LECs.     

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.     

Enhanced carrier balance by organic salt doping in single-layer polymer light-emitting devices

We have showed that the doping of an organic salt into a PVK-based polymer emissive layer could enhance the carrier balance greatly to result in higher luminance and luminous efficiency. It is found out that the salt-doped devices show the similar operating characteristics of frozen-junction light-emitting electrochemical cells (LECs). With the salt doping of 0.6 wt.% and an appropriate salt activation process, the fabricated PVK-based polymer light-emitting diodes (PLEDs) shows the luminous efficiency of 15 cd/A at the highest luminance of 55,000 cd/m² even without an electron-injecting LiF layer. Due to the enhanced carrier balance, the luminous efficiency is found to be maintained from the turn-on voltage to the voltage for the maximum luminance, which means a linear relationship between luminance and current density.     

Enhancing device efficiencies of solid-state near-infrared light-emitting electrochemical cells by employing a tandem device structure

Compared to near-infrared (NIR) organic light-emitting devices, solid-state NIR light-emitting electrochemical cells (LECs) could possess several superior advantages such as simple device structure, low operating voltages and balanced carrier injection. However, intrinsically lower luminescent efficiencies of NIR dyes and self-quenching of excitons in neat-film emissive layers limit device efficiencies of NIR LECs. In this work, we demonstrate a tandem device structure to enhance device efficiencies of phosphorescent sensitized fluorescent NIR LECs. The emissive layers, which are composed of a phosphorescent host and a fluorescent guest to harvest both singlet and triplet excitons of host, are connected vertically via a thin transporting layer, rendering multiplied light outputs. Output electroluminescence (EL) spectra of the tandem NIR LECs are shown to change as the thickness of emissive layer varies due to altered microcavity effect. By fitting the output EL spectra to the simulated model concerning microcavity effect, the stabilized recombination zones of the thicker tandem devices are estimated to be located away from the doped layers. Therefore, exciton quenching near doped layers mitigates and longer device lifetimes can be achieved in the thicker tandem devices. The peak external quantum efficiencies obtained in these tandem NIR LECs were up to 2.75%, which is over tripled enhancement as compare to previously reported NIR LECs based on the same NIR dye. These efficiencies are among the highest reported for NIR LECs and confirm that phosphorescent sensitized fluoresce combined with a tandem device structure would be useful for realizing highly efficient NIR LECs.     

Improving device efficiencies of solid-state white light-emitting electrochemical cells by adjusting the emissive-layer thickness

Exciton quenching in the recombination zone close to electrochemically doped regions would be one of the bottlenecks for improving device efficiencies of solid-state white light-emitting electrochemical cells (LECs). To further enhance device efficiencies of white LECs for practical applications, we adjust the emissive-layer thickness to reduce exciton quenching. In white LECs with properly thickened emissive-layer thickness, the recombination zone can be situated near the center of the emissive layer, rendering mitigated exciton quenching and thus enhanced device efficiencies. High external quantum efficiencies and power efficiencies of optimized devices reach ca. 11% and 20 lm/W, respectively, which are among the highest reported for white LECs. These results confirm that tailoring the thickness of the emissive layer to avoid exciton quenching would be a feasible approach to improve device efficiencies of white LECs.     

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.     

Insights into charge balance and its limitations in simplified phosphorescent organic light-emitting devices

Simplified phosphorescent organic light-emitting device (PHOLED), which utilizes only two organic layers, showed record-high efficiency when first introduced. It is quite surprising that this device can have such high efficiency without the use of complex carrier and exciton confinement layers that are common in the state-of-the-art PHOLEDs nowadays. Therefore, it is important to understand how good charge balance is in simplified PHOLED and why. In this work, we study the effects of altering charge balance in simplified PHOLED through means of changing layer thickness in the hole transport layer (HTL) and electron transport layer (ETL) as well as intentionally doping hole and electron traps in the HTL and ETL, respectively, on device efficiency. The results show that when using high carrier mobility charge transport materials, changing layer thickness does not impact charge balance appreciably. On the other hand, introducing charge traps in a thin layer within the HTL or ETL can, in comparison, influence charge balance more significantly, and proves to be a more effective approach for studying the factors limiting charge balance in these devices. The results reveal that simplified PHOLEDs are generally hole-rich, and that the leakage of electrons to the counter electrode is also a major mechanism behind the poor charge balance and efficiency loss in these devices. In order to optimize charge balance in simplified PHOLED, it is important to reduce hole transport in the device so that e-h ratio can be brought closer to unity, as well as eliminate electron leakage. Finally, we show that by simply using an electron blocking HTL, the efficiency of the device can be enhanced by as much as 25%, representing the highest reported for simplified PHOLEDs.     

Solution-processable tandem solid-state light-emitting electrochemical cells

Compared to organic light-emitting diodes (OLEDs), solid-state light-emitting electrochemical cells (LECs) exhibit simple single-layered structure and low operating voltages due to in situ electrochemical doped layers. However, device efficiencies of LECs are usually lower than those of sophisticatedly designed OLEDs. Furthermore, device efficiencies and lifetimes of LECs degrade significantly as brightness increases. In this work, we demonstrate tandem LECs to obtain nearly doubled light outputs (μW cm⁻²) in comparison with single-layered LECs under similar current densities. Since the output EL emission is modified by microcavity effect of the device structure, the EL spectra of tandem LECs exhibit EL emission peak at ca. 625 nm while the EL spectra of single-layered LECs center at ca. 660 nm. Better spectral overlap between the EL spectrum of tandem LECs and the luminosity function results in further enhanced candela values, rendering a tripled brightness (cd m⁻²). The device efficiencies can be optimized by adjusting the thickness of the connecting layer between the two emitting units of the tandem devices. The peak external quantum efficiency achieved in tandem LECs is up to 5.83%, which is higher than twice of that obtained in single-layered LECs due to improved carrier balance. When single-layered and tandem LECs are biased under higher voltages to reach similarly higher brightness, tandem LECs show higher device efficiencies and longer lifetimes simultaneously. These results indicate that device efficiencies and lifetimes of LECs can be improved by employing a tandem device structure.     

The Synergistic Effect of Pemirolast Potassium on Carrier Management and Strain Release for High-Performance Inverted Perovskite Solar Cells

The quality of the perovskite absorption layer is critical for the high efficiency and long-term stability of perovskite solar cells (PSCs). The inhomogeneity due to local lattice mismatch causes severe residual strain in low-quality perovskite films, which greatly limits the availability of high-performance PSCs. In this study, a multi-active-site potassium salt, pemirolast potassium (PP), is added to perovskite films to improve carrier dynamics and release residual stress. X-ray photoelectron spectroscopy (XPS) and Fourier-transform infrared spectroscopy (FTIR) measurements suggest that the proposed multifunctional additive bonds with uncoordinated Pb²⁺ through the carbonyl group/tetrazole N and passivated I atom defects. Moreover, the residual stress release is effective from the surface to the entire perovskite layer, and carrier extraction/transport is promoted in PP-modified perovskite films. As a result, a champion power conversion efficiency (PCE) of 23.06% with an ultra-high fill factor (FF) of 84.36% is achieved in the PP-modified device, which ranks among the best in formamidinium-cesium (FACs) PSCs. In addition, the PP-modified device exhibits excellent thermal stability due to the inhibited phase separation. This work provides a reliable way to improve the efficiency and stability of PSCs by releasing residual stress in perovskite films through additive engineering.     

Enhancing extracted electroluminescence from light-emitting electrochemical cells by employing high-refractive-index substrates

Solid-state light-emitting electrochemical cells (LECs) show several advantages over conventional organic light-emitting devices (OLEDs) such as simple device structure compatible with solution processes, low operation voltage and capability of utilizing inert cathode metals. However, device performance of LECs must be improved, e.g. enhancing light extraction, to meet the requirements for practical applications. Among the optical modes trapped in LECs, light trapped in substrate mode is easier to be extracted, e.g., by simply roughing the output surface. Therefore, increasing the percentage of substrate mode is beneficial in improving light extraction. In this work, the contributions of optical modes in LECs employing substrates with various refractive indices are analyzed. Higher-refractive-index substrates are shown to trap more light in the substrates. Smaller refractive index difference between higher-refractive-index substrate and indium tin oxide (ITO) layer also increases the cutoff spectral range of light waveguided in ITO layer. Furthermore, light intensity in surface plasmon mode significantly reduces as the refractive index of the substrate increases. Reducing the percentage of surface plasmon mode facilitates light extraction since it requires more complicated methods for outcoupling light in this mode. With commercially available unpolished sapphire substrates, light output of LECs is enhanced by 56%. When a scattering layer was inserted between ITO and sapphire substrate, more light in substrate mode can be extracted and 71% enhancement in light output is realized. High external quantum efficiency up to 5.5% is consequently obtained in LECs based on a ruthenium complex. Such device efficiency is among the highest reported values for red-emitting LECs and thus confirms that utilizing higher-refractive-index substrates would offer a simple and feasible approach to improve light output of LECs. In comparison to OLEDs, increased EL trapped in substrates of LECs mainly comes from surface plasmon mode rather than waveguide mode.     

Polymer Light-Emitting Electrochemical Cells for High-Efficiency Low-Voltage Electroluminescent Devices

Organic light-emitting devices exhibiting high power conversion efficiency and long operating lifetime may potentially be achieved with the polymer light-emitting electrochemical cell (LEC) configuration. An LEC device typically uses a thin layer of conjugated polymer sandwiched between two contact electrodes. The polymer layer contains an ionically conductive species that are essential in the formation of a light-emitting p-i-n junction. LEC devices are characterized with balanced electron and hole injections, high current density at relatively low bias voltages (2-4 V), and high electroluminescent power efficiency. We will describe the working mechanism of the LECs and review the recent developments in LEC materials, device fabrication and performance. Among the important developments are planar (surface-typed) LECs, bilayer LECs that emit different colors at forward and reverse biases, frozen p-i-n junction LECs that functions like diodes, and phosphorescent LECs. Extensive efforts have been made to improve the LEC performance by controlling the blend morphology, including the use of bipolar surfactant additives and new electrolytes, the synthesis of conjugated polymers with ion-transporting main chain segments or side groups and polyelectrolyte. Degradation mechanisms that limit the lifetime of the LECs will also be discussed     

Boosting the performance of solution-processed quantum dots light-emitting diodes by a hybrid emissive layer via doping small molecule hole transport materials into quantum dots

Solution-processed colloidal quantum dot light-emitting diodes (QLED) have attracted many attentions with significant progress in recent years. However, QLED devices still face some challenges. The energy barrier between Cd-base quantum dots (QDs) and commonly used hole transport materials is larger than that between QDs and electron transport materials, which leads to the imbalance of carriers in the light emitting layer (EML) and the low performance of QLED devices. Herein, we report a simple strategy to improve the device performance by doping small molecule transport material 4,4′-cyclohexylidenebis[N,N-bis(p-tolyl)aniline] (TAPC) into red CdSe/ZnS QDs. The optimized red QLED devices with TAPC-doped emissive layer at a ratio of 3.2 wt% achieve 20.0 cd/A of maximum current efficiency, 16.6 lm/W of power efficiency and 15.7% of external quantum efficiency, which is 30%, 58% and 33% higher than the control device. The improved performance of devices can be ascribed to the increase of hole current density, decrease of leakage electrons and more balanced quantity of carriers in EML. This work put forward a viewpoint to improve the performance of QLED devices via doping high hole mobility materials into emission layer.     

基于超薄发光层的有机发光二极管器件的研究

文章采用具有电子捕捉能力的橙红色磷光材料iridium(Ⅲ)bis(2-methyldibenzo-[f,h] quinoxaline) (acetylacetonate) (Ir(MDQ)2 (acac))作为超薄发光层应用于有机发光二极管中.通过对其厚度的优化,发现当发光层厚度为0.1 nm时,器件性能最好,最大电流效率达到了28.1 cd/A,明显优于采用掺杂发光层的器件.分析了发光材料的载流子捕捉作用对器件载流子平衡及器件电流效率的影响,发现超薄发光层结构几乎不改变器件的电学特性,不会进一步破坏器件载流子平衡,正因如此,大多数磷光材料都可以采用超薄发光层获得很高的效率.     

以ZnO为空穴缓冲层的高效率有机电致发光器件

研制了在传统双层有机电致发光器件(OLED) ITO/NPB/AlQ/Al的阳极与空穴传输层间加入ZnO缓冲层的新型器件.研究了加入缓冲层后对OLED性能的影响,并比较了新型与传统OLED的性能,结果表明,新型器件比传统器件的耐压能力有了显著提高;当电压达到7 V时,发光效率提高了35%.分析认为,ZnO缓冲层的加入,改善了界面, 减少了漏电流,并且阻碍了空穴的注入,有利于改善空穴和电子的注入平衡,提高复合效率.     

载流子平衡方法提高量子点发光二极管效率的研究

尝试采用三种方式来平衡载流子的浓度,以提高量子点发光二极管(QLED)的外量子效率等性能:在正装结构(ITO/HIL/HTL/QD/ETL/EIL/金属阴极)的QLED的发光层和电子传输层中间插入超薄聚甲基丙烯酸甲脂(PMMA)电子阻挡层;在空穴注入和传输层方面,通过使用更加优化的HIL等来提高空穴注入和传输几率;在QD发光层方面,用短链配体来置换量子点的长链配体以增加载流子向量子点发光层中的传输效率等。在进行量子点配体交换的同时带来了量子点在正交溶剂中的可溶性优势,有利于QLED器件的全溶液法制备。     

Highly efficient blue polyfluorenes using blending materials as hole transport layer

Efficient blue polyfluorenes have been generated by incorporating the hole transport material N-([1,1′-biphenyl]-4-yl)-9,9-dimethyl-N-(4-(9-phenyl-9H-carbazol-3-yl)- phenyl)-9H-fluoren-2-amine (BCFN) into poly(9,9-dioctylfluorene) (PFO) as an emissive layer. BCFN has an appropriate highest occupied molecular orbital (HOMO) energy level and high hole transport/electron barrier properties, which can effectively reduce the hole injection barrier and improve the charge carrier injection and transport. These properties resulted in a significant improvement in the electroluminescent (EL) performance of PFO. To further improve the EL performance of PFO, the blend hole transport layer, PVK [Poly(N-vinylcarbazole)]:BCFN with weight ratio of 3:7, was inserted between the PEDOT:PSS and the emissive layer. The blend hole transport layer effectively reduced exciton quenching and markedly decreased the hole injected barrier. A maximum luminous efficiency (LE_max) of 4.31 cd A⁻¹ was obtained with the CIE coordinates of (0.17, 0.13). The device maintained a LE_max of 4.27 cd A⁻¹ at a luminance of 1000 cd m⁻². In addition, stable EL spectra were obtained and were nearly identical when the applied voltage was increased from 5 to 11 V. These results indicate that blending the appropriate hole transport material can be an efficient method to improve device performance based on the large band gap of blue-lighting materials.     

UV light-emitting electrochemical cells based on an ionic 2,2′-bifluorene derivative

UV light-emitting electrochemical cells (LECs) were, for the first time, achieved by the ionic 2,2′-bifluorene derivative, 1, which was synthesized through covalent tethering of methylimidazolium moieties as pendent groups. LEC devices incorporating ionic bifluorene 1 without (Device I) and with (Device III) the presence of poly(methyl methacrylate) (PMMA) exhibited UV EL emissions centered at 388 and 386 nm with maximum external quantum efficiencies and power efficiencies of 1.06% and 7.44 mW W⁻¹ for Device III and 0.15% and 1.06 mW W⁻¹ for Device I, respectively. Transmission electron microscopy (TEM) images showed that 1 tends to form nanospheres due to amphiphilic nature. The presence of PMMA unified the size of nanospheres which greatly reduced the void area in films, suppressing the current leakage and enhancing the device efficiency. Furthermore, thicker thickness of the emissive layer of LECs increases the distance between carrier recombination zone and electrodes to avoid exciton quenching. Thus, a sevenfold increase in device efficiency was obtained in thicker UV LECs containing PMMA (Device III) as compared to thinner UV LECs based on neat films of 1 (Device I). The EL emissions in the UV region are successfully achieved by LECs based on 1, which are so far the shortest emission wavelength achieved in LECs.     

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.     

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.